CN113025961B - Preparation method of electrode foil for aluminum electrolytic capacitor - Google Patents

Preparation method of electrode foil for aluminum electrolytic capacitor Download PDF

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CN113025961B
CN113025961B CN202110242134.4A CN202110242134A CN113025961B CN 113025961 B CN113025961 B CN 113025961B CN 202110242134 A CN202110242134 A CN 202110242134A CN 113025961 B CN113025961 B CN 113025961B
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mixed treatment
treatment solution
waste liquid
aluminum foil
solution
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CN113025961A (en
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谢悦
江露莹
李健华
伍婉莹
冯智源
包艳萍
杨富国
张玉红
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Foshan University
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/068—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors compounds containing a C=C bond
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C23G1/125—Light metals aluminium

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Abstract

The invention provides a preparation method of an electrode foil for an aluminum electrolytic capacitor, which comprises the steps of soaking an aluminum foil in a front treatment solution, plating nano-titanium, soaking in a first mixed treatment solution, soaking in a second mixed treatment solution and soaking in a third mixed treatment solution. The preparation method of the electrode foil for the aluminum electrolytic capacitor is simple, can effectively recycle hydrochloric acid, sulfuric acid and nitric acid, has the recovery rates of the hydrochloric acid and the sulfuric acid in the pre-treatment waste liquid and the first mixed treatment waste liquid of 85 percent, and has Al content 3+ The retention rate of the product reaches 95 percent; in the second mixed waste liquid and the third mixed waste liquid, the recovery rate of the nitric acid reaches 80 percent, and Al is contained 3+ The retention rate of the composite reaches 95 percent; in addition, no current is required to be applied in the second mixed treatment solution soaking and the third mixed treatment solution soaking, so that the method has the advantages of energy conservation and emission reduction, and the prepared electrode foil has better pore forming uniformity and bending performance.

Description

Preparation method of electrode foil for aluminum electrolytic capacitor
Technical Field
The invention relates to a preparation method of an electrode foil for a capacitor, in particular to a preparation method of an electrode foil for an aluminum electrolytic capacitor.
Background
The aluminum electrolytic capacitor is developing toward miniaturization and miniaturization, and the requirements on the specific volume and the bending performance of the electrode foil for the aluminum electrolytic capacitor are continuously improved so as to meet the manufacturing requirements of cutting smaller width and winding smaller diameter. The formation of uniformly distributed high-density tunnel holes with reasonable hole diameter and hole length on the surface of the electrode foil is the key to obtain high specific capacitance. The electrode foil is obtained by etching, for example, an aluminum metal foil. This increases the surface area of the electrode foil, thereby increasing the capacitance. At present, a large amount of waste acid liquor, such as hydrochloric acid, sulfuric acid, nitric acid and the like, is generated in the production process of the electrode foil for the aluminum electrolytic capacitor, the generated waste acid liquor is high in concentration on the whole, the treatment cost is high, and a large amount of discharge can seriously affect the environment, so that the research on the preparation process of the electrode foil has an extremely important significance in environmental protection. In addition, while the environment-friendly electrode foil preparation method is ensured, the electrode foil for preparing the aluminum electrolytic capacitor in the prior art cannot completely obtain uniform etching holes, so that the problems that the electrode foil cannot meet the market demand due to high electrostatic capacity dispersion rate and low bending strength are caused.
In summary, the above-mentioned problems still remain to be solved in the field of preparing electrode foils.
Disclosure of Invention
Based on the above, in order to solve the problems of poor environmental protection, high waste acid treatment component, high electrode foil electrostatic capacity dispersion rate and low bending strength of the electrode foil in the prior art, the invention provides a preparation method of the electrode foil for an aluminum electrolytic capacitor, which has the following specific technical scheme:
a preparation method of an electrode foil for an aluminum electrolytic capacitor comprises the following steps:
placing the aluminum foil in a pretreatment solution at the temperature of 55-75 ℃ to be soaked for 45-75 s to obtain the aluminum foil soaked by the pretreatment solution and pretreatment waste liquid;
placing the aluminum foil soaked by the pretreatment solution in a vacuum chamber of a coating machine for nano titanium coating;
placing the aluminum foil subjected to the nano titanium plating treatment in a first mixed treatment solution at the temperature of 45-82 ℃ for soaking for 50-85 s, draining for 10-20 s, and continuously spraying the first mixed treatment solution for 0.5-3 h under the condition that the spraying flow is 10-15L/h to obtain the aluminum foil treated by the first mixed treatment solution and a first mixed treatment waste liquid;
mixing the pre-treatment waste liquid and the first mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain sulfuric acid and hydrochloric acid;
cleaning the aluminum foil treated by the first mixed treatment solution by using pure water, and soaking the aluminum foil in a second mixed treatment solution at the temperature of 45-75 ℃ for 60-150 s after the cleaning is finished to obtain the aluminum foil treated by the second mixed treatment solution and a second mixed treatment waste liquid;
placing the aluminum foil treated by the second mixed treatment solution into a third mixed treatment solution at the temperature of 75-90 ℃ to be soaked for 120-250 s to obtain the aluminum foil treated by the third mixed treatment solution and a third mixed treatment waste liquid;
collecting the second mixed treatment waste liquid and the third mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain nitric acid;
and (3) placing the aluminum foil treated by the third mixed treatment solution in a nitric acid solution at the temperature of 45-60 ℃ for soaking for 120-180 s to obtain the electrode foil for the aluminum electrolytic capacitor.
Preferably, the pretreatment solution contains 7-12% of hydrochloric acid and 6-9% of Al in percentage by mass 3+ And 2 to 6 percent of sulfuric acid.
Preferably, the nano titanium plating treatment is as follows: the vacuum degree of the vacuum chamber of the film plating machine is adjusted to be 5.0 multiplied by 10 -3 Pa, the temperature is 200-250 ℃, and the heat preservation time is 20-30 min; introducing Ar into the vacuum chamber of the film plating machine, and keeping the pressure at 0.1-0.4 Pa; then turning on a bias power supply, adjusting the bias voltage to be 250-280V, and discharging and cleaning for 20-30 min; adjusting the bias voltage to be 120V-170V, starting ion source ion cleaning for 20 min-30 min, starting an arc source Ti target, adjusting the bias voltage to be 200V-300V, the target current to be 60A-80A, and bombarding the Ti target by ions for 7 min-8 min; adjusting the air pressure to 0.36 Pa-0.39 Pa, adjusting the bias voltage to 50V-60V, and arc plating Ti for 5 min-7 min.
Preferably, the first mixed treatment solution contains 2 to 6 mass percent of hydrochloric acid and 3 mass percent of hydrochloric acid5% of Al 3+ 2 to 6 percent of sulfuric acid.
Preferably, the second mixed treatment solution contains 3 to 5 mass percent of nitric acid, 0.1 to 0.3 mass percent of graphene and 3 to 5 mass percent of Al in the second mixed treatment solution 3+ And 0.6 to 1.2 percent of corrosion inhibitor.
Preferably, the third mixed treatment solution contains 3 to 5 mass percent of nitric acid, 0.1 to 0.3 mass percent of graphene and 3 to 5 mass percent of Al in the third mixed treatment solution 3+ And 0.6 to 1.2 percent of corrosion inhibitor.
Preferably, the nitric acid solution contains 1 to 3 mass percent of nitric acid.
Preferably, the corrosion inhibitor is one or any combination of two of sodium polystyrene sulfonate and phosphoric acid.
Preferably, the first mixed treatment solution is soaked in 20A/dm 2 ～30A/dm 2 The current density of (1).
The preparation method of the electrode foil for the aluminum electrolytic capacitor in the scheme is simple in whole, can effectively recover the components of hydrochloric acid, sulfuric acid and nitric acid, can be recycled in the preparation of the electrode foil for the aluminum electrolytic capacitor, is environment-friendly, and can reduce the production cost, wherein in the pre-treatment waste liquid and the first mixed treatment waste liquid, the recovery rates of the hydrochloric acid and the sulfuric acid are 85%, and the Al content in the pre-treatment waste liquid and the first mixed treatment waste liquid is low 3+ The retention rate of the product reaches 95 percent; in the second mixed waste liquid and the third mixed waste liquid, the recovery rate of the nitric acid reaches 80 percent, and Al is contained 3+ The retention rate of the electrode foil reaches 95%, the environmental protection performance of the electrode foil production process and the utilization rate of components are further improved, and in the process of preparing the electrode foil, current does not need to be applied to the second mixed treatment solution for soaking and the third mixed treatment solution for soaking, so that the electrode foil has the advantages of energy conservation and emission reduction; in addition, the electrode foil prepared by the invention has an integral coordination effect under the combined action of the process and the components, the specific volume of the electrode foil is improved by more than 15% compared with the aluminum foil subjected to reaming corrosion by adopting a single corrosion inhibitor system, and the electrode foil has better pore-forming uniformity and bending performance and an increased application range.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments thereof. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
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. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The preparation method of the electrode foil for the aluminum electrolytic capacitor in one embodiment of the invention comprises the following steps:
placing the aluminum foil in a pretreatment solution at the temperature of 55-75 ℃ to be soaked for 45-75 s to obtain the aluminum foil soaked by the pretreatment solution and pretreatment waste liquid;
placing the aluminum foil soaked by the pretreatment solution in a vacuum chamber of a coating machine for nano titanium coating;
placing the aluminum foil subjected to the nano titanium plating treatment in a first mixed treatment solution at the temperature of 45-82 ℃ for soaking for 50-85 s, draining for 10-20 s, and continuously spraying the first mixed treatment solution for 0.5-3 h under the condition that the spraying flow is 10-15L/h to obtain the aluminum foil treated by the first mixed treatment solution and a first mixed treatment waste liquid;
mixing the pre-treatment waste liquid and the first mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain sulfuric acid and hydrochloric acid;
cleaning the aluminum foil treated by the first mixed treatment solution by pure water, and soaking the aluminum foil in a second mixed treatment solution at the temperature of 45-75 ℃ for 60-150 s after the cleaning is finished to obtain the aluminum foil treated by the second mixed treatment solution and a second mixed treatment waste liquid;
placing the aluminum foil treated by the second mixed treatment solution into a third mixed treatment solution at the temperature of 75-90 ℃ to be soaked for 120-250 s to obtain the aluminum foil treated by the third mixed treatment solution and a third mixed treatment waste liquid;
collecting the second mixed treatment waste liquid and the third mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain nitric acid;
and (3) placing the aluminum foil treated by the third mixed treatment solution into a nitric acid solution at the temperature of 45-60 ℃ to soak for 120-180 s to obtain the electrode foil for the aluminum electrolytic capacitor.
In one embodiment, the pretreatment solution contains 7-12% hydrochloric acid and 6-9% Al by mass 3+ And 2 to 6 percent of sulfuric acid.
In one embodiment, the nano-titanium plating treatment is as follows: the vacuum degree of the vacuum chamber of the film plating machine is adjusted to be 5.0 multiplied by 10 -3 Pa, the temperature is 200-250 ℃, and the heat preservation time is 20-30 min; introducing Ar into the vacuum chamber of the film plating machine, and keeping the pressure at 0.1-0.4 Pa; then starting a bias power supply, adjusting the bias voltage to be 250-280V, and discharging and cleaning for 20-30 min; adjusting the bias voltage to be 120V-170V, starting ion source ion cleaning for 20 min-30 min, starting an arc source Ti target, adjusting the bias voltage to be 200V-300V, the target current to be 60A-80A, and bombarding the Ti target by ions for 7 min-8 min; adjusting the air pressure to 0.36 Pa-0.39 Pa, adjusting the bias voltage to 50V-60V, and arc plating Ti for 5 min-7 min.
In one embodiment, the first mixed treatment solution contains 2-6% of hydrochloric acid and 3-5% of Al in percentage by mass of the first mixed treatment solution 3+ 2 to 6 percent of sulfuric acid.
In one embodiment, the second mixed treatment solution contains 3 to 5 mass percent of nitric acid, 0.1 to 0.3 mass percent of graphene and 3 to 5 mass percent of Al in the second mixed treatment solution 3+ And 0.6 to 1.2 percent of corrosion inhibitor.
In one embodiment, the third mixed processing solution comprisesThe third mixed treatment solution comprises, by mass, 3% -5% of nitric acid, 0.1% -0.3% of graphene and 3% -5% of Al 3+ And 0.6 to 1.2 percent of corrosion inhibitor.
In one embodiment, the nitric acid solution contains 1-3% by weight of nitric acid.
In one embodiment, the corrosion inhibitor is one or any combination of sodium polystyrene sulfonate and phosphoric acid.
In one embodiment, the first mixed treatment solution is soaked in the solution at a rate of 20A/dm 2 ～30A/dm 2 The current density of (2).
In one embodiment, the aluminum foil has a purity of 99.99%.
In one embodiment, the aluminum foil has a thickness of 120 μm.
After an aluminum foil is placed in pretreatment liquid for treatment, a vacuum film plating technology is adopted, and trace Ti is uniformly added on the surface of the aluminum foil, so that a certain number of Al-Ti micro batteries are formed on the aluminum foil in a direct current electrolytic corrosion process, the corrosion effect of the aluminum foil is improved, the density of tunnel holes is increased, the corrosion of the holes is reduced, a composite oxide film with a high dielectric constant is formed on the foil, and the specific volume is increased; after the first mixed treatment liquid is soaked and sprayed, and the second mixed treatment liquid and the third mixed treatment liquid are treated, the dissolution and passivation can be effectively balanced in the hydrochloric acid hole expanding process, so that the hole expanding efficiency is improved, and the specific volume of the electrode foil is improved. In addition, by adopting a diffusion dialysis membrane separator, the recovery rate of hydrochloric acid and sulfuric acid in the pre-treated waste liquid and the first mixed treated waste liquid reaches 85 percent, and Al is contained 3+ The retention rate of the composite reaches 95 percent; in the second mixed waste liquid and the third mixed waste liquid, the recovery rate of the nitric acid reaches 80 percent, and Al is contained 3+ The retention rate of the electrode foil reaches 95 percent, and the energy-saving and environment-friendly performance of the electrode foil preparation is improved.
Embodiments of the present invention will be described in detail below with reference to specific examples.
Example 1:
a preparation method of an electrode foil for an aluminum electrolytic capacitor comprises the following steps:
placing an aluminum foil with the purity of 99.99% and the thickness of 120 mu m in a pretreatment solution at the temperature of 55 ℃ to be soaked for 45s to obtain the aluminum foil soaked by the pretreatment solution and a pretreatment waste liquid, wherein the pretreatment solution contains hydrochloric acid accounting for 7% of the mass percent of the pretreatment solution and Al accounting for 6% of the mass percent of the pretreatment solution 3+ And 2% sulfuric acid;
placing the aluminum foil soaked by the pretreatment solution into a vacuum chamber of a film plating machine for nano titanium plating treatment, which comprises the following steps: the vacuum degree of the vacuum chamber of the film plating machine is adjusted to be 5.0 multiplied by 10 -3 Pa, the temperature is 200 ℃, and the heat preservation time is 20min; introducing Ar into the vacuum chamber of the film plating machine, and keeping the pressure at 0.1Pa; then, starting a bias power supply, adjusting the bias voltage to 250V, and performing discharge cleaning for 20min; adjusting the bias voltage to 120V, starting ion source ion cleaning for 20min, starting an arc source Ti target, adjusting the bias voltage to 200V, adjusting the target current to 60A, and bombarding the Ti target by ions for 7min; adjusting the air pressure to 0.36Pa, adjusting the bias voltage to 50V, and arc plating Ti for 5min;
placing the aluminum foil subjected to the nano titanium plating treatment at the temperature of 45 ℃ and the applied current density of 20A/dm 2 Soaking the first mixed treatment solution for 50s, draining for 10s, and continuously spraying the first mixed treatment solution for 0.5h under the condition that the spraying flow is 10L/h to obtain the aluminum foil treated by the first mixed treatment solution and the first mixed treatment waste liquid, wherein the first mixed treatment solution comprises 2 mass percent of hydrochloric acid and 3 mass percent of Al 3+ 2% sulfuric acid;
mixing the pre-treatment waste liquid and the first mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain sulfuric acid and hydrochloric acid;
cleaning the aluminum foil treated by the first mixed treatment solution by adopting pure water, soaking the aluminum foil in a second mixed treatment solution at the temperature of 45 ℃ for 60s after the cleaning is finished, obtaining the aluminum foil treated by the second mixed treatment solution and a second mixed treatment waste liquid, wherein the second mixed treatment solution contains 3% of nitric acid, 0.1% of graphene and 3% of Al in percentage by mass 3+ And 0.6% of a corrosion inhibitor;
placing the aluminum foil treated by the second mixed treatment solution into a third mixed treatment solution at the temperature of 75 ℃ to soak for 120s to obtain the aluminum foil treated by the third mixed treatment solution and a third mixed treatment waste liquid, wherein the third mixed treatment solution contains 3% by mass of nitric acid, 0.1% by mass of graphene and 3% by mass of Al in the third mixed treatment solution 3+ And 0.6% of a corrosion inhibitor;
collecting the second mixed treatment waste liquid and the third mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain nitric acid;
and (3) placing the aluminum foil treated by the third mixed treatment solution into a nitric acid solution with the temperature of 45 ℃ and the mass percent of 1-3% for soaking for 120s to obtain the electrode foil for the aluminum electrolytic capacitor.
Example 2:
a preparation method of an electrode foil for an aluminum electrolytic capacitor comprises the following steps:
placing an aluminum foil with the purity of 99.99 percent and the thickness of 120 mu m in a pretreatment solution at the temperature of 75 ℃ to be soaked for 75s to obtain the aluminum foil soaked by the pretreatment solution and a pretreatment waste liquid, wherein the pretreatment solution contains hydrochloric acid accounting for 12 percent of the mass of the pretreatment solution and Al accounting for 9 percent of the mass of the pretreatment solution 3+ And 6% sulfuric acid;
placing the aluminum foil soaked by the pretreatment solution in a vacuum chamber of a coating machine for nano titanium coating treatment, and specifically comprising the following steps: the vacuum degree of the vacuum chamber of the film plating machine is adjusted to be 5.0 multiplied by 10 -3 Pa, the temperature is 250 ℃ below zero, and the heat preservation time is 30min; introducing Ar into the vacuum chamber of the film plating machine, and keeping the pressure at 0.4Pa; then starting a bias power supply, adjusting the bias voltage to be 250-280V, and discharging and cleaning for 20-30 min; adjusting the bias voltage to be 120V-170V, starting ion source ion cleaning for 30min, starting an arc source Ti target, adjusting the bias voltage to be 300V, adjusting the target current to be 80A, and bombarding the Ti target by ions for 8min; adjusting the air pressure to 0.39Pa, adjusting the bias voltage to 60V, and arc plating Ti for 7min;
placing the aluminum foil subjected to the nano titanium plating treatment at 82 deg.C and with an applied current density of 30A/dm 2 Soaking the first mixed treatment solution for 85s, draining for 20s, and continuously spraying the first mixed treatment solution for 3h under the condition that the spraying flow is 15L/h to obtain the aluminum foil treated by the first mixed treatment solution and the first mixed treatment waste liquid, wherein the first mixed treatment solution comprises 6 mass percent of hydrochloric acid and 5 mass percent of Al 3+ 6% sulfuric acid;
mixing the pre-treatment waste liquid and the first mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain sulfuric acid and hydrochloric acid;
cleaning the aluminum foil treated by the first mixed treatment solution by using pure water, soaking the aluminum foil in a second mixed treatment solution at the temperature of 75 ℃ for 150s after cleaning to obtain the aluminum foil treated by the second mixed treatment solution and a second mixed treatment waste liquid, wherein the second mixed treatment solution contains 5 mass percent of nitric acid, 0.3 mass percent of graphene and 5 mass percent of Al 3+ And 1.2% of a corrosion inhibitor;
placing the aluminum foil treated by the second mixed treatment solution into a third mixed treatment solution at the temperature of 90 ℃ for soaking for 250s to obtain the aluminum foil treated by the third mixed treatment solution and a third mixed treatment waste liquid, wherein the third mixed treatment solution contains 5% by mass of nitric acid, 0.3% by mass of graphene and 3% by mass of Al in the third mixed treatment solution 3+ And 0.6% of a corrosion inhibitor;
collecting the second mixed treatment waste liquid and the third mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain nitric acid;
and (3) placing the aluminum foil treated by the third mixed treatment solution in a nitric acid solution with the mass percentage of 3% at the temperature of 50 ℃ for soaking for 180s to obtain the electrode foil for the aluminum electrolytic capacitor.
Example 3:
a preparation method of an electrode foil for an aluminum electrolytic capacitor comprises the following steps:
soaking aluminum foil with purity of 99.99% and thickness of 120 μm in pretreatment solution at 60 deg.C for 60s to obtain pretreatment solutionThe aluminum foil after soaking and pretreatment waste liquid, wherein the pretreatment solution contains hydrochloric acid accounting for 12 percent of the mass percent of the pretreatment solution and Al accounting for 9 percent of the mass percent of the pretreatment solution 3+ And 4% sulfuric acid;
placing the aluminum foil soaked by the pretreatment solution in a vacuum chamber of a coating machine for nano titanium coating treatment, and specifically comprising the following steps: the vacuum degree of the vacuum chamber of the film plating machine is adjusted to be 5.0 multiplied by 10 -3 Pa, at the temperature of 220 ℃, and keeping the temperature for 25min; introducing Ar into the vacuum chamber of the film plating machine, and keeping the pressure at 0.3Pa; then starting a bias power supply, adjusting the bias voltage to 260V, and carrying out discharge cleaning for 25min; adjusting the bias voltage to 180V, starting ion source ion cleaning for 25min, starting an arc source Ti target, adjusting the bias voltage to 250V, adjusting the target current to 65A, and bombarding the Ti target by ions for 8min; adjusting the air pressure to 0.39Pa, adjusting the bias voltage to 55V, and arc plating Ti for 6min;
placing the aluminum foil subjected to the nano titanium plating treatment at the temperature of 60 ℃ and the applied current density of 25A/dm 2 Soaking the first mixed treatment solution for 70s, draining for 15s, and continuously spraying the first mixed treatment solution for 2h under the condition that the spraying flow is 12L/h to obtain the aluminum foil treated by the first mixed treatment solution and the first mixed treatment waste liquid, wherein the first mixed treatment solution comprises 3% of hydrochloric acid and 4% of Al in percentage by mass 3+ 4% sulfuric acid;
mixing the pre-treatment waste liquid and the first mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain sulfuric acid and hydrochloric acid;
cleaning the aluminum foil treated by the first mixed treatment solution by using pure water, soaking the aluminum foil in a second mixed treatment solution at the temperature of 60 ℃ for 120s after cleaning to obtain the aluminum foil treated by the second mixed treatment solution and a second mixed treatment waste liquid, wherein the second mixed treatment solution contains 4% by mass of nitric acid, 0.2% by mass of graphene and 4% by mass of Al 3+ And 0.7% of a corrosion inhibitor;
placing the aluminum foil treated by the second mixed treatment solution into a third mixed treatment solution at the temperature of 80 ℃ for soaking for 150s to obtain a third mixed treatment solutionThe treated aluminum foil and the third mixed treatment waste liquid contain 4% by mass of nitric acid, 0.2% by mass of graphene and 4% by mass of Al in the third mixed treatment solution 3+ And 0.7% of a corrosion inhibitor;
collecting the second mixed treatment waste liquid and the third mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain nitric acid;
and (3) placing the aluminum foil treated by the third mixed treatment solution into a nitric acid solution with the mass percentage of 1% at the temperature of 50 ℃ for soaking for 160s to obtain the electrode foil for the aluminum electrolytic capacitor.
Example 4:
a preparation method of an electrode foil for an aluminum electrolytic capacitor comprises the following steps:
placing an aluminum foil with the purity of 99.99 percent and the thickness of 120 mu m in a pretreatment solution at the temperature of 70 ℃ to be soaked for 70s to obtain the aluminum foil soaked by the pretreatment solution and a pretreatment waste liquid, wherein the pretreatment solution contains hydrochloric acid accounting for 12 percent of the mass of the pretreatment solution and Al accounting for 9 percent of the mass of the pretreatment solution 3+ And 4% sulfuric acid;
placing the aluminum foil soaked by the pretreatment solution into a vacuum chamber of a film plating machine for nano titanium plating treatment, which comprises the following steps: the vacuum degree of the vacuum chamber of the film plating machine is adjusted to be 5.0 multiplied by 10 -3 Pa, the temperature is 240 ℃, and the heat preservation time is 25min; introducing Ar into the vacuum chamber of the film plating machine, and keeping the pressure at 0.3Pa; then starting a bias power supply, adjusting the bias voltage to 260V, and carrying out discharge cleaning for 25min; adjusting the bias voltage to 160V, starting ion source ion cleaning for 26min, starting an arc source Ti target, adjusting the bias voltage to 260V, setting the target current to 75A, and bombarding the Ti target by ions for 8min; adjusting the air pressure to 0.39Pa, adjusting the bias voltage to 55V, and arc plating Ti for 6min;
placing the aluminum foil subjected to the nano titanium plating treatment at the temperature of 75 ℃ and the applied current density of 28A/dm 2 Soaking the first mixed treatment solution for 75s, draining for 20s, and continuously spraying the first mixed treatment solution for 3h under the condition that the spraying flow is 15L/h to obtain the aluminum foil treated by the first mixed treatment solution and the aluminum foil treated by the first mixed treatment solutionA first mixed treatment waste liquid, wherein the first mixed treatment solution comprises 4% of hydrochloric acid and 4% of Al in percentage by mass 3+ 3% sulfuric acid;
mixing the pre-treatment waste liquid and the first mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain sulfuric acid and hydrochloric acid;
cleaning the aluminum foil treated by the first mixed treatment solution by using pure water, soaking the aluminum foil in a second mixed treatment solution at the temperature of 60 ℃ for 120s after cleaning to obtain the aluminum foil treated by the second mixed treatment solution and a second mixed treatment waste liquid, wherein the second mixed treatment solution contains 5 mass percent of nitric acid, 0.3 mass percent of graphene and 4 mass percent of Al 3+ And 1.1% of a corrosion inhibitor;
placing the aluminum foil treated by the second mixed treatment solution into a third mixed treatment solution at the temperature of 80 ℃ to soak for 200s to obtain the aluminum foil treated by the third mixed treatment solution and a third mixed treatment waste liquid, wherein the third mixed treatment solution contains 4% by mass of nitric acid, 0.2% by mass of graphene and 4% by mass of Al 3+ And 0.8% of a corrosion inhibitor;
collecting the second mixed treatment waste liquid and the third mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain nitric acid;
and (3) placing the aluminum foil treated by the third mixed treatment solution in a nitric acid solution with the mass percentage of 3% at the temperature of 50 ℃ for soaking for 150s to obtain the electrode foil for the aluminum electrolytic capacitor.
Example 5:
a preparation method of an electrode foil for an aluminum electrolytic capacitor comprises the following steps:
placing an aluminum foil with the purity of 99.99% and the thickness of 120 mu m in a pretreatment solution at the temperature of 55 ℃ to be soaked for 45s to obtain the aluminum foil soaked in the pretreatment solution and a pretreatment waste liquid, wherein the pretreatment solution contains hydrochloric acid accounting for 8% of the mass percent of the pretreatment solution and Al accounting for 7% of the mass percent of the pretreatment solution 3+ And 2% sulfuric acid;
placing the aluminum foil soaked by the pretreatment solution in a vacuum chamber of a coating machine for nano titanium coating treatment, and specifically comprising the following steps: the vacuum degree of the vacuum chamber of the film plating machine is adjusted to be 5.0 multiplied by 10 -3 Pa, the temperature is 210 ℃, and the heat preservation time is 22min; introducing Ar into the vacuum chamber of the film plating machine, and keeping the pressure at 0.1; then, starting a bias power supply, adjusting the bias voltage to 250, and performing discharge cleaning for 20min; adjusting the bias voltage to 120V, starting ion source ion cleaning for 20min, starting an arc source Ti target, adjusting the bias voltage to 200V, and the target current to 65A, and bombarding the Ti target by ions for 7min; adjusting the air pressure to 0.37Pa, adjusting the bias voltage to 55V, and arc plating Ti for 5min;
placing the aluminum foil subjected to the nano titanium plating treatment at the temperature of 45 ℃ and the applied current density of 20A/dm 2 Soaking the first mixed treatment solution for 50s, draining for 10s, and continuously spraying the first mixed treatment solution for 0.5h under the condition that the spraying flow is 10L/h to obtain the aluminum foil treated by the first mixed treatment solution and the first mixed treatment waste liquid, wherein the first mixed treatment solution comprises 3 mass percent of hydrochloric acid and 3 mass percent of Al 3+ 2% sulfuric acid;
mixing the pre-treatment waste liquid and the first mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain sulfuric acid and hydrochloric acid;
cleaning the aluminum foil treated by the first mixed treatment solution by using pure water, soaking the aluminum foil in a second mixed treatment solution at the temperature of 45 ℃ for 60s after cleaning to obtain the aluminum foil treated by the second mixed treatment solution and a second mixed treatment waste liquid, wherein the second mixed treatment solution contains 3% by mass of nitric acid, 0.1% by mass of graphene and 3% by mass of Al 3+ And 0.6% of a corrosion inhibitor;
placing the aluminum foil treated by the second mixed treatment solution into a third mixed treatment solution at the temperature of 80 ℃ for soaking for 120s to obtain the aluminum foil treated by the third mixed treatment solution and a third mixed treatment waste liquid, wherein the third mixed treatment solution contains 3% by mass of nitric acid, 0.1% by mass of graphene and 4% by mass of Al in the third mixed treatment solution 3+ And 0.7%The corrosion inhibitor of (1);
collecting the second mixed treatment waste liquid and the third mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain nitric acid;
and (3) placing the aluminum foil treated by the third mixed treatment solution in a nitric acid solution with the mass percentage of 3% at the temperature of 45 ℃ for soaking for 130s to obtain the electrode foil for the aluminum electrolytic capacitor.
Comparative example 1:
a preparation method of an electrode foil for an aluminum electrolytic capacitor comprises the following steps:
placing an aluminum foil with the purity of 99.99% and the thickness of 120 mu m in a pretreatment solution at the temperature of 55 ℃ to be soaked for 45s to obtain the aluminum foil soaked by the pretreatment solution and a pretreatment waste liquid, wherein the pretreatment solution contains hydrochloric acid accounting for 7% of the mass percent of the pretreatment solution and Al accounting for 6% of the mass percent of the pretreatment solution 3+ And 2% sulfuric acid;
placing the aluminum foil soaked in the pretreatment solution at 45 deg.C and with an applied current density of 20A/dm 2 Soaking the first mixed treatment solution for 50s, draining for 10s, and continuously spraying the first mixed treatment solution for 0.5h under the condition that the spraying flow is 10L/h to obtain the aluminum foil treated by the first mixed treatment solution and first mixed treatment waste liquid, wherein the first mixed treatment solution comprises 2% of hydrochloric acid and 3% of Al in percentage by mass 3+ 2% sulfuric acid;
mixing the pre-treatment waste liquid and the first mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain sulfuric acid and hydrochloric acid;
cleaning the aluminum foil treated by the first mixed treatment solution by adopting pure water, soaking the aluminum foil in a second mixed treatment solution at the temperature of 45 ℃ for 60s after the cleaning is finished, obtaining the aluminum foil treated by the second mixed treatment solution and a second mixed treatment waste liquid, wherein the second mixed treatment solution contains 3% of nitric acid, 0.1% of graphene and 3% of Al in percentage by mass 3+ And 0.6% of a corrosion inhibitor;
placing the aluminum foil treated by the second mixed treatment solutionSoaking the aluminum foil in a third mixed treatment solution at the temperature of 75 ℃ for 120s to obtain an aluminum foil treated by the third mixed treatment solution and a third mixed treatment waste liquid, wherein the third mixed treatment solution contains 3 mass percent of nitric acid, 0.1 mass percent of graphene and 3 mass percent of Al in the third mixed treatment solution 3+ And 0.6% of a corrosion inhibitor;
collecting the second mixed treatment waste liquid and the third mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain nitric acid;
and (3) placing the aluminum foil treated by the third mixed treatment solution into a nitric acid solution with the mass percent of 1-3% and the temperature of 45 ℃ to soak for 120s to obtain the electrode foil for the aluminum electrolytic capacitor.
Comparative example 2:
a preparation method of an electrode foil for an aluminum electrolytic capacitor comprises the following steps:
placing an aluminum foil with the purity of 99.99% and the thickness of 120 mu m in a pretreatment solution at the temperature of 55 ℃ to be soaked for 45s to obtain the aluminum foil soaked in the pretreatment solution and a pretreatment waste liquid, wherein the pretreatment solution contains hydrochloric acid accounting for 7% of the mass of the pretreatment solution and Al accounting for 6% of the mass of the pretreatment solution 3+ And 2% sulfuric acid;
placing the aluminum foil soaked in the pretreatment solution at 45 deg.C and with an applied current density of 20A/dm 2 The first mixed treatment solution is soaked for 50s, and the mass percentage of the first mixed treatment solution is 2 percent of hydrochloric acid and 3 percent of Al 3+ 2% sulfuric acid;
mixing the pre-treatment waste liquid and the first mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain sulfuric acid and hydrochloric acid;
cleaning the aluminum foil treated by the first mixed treatment solution by using pure water, soaking the aluminum foil in a second mixed treatment solution at the temperature of 45 ℃ for 60s after cleaning to obtain the aluminum foil treated by the second mixed treatment solution and a second mixed treatment waste liquid, wherein the second mixed treatment solution contains 3% by mass of nitric acid, 0.1% by mass of graphene and 3% by mass of Al 3+ And 0.6% of a corrosion inhibitor;
placing the aluminum foil treated by the second mixed treatment solution in a third mixed treatment solution at the temperature of 75 ℃ for soaking for 120s to obtain the aluminum foil treated by the third mixed treatment solution and a third mixed treatment waste liquid, wherein the third mixed treatment solution contains 3% by mass of nitric acid, 0.1% by mass of graphene and 3% by mass of Al in the third mixed treatment solution 3+ And 0.6% of a corrosion inhibitor;
collecting the second mixed treatment waste liquid and the third mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain nitric acid;
and (3) placing the aluminum foil treated by the third mixed treatment solution into a nitric acid solution with the mass percent of 1-3% and the temperature of 45 ℃ to soak for 120s to obtain the electrode foil for the aluminum electrolytic capacitor.
Comparative example 3:
a preparation method of an electrode foil for an aluminum electrolytic capacitor comprises the following steps:
placing an aluminum foil with the purity of 99.99% and the thickness of 120 mu m in a pretreatment solution at the temperature of 55 ℃ to be soaked for 45s to obtain the aluminum foil soaked by the pretreatment solution and a pretreatment waste liquid, wherein the pretreatment solution contains hydrochloric acid accounting for 7% of the mass percent of the pretreatment solution and Al accounting for 6% of the mass percent of the pretreatment solution 3+ And 2% sulfuric acid;
placing the aluminum foil soaked in the pretreatment solution at 45 deg.C and with an applied current density of 20A/dm 2 The first mixed treatment solution is soaked for 50s, and the first mixed treatment solution comprises 2% of hydrochloric acid and 3% of Al in percentage by mass 3+ 2% sulfuric acid;
mixing the pre-treatment waste liquid and the first mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain sulfuric acid and hydrochloric acid;
cleaning the aluminum foil treated by the first mixed treatment solution by pure water, soaking the aluminum foil in a second mixed treatment solution at the temperature of 45 ℃ for 60s after the cleaning is finished, obtaining the aluminum foil treated by the second mixed treatment solution and a second mixed treatment waste liquid, wherein the second mixed treatment waste liquid isThe mixed treatment solution contains 3 percent of nitric acid and 3 percent of Al in percentage by mass of the second mixed treatment solution 3+ And 0.6% of a corrosion inhibitor;
placing the aluminum foil treated by the second mixed treatment solution into a third mixed treatment solution at the temperature of 75 ℃ to soak for 120s to obtain the aluminum foil treated by the third mixed treatment solution and a third mixed treatment waste liquid, wherein the third mixed treatment solution contains 3% by mass of nitric acid and 3% by mass of Al in the third mixed treatment solution 3+ And 0.6% of a corrosion inhibitor;
collecting the second mixed treatment waste liquid and the third mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain nitric acid;
and (3) placing the aluminum foil treated by the third mixed treatment solution into a nitric acid solution with the mass percent of 1-3% and the temperature of 45 ℃ to soak for 120s to obtain the electrode foil for the aluminum electrolytic capacitor.
(1) The corrosion foils manufactured in examples 1 to 5 and the corrosion foil manufactured in comparative example 1 were subjected to the relevant performance test using a specific volume meter, and the results are shown in table 1 below.
Table 1:
Figure BDA0002962579410000161
Figure BDA0002962579410000171
(2) The corrosion foils manufactured in examples 1 to 5 and the corrosion foil prepared in comparative example 2 were subjected to the relevant performance test using a specific volume measuring instrument, and the results are shown in table 2 below.
Table 2:
Figure BDA0002962579410000172
(3) The corrosion foils manufactured in examples 1 to 5 and the corrosion foil prepared in comparative example 3 were subjected to the relevant performance test using a specific volume measuring instrument, and the results are shown in table 3 below.
Table 3:
Figure BDA0002962579410000173
Figure BDA0002962579410000181
from the data combination analysis in table 1, table 2 and table 3, it can be seen that the nano titanium is vacuum-plated on the surface of the aluminum foil after the pretreatment soaking, the first mixed treatment solution is soaked and the liquid is sprayed, the graphene is added into the second mixed treatment solution and the third mixed treatment solution, and the added graphene and Al are combined for analysis 3+ The corrosion inhibitor has synergistic effect, is beneficial to increasing the bending strength and specific volume of the aluminum foil and reducing the dispersion rate of the specific volume of the corrosion foil, and compared with the comparative example 1 in which nano titanium is not vacuum-plated on the surface of the aluminum foil, the specific volume increase rate of the corrosion foil manufactured in the examples 1-5 is more than 5%; in comparative example 2, no nano titanium was vacuum-plated on the surface of the aluminum foil, no liquid spraying was performed, the specific volume dispersion rate was more than 8%, and the specific volume increase rate of the corrosion foil manufactured in examples 1 to 5 was more than 5%; in comparative example 3, no nano titanium was vacuum-plated on the surface of the aluminum foil, no liquid spraying was performed, no graphene was added to the second mixed treatment solution and the third mixed treatment solution, the specific volume dispersion rate was greater than 8%, and the specific volume increase rate of the corrosion foil manufactured in examples 1 to 5 was greater than 15%. The electrode foil prepared by the invention has excellent comprehensive performance.
In addition, in the process of preparing the electrode foil, extra current does not need to be applied to the second mixed treatment solution and the third mixed treatment solution, so that the electrode foil has the advantages of energy conservation and environmental protection.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.

Claims (6)

1. A preparation method of an electrode foil for an aluminum electrolytic capacitor is characterized by comprising the following steps:
placing an aluminum foil in a pretreatment solution at a temperature of 55-75 ℃ for soaking for 45s-75s to obtain the aluminum foil soaked in the pretreatment solution and pretreatment waste liquid;
placing the aluminum foil soaked by the pretreatment solution in a vacuum chamber of a coating machine for nano titanium coating;
placing the aluminum foil subjected to the nano titanium plating treatment in a first mixed treatment solution at the temperature of 45-82 ℃ for soaking for 50s-85s, draining for 10s-20s, and then continuously spraying the first mixed treatment solution for 0.5h-3h under the condition that the spraying flow is 10-15L/h to obtain the aluminum foil treated by the first mixed treatment solution and a first mixed treatment waste liquid;
mixing the pre-treatment waste liquid and the first mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain sulfuric acid and hydrochloric acid;
cleaning the aluminum foil treated by the first mixed treatment solution by pure water, and after cleaning, placing the aluminum foil in a second mixed treatment solution at the temperature of 45-75 ℃ for soaking for 60s-150s to obtain the aluminum foil treated by the second mixed treatment solution and a second mixed treatment waste liquid;
placing the aluminum foil treated by the second mixed treatment solution into a third mixed treatment solution at the temperature of 75-90 ℃ for soaking for 120s-250s to obtain the aluminum foil treated by the third mixed treatment solution and a third mixed treatment waste liquid;
collecting the second mixed treatment waste liquid and the third mixed treatment waste liquid, treating by adopting a diffusion dialysis membrane separator, and recovering to obtain nitric acid;
placing the aluminum foil treated by the third mixed treatment solution in a nitric acid solution at the temperature of 45-60 ℃ to soak for 120-180 s to obtain an electrode foil for an aluminum electrolytic capacitor;
wherein the second mixed treatment solution contains 3-5% of nitric acid, 0.1-0.3% of graphene and 3-5% of Al in percentage by mass 3+ And 0.6 to 1.2 percent of corrosion inhibitor;
the third mixed treatment solution contains 3 to 5 mass percent of nitric acid, 0.1 to 0.3 mass percent of graphene and 3 to 5 mass percent of Al 3+ And 0.6 to 1.2 percent of corrosion inhibitor;
the corrosion inhibitor is one or any combination of two of sodium polystyrene sulfonate and phosphoric acid.
2. The method of manufacturing an electrode foil for an aluminum electrolytic capacitor as recited in claim 1, wherein the pretreatment solution contains 7 to 12 mass% of hydrochloric acid and 6 to 9 mass% of Al based on the mass of the pretreatment solution 3+ And 2 to 6 percent of sulfuric acid.
3. The method for producing an electrode foil for an aluminum electrolytic capacitor as recited in claim 1, wherein the nano titanium plating treatment is: the vacuum degree of the vacuum chamber of the film plating machine is adjusted to be 5.0 multiplied by 10 -3 Pa, the temperature is 200-250 ℃, and the heat preservation time is 20-30 min; introducing Ar into the vacuum chamber of the film plating machine, and keeping the pressure at 0.1Pa to 0.4Pa; then starting a bias power supply, adjusting the bias voltage to 250V to 280V, and discharging and cleaning for 20min to 30min; adjusting bias voltage to be 120V to 170V, starting an ion source to perform ion cleaning for 20min to 30min, and starting an arc source Ti target, wherein the bias voltage is adjusted to be 200V to 300V, the target current is 60A to 80A, and the Ti target is bombarded by ions for 7min to 8min;adjusting the air pressure to 0.36 Pa-0.39 Pa, adjusting the bias voltage to 50V-60V, and arc plating Ti for 5 min-7 min.
4. The method for producing an electrode foil for an aluminum electrolytic capacitor as recited in claim 1, wherein the first mixed treatment solution contains 2 to 6 mass% of hydrochloric acid and 3 to 5 mass% of Al based on the first mixed treatment solution 3+ 2 to 6 percent of sulfuric acid.
5. The method for producing an electrode foil for an aluminum electrolytic capacitor as recited in claim 1, wherein the nitric acid solution contains 1 to 3 mass% of nitric acid.
6. The method for preparing an electrode foil for an aluminum electrolytic capacitor as recited in claim 1 in which the first mixed treatment solution is soaked at a rate of 20A/dm 2 ～30A/dm 2 The current density of (1).
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