WO2023236573A1 - Method for preparing high-specific-volume low-voltage electrode foil for automotive electronics - Google Patents

Method for preparing high-specific-volume low-voltage electrode foil for automotive electronics Download PDF

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WO2023236573A1
WO2023236573A1 PCT/CN2023/075328 CN2023075328W WO2023236573A1 WO 2023236573 A1 WO2023236573 A1 WO 2023236573A1 CN 2023075328 W CN2023075328 W CN 2023075328W WO 2023236573 A1 WO2023236573 A1 WO 2023236573A1
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foil
formation
controlled
minutes
dip
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PCT/CN2023/075328
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French (fr)
Chinese (zh)
Inventor
王建中
陈辰
徐中均
周红炎
刘慧�
冒慧敏
何桂丽
王贵州
金学军
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南通海星电子股份有限公司
南通海一电子有限公司
宁夏海力电子有限公司
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Priority to KR1020237034833A priority Critical patent/KR20240009387A/en
Publication of WO2023236573A1 publication Critical patent/WO2023236573A1/en

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    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/77—Controlling or regulating of the coating process
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/12—Anodising more than once, e.g. in different baths
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/16—Pretreatment, e.g. desmutting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/055—Etched foil electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the invention relates to the technical field of electrode foil manufacturing, in particular to a preparation method of high specific volume and low voltage electrode foil for automotive electronics.
  • multi-stage formation of corroded foil is usually used to prepare electrode foil.
  • the general operation steps are: four-stage formation, one-stage formation: 7% ammonium adipate, 1% borate, temperature 70°C, time 7 minutes , after washing with water, enter the secondary formation: 5% ammonium adipate, 1% borate, temperature 70°C, time 6 minutes, third-level formation: 3% ammonium adipate, 1% borate, temperature 70°C, time 8min, after washing with water, carry out four-stage formation: 5% phosphate, temperature 70°C, time 15min, the latter one: 1% phosphate, temperature 80°C, time 12min, after washing with water, enter 7% phosphoric acid solution, time 5min, after washing High temperature (450-500°C) treatment for 1.5min, the last two: 3% phosphate, temperature 70°C, time 5min, the last three: 1% phosphate, temperature 70°C, time 5.5min, wash with water and dry.
  • the preparation process route is simple and the cost is low, the capacitance and boiling life of the prepared electrode foil are low, and the defective rate remains high.
  • the reason is that the aluminum oxide crystal content in the oxide film on the surface of the electrode foil is low, and a large number of defects remain on the oxide film after chemical conversion treatment. Therefore, technicians are urgently needed to solve the above problems.
  • the present invention relates to a preparation method of high specific volume low voltage electrode foil for automotive electronics, which includes the following steps:
  • Multi-level formation including the following sub-steps:
  • First-level formation immerse the corroded foil obtained in step S1 into a mixed solution containing 5-10wt% ammonium sulfate, 1-2wt% borate, and 0.5-1wt% amine salt, controlled at a temperature of 65-85°C. The formation is carried out at a voltage of 20 to 160V, and the time is controlled between 5 and 10 minutes, to produce a first-level formation foil;
  • Secondary formation Dip the primary formation foil processed in step S22 into a mixed solution containing 3-7wt% ammonium sulfate and 1-2wt% borate at a temperature controlled at 65-85°C, 20-160V The formation is carried out under voltage and the time is controlled between 5 and 10 minutes to produce a secondary formation foil;
  • Step S26 Intermediate treatment: Dip the tertiary chemical foil processed in step S25 into a quaternary ammonium salt solution with a temperature controlled at 40 to 60°C and 5 to 10 wt%, and the duration is controlled at 5 to 10 minutes;
  • step S27 Four-stage formation: Dip the three-stage formation foil obtained in step S26 into a solution containing 5-7wt% phosphate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V, and the duration is controlled at 15-15%. 20 minutes to make a fourth-stage chemical foil;
  • Step S31 First-level post-processing: Dip the fourth-level chemical foil obtained in step S27 into a phosphate aqueous solution with a temperature controlled at 65-85°C and 1-5wt%, apply a voltage of 20-160V, and control the duration at 10-15 minutes. Made into primary treated foil;
  • Step S33 Pickling treatment: Dip the first-level treated foil treated in step S32 into a mixed solution containing 7 to 10 wt% phosphoric acid and oxidizing acid, and the time is controlled to 5 to 10 minutes;
  • step S34 Heat treatment: perform water washing and drying operations on the first-level treated foil obtained in step S33, and the drying temperature is controlled at 450 ⁇ 500°C, and the duration is controlled at 1 ⁇ 2 min;
  • Secondary post-processing Dip the primary-processed foil obtained in step S34 into a phosphate aqueous solution with a temperature controlled at 65-85°C and 1-5wt%, apply a voltage of 20-160V, and control the duration at 5-10 minutes. Made into secondary treated foil;
  • step S36 Third-level post-processing: Dip the secondary-processed foil obtained in step S35 into a phosphate aqueous solution with a temperature controlled at 65 to 85°C and 1 to 5 wt%, apply a voltage of 20 to 160 V, and control the duration to 5 to 10 minutes.
  • a temperature controlled at 65 to 85°C and 1 to 5 wt% a temperature controlled at 65 to 85°C and 1 to 5 wt%
  • apply a voltage of 20 to 160 V and control the duration to 5 to 10 minutes.
  • step S37 Surface cleaning: Wash and air-dry the three-level treated foil obtained in step S36 to obtain a high specific volume low-voltage electrode foil.
  • the borate is preferably any one of borax or sodium metaborate or a mixture thereof.
  • the amine salt is preferably hexylbenzylamine salt, dicyclohexylamine salt, bis-tert-butoxycarbonylhistidine dicyclohexylamine salt, dimethylamine hydrochloride, and triethanolamine , any one of piroctone ethanolamine salts or their mixtures.
  • the quaternary ammonium salt is preferably any one of sodium lauryl sulfate, dodecyl trimethyl ammonium bromide, ammonium lauryl alcohol ether sulfate or their combinations. mixture.
  • the phosphate is preferably any one of diammonium phosphate, sodium hexametaphosphate, disodium hydrogen phosphate or a mixture thereof.
  • the preparation method of high specific volume low-voltage electrode foil for automotive electronics has achieved at least the following beneficial effects:
  • a constant density of current is applied to the formation bath liquid to ensure that the oxide film is stably and rapidly formed on the surface of the corroded foil. , and the distribution shape of the formed channels in different areas is more balanced;
  • the voltage, temperature, time, and composition and ratio of the formation liquid used are adjusted so that the density of each layer of the formed oxide film becomes consistent, which is beneficial to improving the boiling properties of the electrode foil. life;
  • step S21 adding amine treatment liquid during the first-level formation can improve the concentration of the oxide film.
  • Figure 1 is a metallographic photograph of a shaped electrode foil prepared by conventional multi-stage formation as described in the background art.
  • Figure 2 is a metallographic photograph of the shaped electrode foil prepared by the method in Example 1.
  • Figure 3 is a metallographic photograph of the shaped electrode foil prepared by the method in Example 2.
  • Figure 4 is a metallographic photograph of the shaped electrode foil prepared by the method in Example 3.
  • Figure 5 is a metallographic photograph of the shaped electrode foil prepared by the method in Example 4.
  • the electrode foil is prepared with reference to the multi-stage formation method disclosed in the background art above.
  • a method for preparing high specific volume low voltage electrode foil for automotive electronics which includes the following steps:
  • Multi-level formation including the following sub-steps:
  • First-level formation Immerse the corroded foil obtained in step S1 into a mixed solution containing 5wt% ammonium sulfate, 1wt% sodium metaborate, and 0.5wt% hexyl benzylamine salt, controlled at a temperature of 65 to 85°C, for 20 to The formation is carried out at a voltage of 160V and the time is controlled at 10 minutes to produce a first-level formation foil;
  • step S22 Surface cleaning: perform water washing and air-drying operations on the primary chemical foil obtained in step S21 (the air-drying temperature does not exceed 20°C);
  • Secondary formation Dip the primary formation foil processed in step S22 into a mixed solution containing 3wt% ammonium sulfate and 1wt% sodium metaborate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V. , and the duration should be controlled at 10 minutes to make a secondary formation foil;
  • step S24 Tertiary formation: Dip the secondary formation foil obtained in step S23 into a mixed solution containing 3wt% ammonium sulfate and 1wt% sodium metaborate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V, and The time is controlled at 15 minutes to make a three-stage chemical foil;
  • step S26 Intermediate treatment: Dip the tertiary chemical foil processed in step S25 into a 5wt% sodium dodecyl sulfate aqueous solution with a temperature controlled at 40-60°C, and the duration is controlled at 10 minutes;
  • step S27 Four-stage formation: Dip the three-stage formation foil obtained in step S26 into a solution containing 5wt% sodium hexametaphosphate and controlled at a temperature of 65 to 85°C. The formation is carried out at a voltage of 20 to 160V, and the duration is controlled to 20 minutes. Made into quaternary formation foil;
  • Step S31 First-level post-processing: Dip the fourth-level chemical foil obtained in step S27 into a 1wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the time to 15 minutes to prepare Primary treatment foil;
  • Acid dipping treatment Dip the first-level treated foil treated in step S32 into an acidic mixed solution containing 7wt% phosphoric acid:perchloric acid in a ratio of 1:1, and the duration is controlled to 6 minutes;
  • step S34 Heat treatment: perform water washing and drying operations on the first-level treated foil obtained in step S33, and the drying temperature is controlled at 450 ⁇ 500°C, and the drying time is controlled at 1.5 minutes;
  • Secondary post-processing Dip the primary-processed foil obtained in step S34 into a 1wt% sodium hexametaphosphate aqueous solution controlled at a temperature of 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 10 minutes to prepare secondary treatment foil;
  • step S36 Third-level post-processing: Dip the secondary-processed foil obtained in step S35 into a 1wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 10 minutes to prepare Tertiary treated foil;
  • step S37 Surface cleaning: Wash and air-dry the three-level treated foil obtained in step S36 to obtain a high specific volume low-voltage electrode foil.
  • a method for preparing high specific volume low voltage electrode foil for automotive electronics which includes the following steps:
  • Multi-level formation including the following sub-steps:
  • step S21 First-level formation: immerse the corroded foil obtained in step S1 into a mixed solution containing 8wt% ammonium sulfate, 1.5wt% sodium metaborate, and 0.7wt% hexyl benzylamine salt at a temperature of 65 to 85°C, 20 The formation is carried out at a voltage of ⁇ 160V, and the time is controlled at 10 minutes, to produce a first-level formation foil;
  • step S22 Surface cleaning: perform water washing and air-drying operations on the primary chemical foil obtained in step S21 (the air-drying temperature does not exceed 20°C);
  • Secondary formation Dip the primary formation foil processed in step S22 into a mixed solution containing 5wt% ammonium sulfate and 1.5wt% sodium metaborate, controlled at a temperature of 65 to 85°C, and carried out at a voltage of 20 to 160V. Formation, and the time should be controlled within 10 minutes, to produce a secondary formation foil;
  • step S24 Tertiary formation: Dip the secondary formation foil obtained in step S23 into a mixed solution containing 4wt% ammonium sulfate and 1.5wt% sodium metaborate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V. And the time is controlled at 15 minutes to make a three-stage chemical foil;
  • step S26 Intermediate treatment: Dip the tertiary chemical foil processed in step S25 into an 8wt% sodium dodecyl sulfate aqueous solution with a temperature controlled at 40-60°C, and the duration is controlled at 10 minutes;
  • step S27 Four-stage formation: Dip the three-stage formation foil obtained in step S26 into a solution containing 6wt% sodium hexametaphosphate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V, and the duration is controlled at 20 minutes.
  • a solution containing 6wt% sodium hexametaphosphate at a temperature controlled at 65-85°C and perform the formation at a voltage of 20-160V, and the duration is controlled at 20 minutes.
  • Step S31 First-level post-processing: Dip the fourth-level chemical foil obtained in step S27 into a 3wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the time to 15 minutes to prepare Primary treatment foil;
  • step S33 Pickling treatment: Dip the first-level treated foil treated in step S32 into an acidic mixed solution containing 8wt% phosphoric acid:perchloric acid in a ratio of 1:1, and the time is controlled to 6 minutes;
  • step S34 Heat treatment: perform water washing and drying operations on the first-level treated foil obtained in step S33, and the drying temperature is controlled at 450 ⁇ 500°C, and the drying time is controlled at 1.5 minutes;
  • Secondary post-processing Dip the primary-processed foil obtained in step S34 into a 3wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 10 minutes to prepare secondary treatment foil;
  • step S36 Third-level post-processing: Dip the secondary-processed foil obtained in step S35 into a 3wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 10 minutes to prepare Tertiary treated foil;
  • step S37 Surface cleaning: Wash and air-dry the three-level treated foil obtained in step S36 to obtain a high specific volume low-voltage electrode foil.
  • a method for preparing high specific volume low voltage electrode foil for automotive electronics which includes the following steps:
  • Multi-level formation including the following sub-steps:
  • step S21 First-level formation: immerse the corroded foil obtained in step S1 into a mixed solution containing 10wt% ammonium sulfate, 2wt% sodium metaborate, and 1wt% hexyl benzylamine salt at a temperature of 65 to 85°C, 20 to 160V Carry out formation under voltage and control the time to 10 minutes to make a first-level formation foil;
  • step S22 Surface cleaning: perform water washing and air-drying operations on the primary chemical foil obtained in step S21 (the air-drying temperature does not exceed 20°C);
  • Secondary formation Dip the primary formation foil processed in step S22 into a mixed solution containing 7wt% ammonium sulfate and 2wt% sodium metaborate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V. , and the duration should be controlled at 10 minutes to make a secondary formation foil;
  • step S26 Intermediate treatment: Dip the tertiary chemical foil processed in step S25 into a 10wt% sodium dodecyl sulfate aqueous solution with a temperature controlled at 40-60°C, and the duration is controlled at 10 minutes;
  • step S27 Four-stage formation: Dip the three-stage formation foil obtained in step S26 into a solution containing 7wt% sodium hexametaphosphate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V, and the duration is controlled at 20 minutes.
  • a solution containing 7wt% sodium hexametaphosphate at a temperature controlled at 65-85°C and perform the formation at a voltage of 20-160V, and the duration is controlled at 20 minutes.
  • Step S31 First-level post-processing: Dip the fourth-level chemical foil obtained in step S27 into a 5wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the time to 15 minutes to prepare Primary treatment foil;
  • Acid dipping treatment Dip the first-level treated foil treated in step S32 into an acidic mixed solution containing 10wt% phosphoric acid: perchloric acid in a ratio of 1:1, and the duration is controlled to 6 minutes;
  • step S34 Heat treatment: perform water washing and drying operations on the first-level treated foil obtained in step S33, and the drying temperature is controlled at 450 ⁇ 500°C, and the drying time is controlled at 1.5 minutes;
  • Secondary post-processing Dip the primary-processed foil obtained in step S34 into a 5wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 10 minutes to prepare secondary treatment foil;
  • step S36 Third-level post-processing: Dip the secondary-processed foil obtained in step S35 into a 5wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 10 minutes to prepare Tertiary treated foil;
  • step S37 Surface cleaning: Wash and air-dry the three-level treated foil obtained in step S36 to obtain a high specific volume low-voltage electrode foil.
  • a method for preparing high specific volume low voltage electrode foil for automotive electronics which includes the following steps:
  • Multi-level synthesis including the following sub-steps:
  • First-level formation Immerse the corroded foil obtained in step S1 into a mixed solution containing 5wt% ammonium sulfate, 1wt% sodium metaborate, and 0.5wt% hexyl benzylamine salt, controlled at a temperature of 65 to 85°C, for 20 to The formation is carried out at a voltage of 160V and the time is controlled at 5 minutes to produce a first-level formation foil;
  • step S22 Surface cleaning: perform water washing and air-drying operations on the primary chemical foil obtained in step S21 (the air-drying temperature does not exceed 20°C);
  • Secondary formation Dip the primary formation foil processed in step S22 into a mixed solution containing 3wt% ammonium sulfate and 1wt% sodium metaborate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V. , and the time should be controlled at 5 minutes to make a secondary formation foil;
  • step S24 Tertiary formation: Dip the secondary formation foil obtained in step S23 into a mixed solution containing 3wt% ammonium sulfate and 1wt% sodium metaborate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V, and The time is controlled at 7 minutes to produce a three-stage chemical foil;
  • step S26 Intermediate treatment: Dip the tertiary chemical foil processed in step S25 into a 5wt% sodium dodecyl sulfate aqueous solution with a temperature controlled at 40-60°C, and the duration is controlled at 10 minutes;
  • step S27 Four-stage formation: Dip the three-stage formation foil obtained in step S26 into a solution containing 5wt% sodium hexametaphosphate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V, and the duration is controlled at 15 minutes.
  • a solution containing 5wt% sodium hexametaphosphate at a temperature controlled at 65-85°C and perform the formation at a voltage of 20-160V, and the duration is controlled at 15 minutes.
  • Step S31 First-level post-processing: Dip the fourth-level chemical foil obtained in step S27 into a 1wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the time to 10 minutes to prepare Primary treatment foil;
  • Acid dipping treatment Dip the first-level treated foil treated in step S32 into an acidic mixed solution containing 7wt% phosphoric acid:perchloric acid in a ratio of 1:1, and the duration is controlled to 6 minutes;
  • step S34 Heat treatment: perform water washing and drying operations on the first-level treated foil obtained in step S33, and the drying temperature is controlled at 450 ⁇ 500°C, and the drying time is controlled at 1.5 minutes;
  • Secondary post-processing Dip the primary-processed foil obtained in step S34 into a 1wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 5 minutes to prepare secondary treatment foil;
  • step S36 Third-level post-processing: Dip the secondary-processed foil obtained in step S35 into a 1wt% sodium hexametaphosphate aqueous solution controlled at a temperature of 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 5 minutes to prepare Tertiary treated foil;
  • step S37 Surface cleaning: Wash and air-dry the three-level treated foil obtained in step S36 to obtain a high specific volume low-voltage electrode foil.
  • Table 1 is a summary of the performance test results of the electrode foils obtained in Comparative Examples and Examples 1 to 4.
  • Vfe the final voltage applied during the forming process of the unformed foil
  • a constant density of current is applied to the formation bath liquid to ensure that the oxide film is stably and rapidly formed on the surface of the corroded foil. , and the distribution shape of the formed channels in different areas is more balanced;
  • the voltage, temperature, time, and composition and ratio of the formation liquid used are adjusted so that the density of each layer of the formed oxide film becomes consistent, which is beneficial to improving the boiling properties of the electrode foil. life;
  • step S21 adding amine treatment liquid during the first-level formation can improve the concentration of the oxide film.
  • defects formed on the oxide film during chemical formation can be effectively and fully repaired, and can also be significantly improved. Improve the specific capacitance of aluminum electrode foil.
  • the cathode Due to the presence of strong oxidizing acid, the cathode is
  • borates such as borax and a mixture of sodium metaborate and borax can also be selected according to the actual situation;
  • dicyclohexylamine salt or dicyclohexylamine salt or di-tert-butoxycarbonyl histidine dicyclohexylamine can also be selected according to the actual situation.
  • Any one of amine salts such as dimethylamine hydrochloride, triethanolamine, piroctone ethanolamine salt, or mixtures thereof;
  • dodecyltrimethylammonium bromide and lauryl alcohol ether can also be selected according to the actual situation. Any one of quaternary ammonium salts such as ammonium sulfate or their mixture;
  • any one of the phosphates such as diammonium phosphate, disodium hydrogen phosphate or the like can also be selected according to the actual situation. Their mixture.

Abstract

The present invention relates to a method for preparing a high-specific-volume low-voltage electrode foil for automotive electronics. The method comprises the following steps: firstly, sequentially performing first-stage formation, second-stage formation, third-stage formation and fourth-stage formation operation on an etching foil, and respectively adjusting the voltage, temperature, time, and the components and proportion of the formation liquid used during performance of single formation; adding an amine treatment solution during the first-stage formation to greatly increase the content of aluminum oxide crystals in a formed oxide film; and then soaking the formed foil in a phosphate solution multiple times to perform a post-treatment operation so as to repair residual defect spots on the formed oxide film. In this way, not only can the water-boiling service life of an electrode foil be effectively prolonged, but a good foundation is also laid for greatly improving the electrical specific volume of an aluminum electrode foil.

Description

一种汽车电子用高比容低压电极箔的制备方法A method for preparing high specific volume low voltage electrode foil for automotive electronics 技术领域Technical field
本发明涉及电极箔制造技术领域，尤其是一种汽车电子用高比容低压电极箔的制备方法。The invention relates to the technical field of electrode foil manufacturing, in particular to a preparation method of high specific volume and low voltage electrode foil for automotive electronics.
背景技术Background technique
如今，全球汽车电气化程度不断提升，尤其是随着电动汽车和自动驾驶的发展，汽车智能化、网络化、电子化程度不断提高，使得在汽车上使用的电子部件也越来越多。在汽车电子系统中，配套使用的电容器种类多、数量大、质量要求高，为电容器发展提高了广阔的前景。电容器作为汽车电子配件中的基础元件，在汽车电子部件开发中起着重要的作用，小型化、长寿命、高可靠性电容器助力汽车电子设计集成化与多样化，而提高电极箔的容量是实现铝电解电容器小型化、高性能化的关键。Today, the degree of electrification of global automobiles continues to increase, especially with the development of electric vehicles and autonomous driving, the degree of automobile intelligence, networking, and electronics continues to increase, resulting in more and more electronic components being used in automobiles. In automotive electronic systems, there are many types, large quantities, and high quality requirements of capacitors used, which provides broad prospects for the development of capacitors. As a basic component in automotive electronic accessories, capacitors play an important role in the development of automotive electronic components. Miniaturization, long life, and high reliability capacitors help the integration and diversification of automotive electronic design, and increasing the capacity of electrode foils is the key to achieving The key to miniaturization and high performance of aluminum electrolytic capacitors.
目前，通常对腐蚀箔采取多级化成的方式以制备出电极箔，大致操作步骤为：四级化成，一级化成：7％己二酸铵，1％硼酸盐，温度70℃，时间7min，水洗后进入二级化成：5％己二酸铵、1％硼酸盐，温度70℃，时间6min，三级化成：3％己二酸铵、1％硼酸盐，温度70℃，时间8min，水洗后进行四级化成：5％磷酸盐，温度70℃，时间15min，后一：1％磷酸盐，温度80℃，时间12min,水洗后进入7％磷酸溶液中，时间5min，水洗后高温(450-500℃)处理1.5min，后二：3％磷酸盐，温度70℃，时间5min,后三：1％磷酸盐，温度70℃，时间5.5min,水洗后干燥。虽说制备工艺路线简洁，且成本低廉，然而，所制备出的电极箔电容量以及水煮寿命偏低，且残次品率居高不下。究其原因，在于电极箔表面氧化膜中氧化铝结晶含量偏低，且氧化膜经化成处理后其上残存有大量瑕疵点，因而，亟待技术人员解决上述问题。At present, multi-stage formation of corroded foil is usually used to prepare electrode foil. The general operation steps are: four-stage formation, one-stage formation: 7% ammonium adipate, 1% borate, temperature 70°C, time 7 minutes , after washing with water, enter the secondary formation: 5% ammonium adipate, 1% borate, temperature 70°C, time 6 minutes, third-level formation: 3% ammonium adipate, 1% borate, temperature 70°C, time 8min, after washing with water, carry out four-stage formation: 5% phosphate, temperature 70℃, time 15min, the latter one: 1% phosphate, temperature 80℃, time 12min, after washing with water, enter 7% phosphoric acid solution, time 5min, after washing High temperature (450-500℃) treatment for 1.5min, the last two: 3% phosphate, temperature 70℃, time 5min, the last three: 1% phosphate, temperature 70℃, time 5.5min, wash with water and dry. Although the preparation process route is simple and the cost is low, the capacitance and boiling life of the prepared electrode foil are low, and the defective rate remains high. The reason is that the aluminum oxide crystal content in the oxide film on the surface of the electrode foil is low, and a large number of defects remain on the oxide film after chemical conversion treatment. Therefore, technicians are urgently needed to solve the above problems.
发明内容 Contents of the invention
故，本发明设计人员鉴于上述现有的问题以及缺陷，乃搜集相关资料，经由多方的评估及考量，并经过从事于此行业的多年研发经验技术人员的不断实验以及修改，最终导致该汽车电子用高比容低压电极箔的制备方法的出现。Therefore, in view of the above-mentioned existing problems and defects, the designers of the present invention collected relevant information, evaluated and considered it from many parties, and after continuous experiments and modifications by technicians with many years of R&D experience in this industry, finally led to the automotive electronics The emergence of preparation methods for low-voltage electrode foils with high specific volumes.
为了解决上述技术问题，本发明涉及了一种汽车电子用高比容低压电极箔的制备方法，其包括以下步骤：In order to solve the above technical problems, the present invention relates to a preparation method of high specific volume low voltage electrode foil for automotive electronics, which includes the following steps:
S1、腐蚀箔的制备：取纯度不低于99.9％的铝箔浸入酸液中，对其表面进行腐蚀；S1. Preparation of corroded foil: Dip aluminum foil with a purity of not less than 99.9% into acid solution and corrode its surface;
S2、多级化成，包括以下子步骤：S2. Multi-level formation, including the following sub-steps:
S21、一级化成：将步骤S1中所得腐蚀箔浸于温度控制在65～85℃、含有5～10wt％硫酸铵、1～2wt％硼酸盐、0.5～1wt％胺盐的混合溶液中，20～160V电压下进行化成，且时长控制在5～10min，制成一级化成箔；S21. First-level formation: immerse the corroded foil obtained in step S1 into a mixed solution containing 5-10wt% ammonium sulfate, 1-2wt% borate, and 0.5-1wt% amine salt, controlled at a temperature of 65-85°C. The formation is carried out at a voltage of 20 to 160V, and the time is controlled between 5 and 10 minutes, to produce a first-level formation foil;
S22、表面清洁：对步骤S21中所得一级化成箔执行水洗、且风干操作；S22. Surface cleaning: perform water washing and air drying operations on the primary formed foil obtained in step S21;
S23、二级化成：将经步骤S22处理后的一级化成箔浸于温度控制在65～85℃、含有3～7wt％硫酸铵、1～2wt％硼酸盐的混合溶液中，20～160V电压下进行化成，且时长控制在5～10min，制成二级化成箔；S23. Secondary formation: Dip the primary formation foil processed in step S22 into a mixed solution containing 3-7wt% ammonium sulfate and 1-2wt% borate at a temperature controlled at 65-85°C, 20-160V The formation is carried out under voltage and the time is controlled between 5 and 10 minutes to produce a secondary formation foil;
S24、三级化成：将步骤S23中所得二级化成箔浸于温度控制在65～85℃、含有3～5wt％硫酸铵、1～2wt％硼酸盐的混合溶液中，20～160V电压下进行化成，且时长控制在7～15min，制成三级化成箔；S24. Tertiary formation: Dip the secondary formation foil obtained in step S23 into a mixed solution containing 3-5wt% ammonium sulfate and 1-2wt% borate at a temperature controlled at 65-85°C under a voltage of 20-160V. Carry out formation, and control the time between 7 and 15 minutes to make a three-stage formation foil;
S25、表面清洁：对步骤S24中所得三级化成箔执行水洗、且风干操作；S25. Surface cleaning: perform water washing and air-drying operations on the tertiary formation foil obtained in step S24;
S26、中间处理：将经步骤S25处理后的三级化成箔浸于温度控制在40～60℃、5～10wt％的季铵盐水溶液中，且时长控制在5～10min；S26. Intermediate treatment: Dip the tertiary chemical foil processed in step S25 into a quaternary ammonium salt solution with a temperature controlled at 40 to 60°C and 5 to 10 wt%, and the duration is controlled at 5 to 10 minutes;
S27、四级化成：将步骤S26中所得三级化成箔浸于温度控制在65～85℃、含有5～7wt％磷酸盐的溶液中，20～160V电压下进行化成，且时长控制在15～20min，制成四级化成箔；S27. Four-stage formation: Dip the three-stage formation foil obtained in step S26 into a solution containing 5-7wt% phosphate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V, and the duration is controlled at 15-15%. 20 minutes to make a fourth-stage chemical foil;
S3、后处理，包括以下子步骤： S3, post-processing, including the following sub-steps:
S31、一级后处理：将步骤S27中所得四级化成箔浸于温度控制在65～85℃、1～5wt％的磷酸盐水溶液中，施加20～160V电压，且时长控制在10～15min，制成一级处理箔；S31. First-level post-processing: Dip the fourth-level chemical foil obtained in step S27 into a phosphate aqueous solution with a temperature controlled at 65-85°C and 1-5wt%, apply a voltage of 20-160V, and control the duration at 10-15 minutes. Made into primary treated foil;
S32、表面清洁：对步骤S31中所得一级处理箔执行水洗、且风干操作；S32. Surface cleaning: perform water washing and air drying operations on the primary treated foil obtained in step S31;
S33、浸酸处理：将经步骤S32处理后的一级处理箔浸于含有7～10wt％磷酸和氧化性酸的混合溶液中，且时长控制在5～10min；S33. Pickling treatment: Dip the first-level treated foil treated in step S32 into a mixed solution containing 7 to 10 wt% phosphoric acid and oxidizing acid, and the time is controlled to 5 to 10 minutes;
S34、热处理：对步骤S33中所得一级处理箔执行水洗、烘干操作，且烘干温度控制在450～500℃，时长控制在1～2min；S34. Heat treatment: perform water washing and drying operations on the first-level treated foil obtained in step S33, and the drying temperature is controlled at 450~500°C, and the duration is controlled at 1~2 min;
S35、二级后处理：将步骤S34中所得一级处理箔浸于温度控制在65～85℃、1～5wt％的磷酸盐水溶液中，施加20～160V电压，且时长控制在5～10min，制成二级处理箔；S35. Secondary post-processing: Dip the primary-processed foil obtained in step S34 into a phosphate aqueous solution with a temperature controlled at 65-85°C and 1-5wt%, apply a voltage of 20-160V, and control the duration at 5-10 minutes. Made into secondary treated foil;
S36、三级后处理：将步骤S35中所得二级处理箔浸于温度控制在65～85℃、1～5wt％的磷酸盐水溶液中，施加20～160V电压，且时长控制在5～10min，制成三级处理箔；S36. Third-level post-processing: Dip the secondary-processed foil obtained in step S35 into a phosphate aqueous solution with a temperature controlled at 65 to 85°C and 1 to 5 wt%, apply a voltage of 20 to 160 V, and control the duration to 5 to 10 minutes. Made into tertiary treated foil;
S37、表面清洁：对步骤S36中所得三级处理箔执行水洗、且风干操作，即得到高比容低压电极箔。S37. Surface cleaning: Wash and air-dry the three-level treated foil obtained in step S36 to obtain a high specific volume low-voltage electrode foil.
作为本发明所公开技术方案的进一步优化，硼酸盐优选为硼砂或偏硼酸钠中的任一种或它们的混合物。As a further optimization of the technical solution disclosed in the present invention, the borate is preferably any one of borax or sodium metaborate or a mixture thereof.
作为本发明所公开技术方案的进一步优化，胺盐优选为己基苄基胺盐、双环己胺盐、双叔丁氧羰酰基组氨酸二环己胺盐、二甲胺盐酸盐、三乙醇胺、吡罗克酮乙醇胺盐中的任一种或它们的混合物。As a further optimization of the technical solution disclosed in the present invention, the amine salt is preferably hexylbenzylamine salt, dicyclohexylamine salt, bis-tert-butoxycarbonylhistidine dicyclohexylamine salt, dimethylamine hydrochloride, and triethanolamine , any one of piroctone ethanolamine salts or their mixtures.
作为本发明所公开技术方案的进一步优化，季铵盐优选为十二烷基硫酸钠、十二烷基三甲基溴化铵、十二烷基醇醚硫酸铵中的任一种或它们的混合物。As a further optimization of the technical solution disclosed in the present invention, the quaternary ammonium salt is preferably any one of sodium lauryl sulfate, dodecyl trimethyl ammonium bromide, ammonium lauryl alcohol ether sulfate or their combinations. mixture.
作为本发明所公开技术方案的进一步优化，磷酸盐优选为磷酸二铵、六偏磷酸钠、磷酸氢二钠中的任一种或它们的混合物。As a further optimization of the technical solution disclosed in the present invention, the phosphate is preferably any one of diammonium phosphate, sodium hexametaphosphate, disodium hydrogen phosphate or a mixture thereof.
作为本发明所公开技术方案的进一步优化，氧化性酸优选为硝酸、 高锰酸、次氯酸中的任一项，且以重量计混酸比例为：磷酸：氧化性酸＝2：1。As a further optimization of the technical solution disclosed in the present invention, the oxidizing acid is preferably nitric acid, Either permanganic acid or hypochlorous acid, and the mixed acid ratio by weight is: phosphoric acid: oxidizing acid = 2:1.
在实际工业应用中，汽车电子用高比容低压电极箔的制备方法至少取得了以下几方面的有益效果：In actual industrial applications, the preparation method of high specific volume low-voltage electrode foil for automotive electronics has achieved at least the following beneficial effects:
1)无论是一级化成阶段，抑或是二级化成、二级化成、四级化成阶段，均通过向着化成槽液中施加恒定密度的电流，以确保氧化膜在腐蚀箔表面得以稳定、快速生成，且不同区域内所成型孔道的分布形态更为均衡；1) Whether it is the first-stage formation stage, or the second-stage formation stage, the second-stage formation stage, or the fourth-stage formation stage, a constant density of current is applied to the formation bath liquid to ensure that the oxide film is stably and rapidly formed on the surface of the corroded foil. , and the distribution shape of the formed channels in different areas is more balanced;
2)针对每次化成步骤，通过所用电压、温度、时间以及所用化成液组分、配比进行调整，以使得成型氧化膜其各分层致密度趋于一致，进而利于提升电极箔的水煮寿命；2) For each formation step, the voltage, temperature, time, and composition and ratio of the formation liquid used are adjusted so that the density of each layer of the formed oxide film becomes consistent, which is beneficial to improving the boiling properties of the electrode foil. life;
3)在步骤S21中，一级化成时加入胺类处理液，可提高氧化膜中3) In step S21, adding amine treatment liquid during the first-level formation can improve the concentration of the oxide film.
γ`或γ-Al2O3的含量。究其原因在于，在弱碱性环境下，腐蚀箔的微孔表面会形成一水合软铝石沉积膜，通过后续高温处理后势必分解生成γ`或γ-Al2O3；γ` or γ-Al 2 O 3 content. The reason is that in a weakly alkaline environment, a monohydrate boehmite deposition film will form on the microporous surface of the corroded foil, which will inevitably decompose to generate γ` or γ-Al 2 O 3 after subsequent high-temperature treatment;
4)在后处理阶段，利于对化成中的氧化膜上所形成的瑕疵点(经过酸浸泡或高温处理过后露出来)进行修补，利于提升其水煮寿命。4) In the post-processing stage, it is helpful to repair the defects formed on the oxide film during the formation (exposed after acid soaking or high temperature treatment), which is helpful to extend its boiling life.
附图说明Description of the drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are only These are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without exerting creative efforts.
图1是采用背景技术中所述常规多级化成所制备成型电极箔的金相照片。Figure 1 is a metallographic photograph of a shaped electrode foil prepared by conventional multi-stage formation as described in the background art.
图2是采用实施例1中方法所制备成型电极箔的金相照片。Figure 2 is a metallographic photograph of the shaped electrode foil prepared by the method in Example 1.
图3是采用实施例2中方法所制备成型电极箔的金相照片。 Figure 3 is a metallographic photograph of the shaped electrode foil prepared by the method in Example 2.
图4是采用实施例3中方法所制备成型电极箔的金相照片。Figure 4 is a metallographic photograph of the shaped electrode foil prepared by the method in Example 3.
图5是采用实施例4中方法所制备成型电极箔的金相照片。Figure 5 is a metallographic photograph of the shaped electrode foil prepared by the method in Example 4.
具体实施方式Detailed ways
为了加深对本发明的理解，下面将结合实施例对本发明作进一步详述，该实施例仅用于解释本发明，并不构成对本发明保护范围的限定。所述方法无特别说明的均为常规方法。In order to deepen the understanding of the present invention, the present invention will be further described in detail below with reference to examples. The examples are only used to explain the present invention and do not constitute a limitation on the scope of protection of the present invention. The methods are conventional methods unless otherwise specified.
对比例1Comparative example 1
参照前文背景技术中所公开多级化成法来制备电极箔。The electrode foil is prepared with reference to the multi-stage formation method disclosed in the background art above.
实施例1Example 1
汽车电子用高比容低压电极箔的制备方法，其包括以下步骤：A method for preparing high specific volume low voltage electrode foil for automotive electronics, which includes the following steps:
S1、腐蚀箔的制备：取纯度不低于99.9％，且厚度为100μm的铝箔浸入酸液中，对其表面进行腐蚀；S1. Preparation of corroded foil: Dip aluminum foil with a purity of not less than 99.9% and a thickness of 100 μm into the acid solution and corrode its surface;
S2、多级化成，包括以下子步骤：S2. Multi-level formation, including the following sub-steps:
S21、一级化成：将步骤S1中所得腐蚀箔浸于温度控制在65～85℃、含有5wt％硫酸铵、1wt％偏硼酸钠、0.5wt％己基苄基胺盐的混合溶液中，20～160V电压下进行化成，且时长控制在10min，制成一级化成箔；S21. First-level formation: Immerse the corroded foil obtained in step S1 into a mixed solution containing 5wt% ammonium sulfate, 1wt% sodium metaborate, and 0.5wt% hexyl benzylamine salt, controlled at a temperature of 65 to 85°C, for 20 to The formation is carried out at a voltage of 160V and the time is controlled at 10 minutes to produce a first-level formation foil;
S22、表面清洁：对步骤S21中所得一级化成箔执行水洗、且风干操作(风干温度不超过20℃)；S22. Surface cleaning: perform water washing and air-drying operations on the primary chemical foil obtained in step S21 (the air-drying temperature does not exceed 20°C);
S23、二级化成：将经步骤S22处理后的一级化成箔浸于温度控制在65～85℃、含有3wt％硫酸铵、1wt％偏硼酸钠的混合溶液中，20～160V电压下进行化成，且时长宜控制在10min，制成二级化成箔；S23. Secondary formation: Dip the primary formation foil processed in step S22 into a mixed solution containing 3wt% ammonium sulfate and 1wt% sodium metaborate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V. , and the duration should be controlled at 10 minutes to make a secondary formation foil;
S24、三级化成：将步骤S23中所得二级化成箔浸于温度控制在65～85℃、含有3wt％硫酸铵、1wt％偏硼酸钠的混合溶液中，20～160V电压下进行化成，且时长控制在15min，制成三级化成箔；S24. Tertiary formation: Dip the secondary formation foil obtained in step S23 into a mixed solution containing 3wt% ammonium sulfate and 1wt% sodium metaborate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V, and The time is controlled at 15 minutes to make a three-stage chemical foil;
S25、表面清洁：对步骤S24中所得三级化成箔执行水洗、且风干操 作；S25. Surface cleaning: wash and air-dry the tertiary formation foil obtained in step S24. do;
S26、中间处理：将经步骤S25处理后的三级化成箔浸于温度控制在40～60℃、5wt％的十二烷基硫酸钠水溶液中，且时长控制在10min；S26. Intermediate treatment: Dip the tertiary chemical foil processed in step S25 into a 5wt% sodium dodecyl sulfate aqueous solution with a temperature controlled at 40-60°C, and the duration is controlled at 10 minutes;
S27、四级化成：将步骤S26中所得三级化成箔浸于温度控制在65～85℃、含有5wt％六偏磷酸钠的溶液中，20～160V电压下进行化成，且时长控制在20min，制成四级化成箔；S27. Four-stage formation: Dip the three-stage formation foil obtained in step S26 into a solution containing 5wt% sodium hexametaphosphate and controlled at a temperature of 65 to 85°C. The formation is carried out at a voltage of 20 to 160V, and the duration is controlled to 20 minutes. Made into quaternary formation foil;
S3、后处理，包括以下子步骤：S3, post-processing, including the following sub-steps:
S31、一级后处理：将步骤S27中所得四级化成箔浸于温度控制在65～85℃、1wt％的六偏磷酸钠水溶液中，施加20～160V电压，且时长控制在15min，制成一级处理箔；S31. First-level post-processing: Dip the fourth-level chemical foil obtained in step S27 into a 1wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the time to 15 minutes to prepare Primary treatment foil;
S32、表面清洁：对步骤S31中所得一级处理箔执行水洗、且风干操作；S32. Surface cleaning: perform water washing and air drying operations on the primary treated foil obtained in step S31;
S33、浸酸处理：将经步骤S32处理后的一级处理箔浸于含有7wt％磷酸:高氯酸为1:1的酸性混合溶液中，且时长控制在6min；S33. Acid dipping treatment: Dip the first-level treated foil treated in step S32 into an acidic mixed solution containing 7wt% phosphoric acid:perchloric acid in a ratio of 1:1, and the duration is controlled to 6 minutes;
S34、热处理：对步骤S33中所得一级处理箔执行水洗、烘干操作，且烘干温度控制在450～500℃，时长控制在1.5min；S34. Heat treatment: perform water washing and drying operations on the first-level treated foil obtained in step S33, and the drying temperature is controlled at 450~500°C, and the drying time is controlled at 1.5 minutes;
S35、二级后处理：将步骤S34中所得一级处理箔浸于温度控制在65～85℃、1wt％的六偏磷酸钠水溶液中，施加20～160V电压，且时长控制在10min，制成二级处理箔；S35. Secondary post-processing: Dip the primary-processed foil obtained in step S34 into a 1wt% sodium hexametaphosphate aqueous solution controlled at a temperature of 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 10 minutes to prepare secondary treatment foil;
S36、三级后处理：将步骤S35中所得二级处理箔浸于温度控制在65～85℃、1wt％的六偏磷酸钠水溶液中，施加20～160V电压，且时长控制在10min，制成三级处理箔；S36. Third-level post-processing: Dip the secondary-processed foil obtained in step S35 into a 1wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 10 minutes to prepare Tertiary treated foil;
S37、表面清洁：对步骤S36中所得三级处理箔执行水洗、且风干操作，即得到高比容低压电极箔。S37. Surface cleaning: Wash and air-dry the three-level treated foil obtained in step S36 to obtain a high specific volume low-voltage electrode foil.
实施例2Example 2
汽车电子用高比容低压电极箔的制备方法，其包括以下步骤：A method for preparing high specific volume low voltage electrode foil for automotive electronics, which includes the following steps:
S1、腐蚀箔的制备：取纯度不低于99.9％，且厚度为100μm的铝箔 浸入酸液中，对其表面进行腐蚀；S1. Preparation of etched foil: Take aluminum foil with a purity of not less than 99.9% and a thickness of 100 μm. Immersed in acid to corrode its surface;
S2、多级化成，包括以下子步骤：S2. Multi-level formation, including the following sub-steps:
S21、一级化成：将步骤S1中所得腐蚀箔浸于温度控制在65～85℃、含有8wt％硫酸铵、1.5wt％偏硼酸钠、0.7wt％己基苄基胺盐的混合溶液中，20～160V电压下进行化成，且时长控制在10min，制成一级化成箔；S21. First-level formation: immerse the corroded foil obtained in step S1 into a mixed solution containing 8wt% ammonium sulfate, 1.5wt% sodium metaborate, and 0.7wt% hexyl benzylamine salt at a temperature of 65 to 85°C, 20 The formation is carried out at a voltage of ~160V, and the time is controlled at 10 minutes, to produce a first-level formation foil;
S22、表面清洁：对步骤S21中所得一级化成箔执行水洗、且风干操作(风干温度不超过20℃)；S22. Surface cleaning: perform water washing and air-drying operations on the primary chemical foil obtained in step S21 (the air-drying temperature does not exceed 20°C);
S23、二级化成：将经步骤S22处理后的一级化成箔浸于温度控制在65～85℃、含有5wt％硫酸铵、1.5wt％偏硼酸钠的混合溶液中，20～160V电压下进行化成，且时长宜控制在10min，制成二级化成箔；S23. Secondary formation: Dip the primary formation foil processed in step S22 into a mixed solution containing 5wt% ammonium sulfate and 1.5wt% sodium metaborate, controlled at a temperature of 65 to 85°C, and carried out at a voltage of 20 to 160V. Formation, and the time should be controlled within 10 minutes, to produce a secondary formation foil;
S24、三级化成：将步骤S23中所得二级化成箔浸于温度控制在65～85℃、含有4wt％硫酸铵、1.5wt％偏硼酸钠的混合溶液中，20～160V电压下进行化成，且时长控制在15min，制成三级化成箔；S24. Tertiary formation: Dip the secondary formation foil obtained in step S23 into a mixed solution containing 4wt% ammonium sulfate and 1.5wt% sodium metaborate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V. And the time is controlled at 15 minutes to make a three-stage chemical foil;
S25、表面清洁：对步骤S24中所得三级化成箔执行水洗、且风干操作；S25. Surface cleaning: perform water washing and air-drying operations on the tertiary formation foil obtained in step S24;
S26、中间处理：将经步骤S25处理后的三级化成箔浸于温度控制在40～60℃、8wt％的十二烷基硫酸钠水溶液中，且时长控制在10min；S26. Intermediate treatment: Dip the tertiary chemical foil processed in step S25 into an 8wt% sodium dodecyl sulfate aqueous solution with a temperature controlled at 40-60°C, and the duration is controlled at 10 minutes;
S27、四级化成：将步骤S26中所得三级化成箔浸于温度控制在65～85℃、含有6wt％六偏磷酸钠的溶液中，20～160V电压下进行化成，且时长控制在20min，制成四级化成箔；S27. Four-stage formation: Dip the three-stage formation foil obtained in step S26 into a solution containing 6wt% sodium hexametaphosphate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V, and the duration is controlled at 20 minutes. Made into quaternary formation foil;
S3、后处理，包括以下子步骤：S3, post-processing, including the following sub-steps:
S31、一级后处理：将步骤S27中所得四级化成箔浸于温度控制在65～85℃、3wt％的六偏磷酸钠水溶液中，施加20～160V电压，且时长控制在15min，制成一级处理箔；S31. First-level post-processing: Dip the fourth-level chemical foil obtained in step S27 into a 3wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the time to 15 minutes to prepare Primary treatment foil;
S32、表面清洁：对步骤S31中所得一级处理箔执行水洗、且风干操作；S32. Surface cleaning: perform water washing and air drying operations on the primary treated foil obtained in step S31;
S33、浸酸处理：将经步骤S32处理后的一级处理箔浸于含有8wt％磷酸:高氯酸为1:1的酸性混合溶液中，且时长控制在6min； S33. Pickling treatment: Dip the first-level treated foil treated in step S32 into an acidic mixed solution containing 8wt% phosphoric acid:perchloric acid in a ratio of 1:1, and the time is controlled to 6 minutes;
S34、热处理：对步骤S33中所得一级处理箔执行水洗、烘干操作，且烘干温度控制在450～500℃，时长控制在1.5min；S34. Heat treatment: perform water washing and drying operations on the first-level treated foil obtained in step S33, and the drying temperature is controlled at 450~500°C, and the drying time is controlled at 1.5 minutes;
S35、二级后处理：将步骤S34中所得一级处理箔浸于温度控制在65～85℃、3wt％的六偏磷酸钠水溶液中，施加20～160V电压，且时长控制在10min，制成二级处理箔；S35. Secondary post-processing: Dip the primary-processed foil obtained in step S34 into a 3wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 10 minutes to prepare secondary treatment foil;
S36、三级后处理：将步骤S35中所得二级处理箔浸于温度控制在65～85℃、3wt％的六偏磷酸钠水溶液中，施加20～160V电压，且时长控制在10min，制成三级处理箔；S36. Third-level post-processing: Dip the secondary-processed foil obtained in step S35 into a 3wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 10 minutes to prepare Tertiary treated foil;
S37、表面清洁：对步骤S36中所得三级处理箔执行水洗、且风干操作，即得到高比容低压电极箔。S37. Surface cleaning: Wash and air-dry the three-level treated foil obtained in step S36 to obtain a high specific volume low-voltage electrode foil.
实施例3Example 3
汽车电子用高比容低压电极箔的制备方法，其包括以下步骤：A method for preparing high specific volume low voltage electrode foil for automotive electronics, which includes the following steps:
S1、腐蚀箔的制备：取纯度不低于99.9％，且厚度为100μm的铝箔浸入酸液中，对其表面进行腐蚀；S1. Preparation of corroded foil: Dip aluminum foil with a purity of not less than 99.9% and a thickness of 100 μm into the acid solution and corrode its surface;
S2、多级化成，包括以下子步骤：S2. Multi-level formation, including the following sub-steps:
S21、一级化成：将步骤S1中所得腐蚀箔浸于温度控制在65～85℃、含有10wt％硫酸铵、2wt％偏硼酸钠、1wt％己基苄基胺盐的混合溶液中，20～160V电压下进行化成，且时长控制在10min，制成一级化成箔；S21. First-level formation: immerse the corroded foil obtained in step S1 into a mixed solution containing 10wt% ammonium sulfate, 2wt% sodium metaborate, and 1wt% hexyl benzylamine salt at a temperature of 65 to 85°C, 20 to 160V Carry out formation under voltage and control the time to 10 minutes to make a first-level formation foil;
S22、表面清洁：对步骤S21中所得一级化成箔执行水洗、且风干操作(风干温度不超过20℃)；S22. Surface cleaning: perform water washing and air-drying operations on the primary chemical foil obtained in step S21 (the air-drying temperature does not exceed 20°C);
S23、二级化成：将经步骤S22处理后的一级化成箔浸于温度控制在65～85℃、含有7wt％硫酸铵、2wt％偏硼酸钠的混合溶液中，20～160V电压下进行化成，且时长宜控制在10min，制成二级化成箔；S23. Secondary formation: Dip the primary formation foil processed in step S22 into a mixed solution containing 7wt% ammonium sulfate and 2wt% sodium metaborate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V. , and the duration should be controlled at 10 minutes to make a secondary formation foil;
S24、三级化成：将步骤S23中所得二级化成箔浸于温度控制在65～85℃、含有5wt％硫酸铵、2wt％偏硼酸钠的混合溶液中，20～160V电压下进行化成，且时长控制在15min，制成三级化成箔；S24. Tertiary formation: Dip the secondary formation foil obtained in step S23 into a mixed solution containing 5wt% ammonium sulfate and 2wt% sodium metaborate and controlled at a temperature of 65 to 85°C. The formation is carried out at a voltage of 20 to 160V, and The time is controlled at 15 minutes to make a three-stage chemical foil;
S25、表面清洁：对步骤S24中所得三级化成箔执行水洗、且风干操 作；S25. Surface cleaning: wash and air-dry the tertiary formation foil obtained in step S24. do;
S26、中间处理：将经步骤S25处理后的三级化成箔浸于温度控制在40～60℃、10wt％的十二烷基硫酸钠水溶液中，且时长控制在10min；S26. Intermediate treatment: Dip the tertiary chemical foil processed in step S25 into a 10wt% sodium dodecyl sulfate aqueous solution with a temperature controlled at 40-60°C, and the duration is controlled at 10 minutes;
S27、四级化成：将步骤S26中所得三级化成箔浸于温度控制在65～85℃、含有7wt％六偏磷酸钠的溶液中，20～160V电压下进行化成，且时长控制在20min，制成四级化成箔；S27. Four-stage formation: Dip the three-stage formation foil obtained in step S26 into a solution containing 7wt% sodium hexametaphosphate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V, and the duration is controlled at 20 minutes. Made into quaternary formation foil;
S3、后处理，包括以下子步骤：S3, post-processing, including the following sub-steps:
S31、一级后处理：将步骤S27中所得四级化成箔浸于温度控制在65～85℃、5wt％的六偏磷酸钠水溶液中，施加20～160V电压，且时长控制在15min，制成一级处理箔；S31. First-level post-processing: Dip the fourth-level chemical foil obtained in step S27 into a 5wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the time to 15 minutes to prepare Primary treatment foil;
S32、表面清洁：对步骤S31中所得一级处理箔执行水洗、且风干操作；S32. Surface cleaning: perform water washing and air drying operations on the primary treated foil obtained in step S31;
S33、浸酸处理：将经步骤S32处理后的一级处理箔浸于含有10wt％磷酸:高氯酸为1:1的酸性混合溶液中，且时长控制在6min；S33. Acid dipping treatment: Dip the first-level treated foil treated in step S32 into an acidic mixed solution containing 10wt% phosphoric acid: perchloric acid in a ratio of 1:1, and the duration is controlled to 6 minutes;
S34、热处理：对步骤S33中所得一级处理箔执行水洗、烘干操作，且烘干温度控制在450～500℃，时长控制在1.5min；S34. Heat treatment: perform water washing and drying operations on the first-level treated foil obtained in step S33, and the drying temperature is controlled at 450~500°C, and the drying time is controlled at 1.5 minutes;
S35、二级后处理：将步骤S34中所得一级处理箔浸于温度控制在65～85℃、5wt％的六偏磷酸钠水溶液中，施加20～160V电压，且时长控制在10min，制成二级处理箔；S35. Secondary post-processing: Dip the primary-processed foil obtained in step S34 into a 5wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 10 minutes to prepare secondary treatment foil;
S36、三级后处理：将步骤S35中所得二级处理箔浸于温度控制在65～85℃、5wt％的六偏磷酸钠水溶液中，施加20～160V电压，且时长控制在10min，制成三级处理箔；S36. Third-level post-processing: Dip the secondary-processed foil obtained in step S35 into a 5wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 10 minutes to prepare Tertiary treated foil;
S37、表面清洁：对步骤S36中所得三级处理箔执行水洗、且风干操作，即得到高比容低压电极箔。S37. Surface cleaning: Wash and air-dry the three-level treated foil obtained in step S36 to obtain a high specific volume low-voltage electrode foil.
实施例4Example 4
汽车电子用高比容低压电极箔的制备方法，其包括以下步骤：A method for preparing high specific volume low voltage electrode foil for automotive electronics, which includes the following steps:
S1、腐蚀箔的制备：取纯度不低于99.9％，且厚度为100μm的铝箔 浸入酸液中，对其表面进行腐蚀；S1. Preparation of etched foil: Take aluminum foil with a purity of not less than 99.9% and a thickness of 100 μm. Immersed in acid to corrode its surface;
S2、多级化成，包括以下子步骤：S2. Multi-level synthesis, including the following sub-steps:
S21、一级化成：将步骤S1中所得腐蚀箔浸于温度控制在65～85℃、含有5wt％硫酸铵、1wt％偏硼酸钠、0.5wt％己基苄基胺盐的混合溶液中，20～160V电压下进行化成，且时长控制在5min，制成一级化成箔；S21. First-level formation: Immerse the corroded foil obtained in step S1 into a mixed solution containing 5wt% ammonium sulfate, 1wt% sodium metaborate, and 0.5wt% hexyl benzylamine salt, controlled at a temperature of 65 to 85°C, for 20 to The formation is carried out at a voltage of 160V and the time is controlled at 5 minutes to produce a first-level formation foil;
S22、表面清洁：对步骤S21中所得一级化成箔执行水洗、且风干操作(风干温度不超过20℃)；S22. Surface cleaning: perform water washing and air-drying operations on the primary chemical foil obtained in step S21 (the air-drying temperature does not exceed 20°C);
S23、二级化成：将经步骤S22处理后的一级化成箔浸于温度控制在65～85℃、含有3wt％硫酸铵、1wt％偏硼酸钠的混合溶液中，20～160V电压下进行化成，且时长宜控制在5min，制成二级化成箔；S23. Secondary formation: Dip the primary formation foil processed in step S22 into a mixed solution containing 3wt% ammonium sulfate and 1wt% sodium metaborate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V. , and the time should be controlled at 5 minutes to make a secondary formation foil;
S24、三级化成：将步骤S23中所得二级化成箔浸于温度控制在65～85℃、含有3wt％硫酸铵、1wt％偏硼酸钠的混合溶液中，20～160V电压下进行化成，且时长控制在7min，制成三级化成箔；S24. Tertiary formation: Dip the secondary formation foil obtained in step S23 into a mixed solution containing 3wt% ammonium sulfate and 1wt% sodium metaborate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V, and The time is controlled at 7 minutes to produce a three-stage chemical foil;
S25、表面清洁：对步骤S24中所得三级化成箔执行水洗、且风干操作；S25. Surface cleaning: perform water washing and air-drying operations on the tertiary formation foil obtained in step S24;
S26、中间处理：将经步骤S25处理后的三级化成箔浸于温度控制在40～60℃、5wt％的十二烷基硫酸钠水溶液中，且时长控制在10min；S26. Intermediate treatment: Dip the tertiary chemical foil processed in step S25 into a 5wt% sodium dodecyl sulfate aqueous solution with a temperature controlled at 40-60°C, and the duration is controlled at 10 minutes;
S27、四级化成：将步骤S26中所得三级化成箔浸于温度控制在65～85℃、含有5wt％六偏磷酸钠的溶液中，20～160V电压下进行化成，且时长控制在15min，制成四级化成箔；S27. Four-stage formation: Dip the three-stage formation foil obtained in step S26 into a solution containing 5wt% sodium hexametaphosphate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V, and the duration is controlled at 15 minutes. Made into quaternary formation foil;
S3、后处理，包括以下子步骤：S3, post-processing, including the following sub-steps:
S31、一级后处理：将步骤S27中所得四级化成箔浸于温度控制在65～85℃、1wt％的六偏磷酸钠水溶液中，施加20～160V电压，且时长控制在10min，制成一级处理箔；S31. First-level post-processing: Dip the fourth-level chemical foil obtained in step S27 into a 1wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the time to 10 minutes to prepare Primary treatment foil;
S32、表面清洁：对步骤S31中所得一级处理箔执行水洗、且风干操作；S32. Surface cleaning: perform water washing and air drying operations on the primary treated foil obtained in step S31;
S33、浸酸处理：将经步骤S32处理后的一级处理箔浸于含有7wt％磷酸:高氯酸为1:1的酸性混合溶液中，且时长控制在6min； S33. Acid dipping treatment: Dip the first-level treated foil treated in step S32 into an acidic mixed solution containing 7wt% phosphoric acid:perchloric acid in a ratio of 1:1, and the duration is controlled to 6 minutes;
S34、热处理：对步骤S33中所得一级处理箔执行水洗、烘干操作，且烘干温度控制在450～500℃，时长控制在1.5min；S34. Heat treatment: perform water washing and drying operations on the first-level treated foil obtained in step S33, and the drying temperature is controlled at 450~500°C, and the drying time is controlled at 1.5 minutes;
S35、二级后处理：将步骤S34中所得一级处理箔浸于温度控制在65～85℃、1wt％的六偏磷酸钠水溶液中，施加20～160V电压，且时长控制在5min，制成二级处理箔；S35. Secondary post-processing: Dip the primary-processed foil obtained in step S34 into a 1wt% sodium hexametaphosphate aqueous solution with a temperature controlled at 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 5 minutes to prepare secondary treatment foil;
S36、三级后处理：将步骤S35中所得二级处理箔浸于温度控制在65～85℃、1wt％的六偏磷酸钠水溶液中，施加20～160V电压，且时长控制在5min，制成三级处理箔；S36. Third-level post-processing: Dip the secondary-processed foil obtained in step S35 into a 1wt% sodium hexametaphosphate aqueous solution controlled at a temperature of 65 to 85°C, apply a voltage of 20 to 160V, and control the duration to 5 minutes to prepare Tertiary treated foil;
S37、表面清洁：对步骤S36中所得三级处理箔执行水洗、且风干操作，即得到高比容低压电极箔。S37. Surface cleaning: Wash and air-dry the three-level treated foil obtained in step S36 to obtain a high specific volume low-voltage electrode foil.
经过将附图1与附图2、3、4、5对比分析可知，所制备电极箔的孔隙率有大幅度提升，平均粒径更小，且分布形态更为均匀，利于电极箔电性能指标的进一步提升。且经过具体实验结果论证，电极箔的耐压性能和电容量得到有效提升，而水煮升压时间明显缩短(具体性能测试数据如表1中所示)。Comparative analysis of Figure 1 and Figures 2, 3, 4 and 5 shows that the porosity of the prepared electrode foil has been greatly improved, the average particle size is smaller, and the distribution shape is more uniform, which is beneficial to the electrical performance of the electrode foil. further improvement. And through specific experimental results, the voltage resistance and capacitance of the electrode foil have been effectively improved, and the boiling pressure rise time has been significantly shortened (specific performance test data are shown in Table 1).
表1是对比例以及实施例1～4得到的电极箔的性能测试结果汇总
Table 1 is a summary of the performance test results of the electrode foils obtained in Comparative Examples and Examples 1 to 4.
Vfe-对未化成箔形成处理时，所加的最终电压；Vfe - the final voltage applied during the forming process of the unformed foil;
Vt-化成箔的耐压值； Vt - the withstand voltage value of the formed foil;
究其原因在于：The reason is:
1)无论是一级化成阶段，抑或是二级化成、二级化成、四级化成阶段，均通过向着化成槽液中施加恒定密度的电流，以确保氧化膜在腐蚀箔表面得以稳定、快速生成，且不同区域内所成型孔道的分布形态更为均衡；1) Whether it is the first-stage formation stage, or the second-stage formation stage, the second-stage formation stage, or the fourth-stage formation stage, a constant density of current is applied to the formation bath liquid to ensure that the oxide film is stably and rapidly formed on the surface of the corroded foil. , and the distribution shape of the formed channels in different areas is more balanced;
2)针对每次化成步骤，通过所用电压、温度、时间以及所用化成液组分、配比进行调整，以使得成型氧化膜其各分层致密度趋于一致，进而利于提升电极箔的水煮寿命；2) For each formation step, the voltage, temperature, time, and composition and ratio of the formation liquid used are adjusted so that the density of each layer of the formed oxide film becomes consistent, which is beneficial to improving the boiling properties of the electrode foil. life;
3)在步骤S21中，一级化成时加入胺类处理液，可提高氧化膜中3) In step S21, adding amine treatment liquid during the first-level formation can improve the concentration of the oxide film.
γ`或γ-Al2O3的含量。究其原因在于，在弱碱性环境下，腐蚀箔的微孔表面会形成一水合软铝石沉积膜，通过后续高温处理后势必分解生成γ`或γ-Al2O3；γ` or γ-Al 2 O 3 content. The reason is that in a weakly alkaline environment, a monohydrate boehmite deposition film will form on the microporous surface of the corroded foil, which will inevitably decompose to generate γ` or γ-Al 2 O 3 after subsequent high-temperature treatment;
在此，需要着重说明的是，在后处理阶段，可以有效、充分地对化成中的氧化膜上所形成的瑕疵点(经过酸浸泡或高温处理过后露出来)进行修补，且还可大幅度提升铝电极箔的电比容。Here, it is important to note that in the post-processing stage, defects formed on the oxide film during chemical formation (exposed after acid immersion or high-temperature treatment) can be effectively and fully repaired, and can also be significantly improved. Improve the specific capacitance of aluminum electrode foil.
原理简述如下：后处理阶段，在酸处理时：The principle is briefly described as follows: post-treatment stage, during acid treatment:
阳极Al→Al3++3e- Anode Al→Al 3+ +3e -
阴极2H++2e→H2 Cathode 2H + +2e→H 2
由于强氧化性酸的存在，阴极为
Due to the presence of strong oxidizing acid, the cathode is
在两相界面上，由于酸度降低，发生Al3+、Mn2+的磷酸盐膜沉积同时产生一水合软铝石结构沉积，以实现对电极箔表面的修复；

At the two-phase interface, due to the decrease in acidity, phosphate films of Al 3+ and Mn 2+ are deposited and a monohydrate boehmite structure is deposited to repair the electrode foil surface;

Al3++2H2O→AlO(OH)+3H+ Al 3+ +2H 2 O→AlO(OH)+3H +
所形成的化学转化膜即使不经过高温处理在其底层仍有γ'或γ -Al2O3成份，提高了氧化膜中氧化铝结晶含量。由于结晶形Al2O3的介电常数高于无定形Al2O3，因此有效地提高了介质膜中结晶型Al2O3的含量，为铝电极箔电比容的大幅度提升了作良好的铺垫。Even if the chemical conversion coating is not subjected to high temperature treatment, there will still be γ' or γ in the bottom layer. -Al 2 O 3 component increases the aluminum oxide crystal content in the oxide film. Since the dielectric constant of crystalline Al 2 O 3 is higher than that of amorphous Al 2 O 3 , the content of crystalline Al 2 O 3 in the dielectric film is effectively increased, which plays a role in greatly increasing the specific capacitance of the aluminum electrode foil. Good foreshadowing.
最后，需要说明的是以下几点：Finally, the following points need to be explained:
1)在腐蚀箔执行化成处理中，除了选用上述实施例中所公开的偏硼酸钠，亦可以根据实际情况择优选择硼砂等硼酸盐以及偏硼酸钠和硼砂的混合物；1) During the chemical formation treatment of the etched foil, in addition to the sodium metaborate disclosed in the above embodiments, borates such as borax and a mixture of sodium metaborate and borax can also be selected according to the actual situation;
2)在腐蚀箔执行化成处理中，除了选用上述实施例中所公开的己基苄基胺盐，亦可以根据实际情况择优选择双环己胺盐、双叔丁氧羰酰基组氨酸二环己胺盐、二甲胺盐酸盐、三乙醇胺、吡罗克酮乙醇胺盐等胺盐中的任一种或它们的混合物；2) During the chemical conversion treatment of the etched foil, in addition to the hexylbenzylamine salt disclosed in the above embodiments, dicyclohexylamine salt or dicyclohexylamine salt or di-tert-butoxycarbonyl histidine dicyclohexylamine can also be selected according to the actual situation. Any one of amine salts such as dimethylamine hydrochloride, triethanolamine, piroctone ethanolamine salt, or mixtures thereof;
3)在腐蚀箔执行化成处理中，除了选用上述实施例中所公开的十二烷基硫酸钠，亦可以根据实际情况择优选择十二烷基三甲基溴化铵、十二烷基醇醚硫酸铵等季铵盐中的任一种或它们的混合物；3) During the chemical conversion treatment of the etched foil, in addition to the sodium lauryl sulfate disclosed in the above embodiments, dodecyltrimethylammonium bromide and lauryl alcohol ether can also be selected according to the actual situation. Any one of quaternary ammonium salts such as ammonium sulfate or their mixture;
4)在对化成箔执行后处理进程中，除了选用上述实施例中所公开的六偏磷酸钠，亦可以根据实际情况择优选择磷酸二铵、磷酸氢二钠等磷酸盐中的任一种或它们的混合物。4) During the post-processing process of the chemical foil, in addition to the sodium hexametaphosphate disclosed in the above embodiments, any one of the phosphates such as diammonium phosphate, disodium hydrogen phosphate or the like can also be selected according to the actual situation. Their mixture.
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。 The above description of the disclosed embodiments enables those skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be practiced in other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (6)

  1. 一种汽车电子用高比容低压电极箔的制备方法，其特征在于，包括以下步骤：A method for preparing high specific volume low voltage electrode foil for automotive electronics, which is characterized by including the following steps:
    S1、腐蚀箔的制备：取纯度不低于99.9％的铝箔浸入酸液中，对其表面进行腐蚀；S1. Preparation of corroded foil: Dip aluminum foil with a purity of not less than 99.9% into acid solution and corrode its surface;
    S2、多级化成，包括以下子步骤：S2. Multi-level synthesis, including the following sub-steps:
    S21、一级化成：将步骤S1中所得腐蚀箔浸于温度控制在65～85℃、含有5～10wt％硫酸铵、1～2wt％硼酸盐、0.5～1wt％胺盐的混合溶液中，20～160V电压下进行化成，且时长控制在5～10min，制成一级化成箔；S21. First-level formation: immerse the corroded foil obtained in step S1 into a mixed solution containing 5-10wt% ammonium sulfate, 1-2wt% borate, and 0.5-1wt% amine salt, controlled at a temperature of 65-85°C. The formation is carried out at a voltage of 20 to 160V, and the time is controlled between 5 and 10 minutes, to produce a first-level formation foil;
    S22、表面清洁：对步骤S21中所得一级化成箔执行水洗、且风干操作；S22. Surface cleaning: perform water washing and air drying operations on the primary formed foil obtained in step S21;
    S23、二级化成：将经步骤S22处理后的一级化成箔浸于温度控制在65～85℃、含有3～7wt％硫酸铵、1～2wt％硼酸盐的混合溶液中，20～160V电压下进行化成，且时长控制在5～10min，制成二级化成箔；S23. Secondary formation: Dip the primary formation foil processed in step S22 into a mixed solution containing 3-7wt% ammonium sulfate and 1-2wt% borate at a temperature controlled at 65-85°C, 20-160V The formation is carried out under voltage and the time is controlled between 5 and 10 minutes to produce a secondary formation foil;
    S24、三级化成：将步骤S23中所得二级化成箔浸于温度控制在65～85℃、含有3～5wt％硫酸铵、1～2wt％硼酸盐的混合溶液中，20～160V电压下进行化成，且时长控制在7～15min，制成三级化成箔；S24. Tertiary formation: Dip the secondary formation foil obtained in step S23 into a mixed solution containing 3-5wt% ammonium sulfate and 1-2wt% borate at a temperature controlled at 65-85°C under a voltage of 20-160V. Carry out formation, and control the time between 7 and 15 minutes to make a three-stage formation foil;
    S25、表面清洁：对步骤S24中所得三级化成箔执行水洗、且风干操作；S25. Surface cleaning: perform water washing and air-drying operations on the tertiary formation foil obtained in step S24;
    S26、中间处理：将经步骤S25处理后的三级化成箔浸于温度控制在40～60℃、5～10wt％的季铵盐水溶液中，且时长控制在5～10min；S26. Intermediate treatment: Dip the tertiary chemical foil processed in step S25 into a quaternary ammonium salt solution with a temperature controlled at 40 to 60°C and 5 to 10 wt%, and the duration is controlled at 5 to 10 minutes;
    S27、四级化成：将步骤S26中所得三级化成箔浸于温度控制在65～85℃、含有5～7wt％磷酸盐的溶液中，20～160V电压下进行化成，且时长控制在15～20min，制成四级化成箔；S27. Four-stage formation: Dip the three-stage formation foil obtained in step S26 into a solution containing 5-7wt% phosphate at a temperature controlled at 65-85°C, and perform the formation at a voltage of 20-160V, and the duration is controlled at 15-15%. 20 minutes to make a fourth-stage chemical foil;
    S3、后处理，包括以下子步骤：S3, post-processing, including the following sub-steps:
    S31、一级后处理：将步骤S27中所得四级化成箔浸于温度控制在65～85℃、1～5wt％的磷酸盐水溶液中，施加20～160V电压，且时长控制在10～15min，制成一级处理箔；S31. First-level post-processing: Dip the fourth-level chemical foil obtained in step S27 into a phosphate aqueous solution with a temperature controlled at 65-85°C and 1-5wt%, apply a voltage of 20-160V, and control the duration at 10-15 minutes. Made into primary treated foil;
    S32、表面清洁：对步骤S31中所得一级处理箔执行水洗、且风干操 作；S32. Surface cleaning: perform water washing and air drying operations on the primary treated foil obtained in step S31. do;
    S33、浸酸处理：将经步骤S32处理后的一级处理箔浸于含有7～10wt％磷酸和氧化性酸的混合溶液中，且时长控制在5～10min；S33. Pickling treatment: Dip the first-level treated foil treated in step S32 into a mixed solution containing 7 to 10 wt% phosphoric acid and oxidizing acid, and the time is controlled to 5 to 10 minutes;
    S34、热处理：对步骤S33中所得一级处理箔执行水洗、烘干操作，且烘干温度控制在450～500℃，时长控制在1～2min；S34. Heat treatment: perform water washing and drying operations on the first-level treated foil obtained in step S33, and the drying temperature is controlled at 450~500°C, and the duration is controlled at 1~2 min;
    S35、二级后处理：将步骤S34中所得一级处理箔浸于温度控制在65～85℃、1～5wt％的磷酸盐水溶液中，施加20～160V电压，且时长控制在5～10min，制成二级处理箔；S35. Secondary post-processing: Dip the primary-processed foil obtained in step S34 into a phosphate aqueous solution with a temperature controlled at 65-85°C and 1-5wt%, apply a voltage of 20-160V, and control the duration at 5-10 minutes. Made into secondary treated foil;
    S36、三级后处理：将步骤S35中所得二级处理箔浸于温度控制在65～85℃、1～5wt％的磷酸盐水溶液中，施加20～160V电压，且时长控制在5～10min，制成三级处理箔；S36. Third-level post-processing: Dip the secondary-processed foil obtained in step S35 into a phosphate aqueous solution with a temperature controlled at 65 to 85°C and 1 to 5 wt%, apply a voltage of 20 to 160 V, and control the duration to 5 to 10 minutes. Made into tertiary treated foil;
    S37、表面清洁：对步骤S36中所得三级处理箔执行水洗、且风干操作，即得到高比容低压电极箔。S37. Surface cleaning: Wash and air-dry the three-level treated foil obtained in step S36 to obtain a high specific volume low-voltage electrode foil.
  2. 根据权利要求1所述汽车电子用高比容低压电极箔的制备方法，其特征在于，硼酸盐为硼砂或偏硼酸钠中的任一种或它们的混合物。The method for preparing high specific volume low-voltage electrode foil for automotive electronics according to claim 1, wherein the borate is any one of borax or sodium metaborate or a mixture thereof.
  3. 根据权利要求1所述汽车电子用高比容低压电极箔的制备方法，其特征在于，胺盐为己基苄基胺盐、双环己胺盐、双叔丁氧羰酰基组氨酸二环己胺盐、二甲胺盐酸盐、三乙醇胺、吡罗克酮乙醇胺盐中的任一种或它们的混合物。The preparation method of high specific volume low voltage electrode foil for automotive electronics according to claim 1, characterized in that the amine salt is hexyl benzyl amine salt, dicyclohexylamine salt, di-tert-butoxycarbonyl histidine dicyclohexylamine salt, dimethylamine hydrochloride, triethanolamine, piroctone ethanolamine salt or a mixture thereof.
  4. 根据权利要求1所述汽车电子用高比容低压电极箔的制备方法，其特征在于，季铵盐为十二烷基硫酸钠、十二烷基三甲基溴化铵、十二烷基醇醚硫酸铵中的任一种或它们的混合物。The preparation method of high specific volume low voltage electrode foil for automotive electronics according to claim 1, characterized in that the quaternary ammonium salt is sodium lauryl sulfate, dodecyl trimethyl ammonium bromide, dodecyl alcohol Any one of ammonium ether sulfates or mixtures thereof.
  5. 根据权利要求1所述汽车电子用高比容低压电极箔的制备方法，其特征在于，磷酸盐为磷酸二铵、六偏磷酸钠、磷酸氢二钠中的任一种或它们的混合物。The method for preparing high specific volume low voltage electrode foil for automotive electronics according to claim 1, wherein the phosphate is any one of diammonium phosphate, sodium hexametaphosphate, disodium hydrogen phosphate or a mixture thereof.
  6. 根据权利要求1所述汽车电子用高比容低压电极箔的制备方法，其特征在于，氧化性酸为硝酸、高锰酸、次氯酸中的任一项，且以重量计混酸比例为：磷酸：氧化性酸＝2：1。 The method for preparing high specific volume low-voltage electrode foil for automotive electronics according to claim 1, wherein the oxidizing acid is any one of nitric acid, permanganic acid, and hypochlorous acid, and the mixed acid ratio by weight is: Phosphoric acid: oxidizing acid = 2:1.
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