WO2022247364A1 - Method for preparing nano microporous structure aluminum electrode foil for automotive electronics - Google Patents

Method for preparing nano microporous structure aluminum electrode foil for automotive electronics Download PDF

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WO2022247364A1
WO2022247364A1 PCT/CN2022/077206 CN2022077206W WO2022247364A1 WO 2022247364 A1 WO2022247364 A1 WO 2022247364A1 CN 2022077206 W CN2022077206 W CN 2022077206W WO 2022247364 A1 WO2022247364 A1 WO 2022247364A1
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foil
treatment
anode foil
automotive electronics
aluminum electrode
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PCT/CN2022/077206
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French (fr)
Chinese (zh)
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王建中
何桂丽
金学军
王贵州
龚煜
宋双喜
肖飞
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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
四川中雅科技有限公司
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Priority to KR1020227026212A priority Critical patent/KR102598338B1/en
Publication of WO2022247364A1 publication Critical patent/WO2022247364A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/04—Etching of light metals
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
    • 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
    • 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
    • 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
    • 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

Definitions

  • the invention belongs to the technical field of capacitor manufacturing, and in particular relates to a method for preparing an aluminum electrode foil with a nanoporous structure for automotive electronics.
  • Aluminum electrolytic containers for automotive electronics not only need to have the characteristics of strong reliability and high stability, but also take into account the development needs of miniaturization and shrinkage.
  • the capacitance of an aluminum electrolytic capacitor is determined by the capacitance of the anode foil.
  • the aluminum foil etching method is crucial.
  • the aluminum foil manufacturing industry uses chemical corrosion to prepare corroded aluminum foil.
  • the size and distribution of corrosion holes are uncontrollable, resulting in low surface expansion efficiency, high foil brittleness, and low mechanical strength, which directly affect the capacity and bending of the electrode foil. performance.
  • the alumina content of the oxide film crystals obtained by the chemical formation method is low, and the dielectric constant is not high.
  • Chinese patent CN 105350064 A discloses a corrosion process method of anode foil for solid aluminum electrolytic capacitors, which is to carry out AC frequency conversion corrosion in a mixed solution of hydrochloric acid, sulfuric acid and aluminum trichloride after the aluminum foil is pretreated, and then The intermediate treatment is carried out in the aqueous solution of phosphoric acid or its acid salt, and then the AC frequency conversion corrosion is repeated several times according to different waveforms and frequencies, and the aluminum foil is subjected to multi-stage hole expansion corrosion, and finally chemical cleaning is carried out.
  • the hole expansion effect of the aluminum foil obtained by this method is better, and the mechanical strength of the aluminum foil has been improved, but the size and uniformity of the corrosion pits need to be further improved.
  • the purpose of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing aluminum electrode foil with nanoporous structure for automotive electronics.
  • the overall process is simple and the energy consumption is low.
  • the prepared anode foil has high specific volume, good mechanical strength, The advantages of low leakage current and long service life are suitable for aluminum electrolytic capacitors used in automotive electronics.
  • a method for preparing an aluminum electrode foil with a nanoporous structure for automotive electronics mainly comprising the following steps:
  • the pretreated anode foil is galvanically corroded in a mixed solution of hydrochloric acid and sulfuric acid to perform multi-stage frequency conversion for porosity;
  • annealing treatment is carried out by adopting gradient variable temperature heat treatment technology
  • the anode foil is electro-oxidized in a mixed solution of ammonium adipate and ammonium dihydrogen phosphate, and a repair is performed;
  • the concentration of phosphoric acid solution used in the primary pretreatment solution is 1-10wt%, the temperature is 40-65°C, and the reaction time is 1-6min; the concentration of hydrochloric acid in the secondary pretreatment solution is 1-10wt%. , the concentration of sulfuric acid is 0.1-2wt%, the temperature is 45-55°C, and the reaction time is 1-6min.
  • step (5) the concentration of the nitric acid solution used is 50-70wt%, the temperature is controlled within 25-40°C, and the reaction time is 60-360s.
  • step (7) the concentration of ammonia water is 20wt%-28wt%, the concentration of ammonium adipate is 0.1-1%, and the reaction time is 30-120s.
  • step (8) when carrying out gradient temperature heat treatment, the first stage temperature is 200-300°C, and the temperature is kept for 1-3min; the second stage temperature is 300-400°C, and the heat preservation is 1-3min; Keep warm for 0.5-2min.
  • step (13) the annealing heat treatment adopts a microwave heating method, the power is 10-40KW, and the heating time is 60-240s.
  • the present invention has the following advantages:
  • the scheme disclosed in this application is improved on the basis of the existing process. After two pretreatment processes in the corrosion stage, it can not only ensure the cleaning effect, but also fully expose the corrosion pits on the surface of the aluminum foil to avoid subsequent porosity. Ineffective holes and parallel holes are generated during the hole expansion process to ensure uniform corrosion pit size and uniform distribution, greatly improving the surface expansion efficiency, and the real specific surface area of the aluminum foil is large. The development needs of modernization and miniaturization;
  • the post-treatment step is added, combined with heat treatment, to form a thin layer of porous aluminum oxide oxide layer on the surface of the corroded foil, which can avoid corrosion on the surface of the foil during storage and transportation. Being eroded and polluted, it can also reduce energy consumption in the subsequent formation process;
  • This application adopts gradient variable temperature heat treatment technology for annealing after the aluminum foil is expanded and cleaned.
  • the gradient variable temperature method can increase the flexibility of the aluminum residual core layer, thereby improving the mechanical strength of the aluminum foil, and finally enhancing the reliability and reliability of the aluminum electrolytic capacitor. stability;
  • This application designs the step of using microwave heat treatment annealing in the middle of the first repair formation and the second repair formation process. This step can selectively heat the structural characteristics of the oxide film, improve the conversion rate of the crystalline oxide film, and thereby reduce the leakage current , prolong the service life of the product, the service life of the electrode foil prepared by the method disclosed in this application is as long as 20000h, which is qualitatively improved compared with the aluminum electrode foil prepared by the traditional process.
  • Fig. 1 is the scanning electron micrograph of the nanoporous structure aluminum electrode foil of automotive electronics prepared in embodiment 1;
  • Fig. 2 is a statistical chart of performance parameters of the nanoporous aluminum electrode foil for automotive electronics prepared in Example 1.
  • Example 1 Preparation method of aluminum electrode foil with nanoporous structure for automotive electronics
  • the anode foil is annealed by gradient variable temperature heat treatment technology.
  • the temperature of the first stage is 220°C, and it is kept for 3 minutes.
  • the temperature of the second stage is 380°C, and it is held for 1.5 minutes.
  • Microwave heat treatment is carried out to the anode foil, the power is 40KW, and the heating time is 60s;
  • the scanning electron microscope picture of the obtained aluminum electrode foil with nanoporous structure is shown in Figure 1. It can be seen from the figure that the nanoporous structure on the obtained aluminum electrode foil is regular, evenly distributed, and the pore size is 100-400nm, with uniformity. High, which in turn helps to improve the capacity and bending performance of the electrode foil.
  • Comparative example the method of preparing aluminum electrode foil with nanoporous structure by using the original process
  • the pretreated anode foil is galvanically corroded in a mixed solution of 5.0mol/L hydrochloric acid and 0.2mol/L sulfuric acid at 30°C to perform three-stage frequency conversion porosity, the primary porosity current frequency is 60Hz, and the secondary The frequency of the first-level porosity current is 45Hz, and the frequency of the third-level porosity current is 30Hz;
  • the performance parameter comparison results of the aluminum electrode foil prepared by using the disclosed scheme of the embodiment and the electrode foil prepared by relying on the existing technology are shown in Figure 2.
  • the disclosed scheme of the embodiment It can effectively improve the specific capacitance and mechanical strength of the electrode foil, reduce the leakage current, and effectively prolong the service life of the product.

Abstract

Disclosed in the present invention is a method for preparing a nano microporous structure aluminum electrode foil for automotive electronics, the method comprising two parts of corrosion and formation. The corrosion process comprises the steps of two pre-treatments, multi-stage hole formation, an intermediate treatment, multi-stage hole expansion, a post-treatment, cleaning, a heat treatment, etc. The formation process comprises the steps of a pre-treatment, multi-stage formation, a phosphoric acid treatment, primary repair formation, a heat treatment, secondary repair formation, drying, etc. The two pre-treatments can fully expose etching hole occurrence sites on the surface of an aluminum foil while ensuring the cleaning effect, such that invalid holes and overlapping holes are prevented from being generated in a subsequent treatment, the size and distribution of the etching holes are more uniform, and the surface expanding efficiency is improved. The post-treatment step and heat treatment are combined during the corrosion process, such that a thin porous aluminum oxide oxidation layer is generated on the surface of the corroded foil, which can prevent the corroded foil from being eroded and contaminated during the storage and transport process thereof, and the energy consumption can also be reduced during formation.

Description

一种汽车电子用纳微孔结构铝电极箔制备方法A preparation method of aluminum electrode foil with nanoporous structure for automotive electronics 技术领域technical field
本发明属于电容器制造技术领域，具体涉及一种汽车电子用纳微孔结构铝电极箔制备方法。The invention belongs to the technical field of capacitor manufacturing, and in particular relates to a method for preparing an aluminum electrode foil with a nanoporous structure for automotive electronics.
背景技术Background technique
汽车电子用铝电解容器不仅需要具有可靠性强、稳定性高的特性，同时还应兼顾小型化、缩体化的发展需求。铝电解电容器的电容量由阳极箔的电容决定。Aluminum electrolytic containers for automotive electronics not only need to have the characteristics of strong reliability and high stability, but also take into account the development needs of miniaturization and shrinkage. The capacitance of an aluminum electrolytic capacitor is determined by the capacitance of the anode foil.
所以在电容器容量一定的前提下，所用阳极箔的比电容越高，电容器的体积越小。为了获得更大的的比表面积，铝箔腐蚀方法至关重要。目前，铝箔制造业采用化学腐蚀的方法制备得到腐蚀铝箔，蚀孔的大小和分布不可控，导致扩面效率较低，而且箔脆性高，机械强度低，直接影响到电极箔的容量和折弯性能。同时，采用的化成方法获得氧化膜结晶的氧化铝含量低，介电常数不高，同时氧化铝膜层中还存在大量缺陷，导致漏电流较大，而且化成过程耗电量较大，成本较高。Therefore, under the premise of a certain capacitor capacity, the higher the specific capacitance of the anode foil used, the smaller the volume of the capacitor. In order to obtain a larger specific surface area, the aluminum foil etching method is crucial. At present, the aluminum foil manufacturing industry uses chemical corrosion to prepare corroded aluminum foil. The size and distribution of corrosion holes are uncontrollable, resulting in low surface expansion efficiency, high foil brittleness, and low mechanical strength, which directly affect the capacity and bending of the electrode foil. performance. At the same time, the alumina content of the oxide film crystals obtained by the chemical formation method is low, and the dielectric constant is not high. At the same time, there are still a large number of defects in the aluminum oxide film layer, resulting in a large leakage current, and the chemical formation process consumes a lot of power and is relatively expensive. high.
为了提高铝电极箔的容量和强度以满足元器件的冗余设计与小型化要求，并能降低铝箔漏电流以提高电解电容器的工作寿命，本领域相关技术人员对铝箔腐蚀工艺进行了探索性改进。In order to increase the capacity and strength of aluminum electrode foil to meet the redundant design and miniaturization requirements of components, and reduce the leakage current of aluminum foil to improve the working life of electrolytic capacitors, relevant technical personnel in the field have made exploratory improvements to the aluminum foil corrosion process .
如中国专利CN 105350064 A公开一种固态铝电解电容器用阳极箔的腐蚀工艺方法，其是将铝箔经过前处理后在盐酸、硫酸和三氯化铝的混合溶液中进行交流变频腐蚀，接着在含有磷酸或其酸式盐的水溶液中进行中间处理，再按不同波形、频率将交流变频腐蚀反复进行数次，对铝箔进行多级扩孔腐蚀，最后进行化学清洗。利用该方法得到的铝箔扩孔效果较好，且铝箔的机械强度有所提升，但是蚀孔的大小和分布的均一性还有待进一步提高。For example, Chinese patent CN 105350064 A discloses a corrosion process method of anode foil for solid aluminum electrolytic capacitors, which is to carry out AC frequency conversion corrosion in a mixed solution of hydrochloric acid, sulfuric acid and aluminum trichloride after the aluminum foil is pretreated, and then The intermediate treatment is carried out in the aqueous solution of phosphoric acid or its acid salt, and then the AC frequency conversion corrosion is repeated several times according to different waveforms and frequencies, and the aluminum foil is subjected to multi-stage hole expansion corrosion, and finally chemical cleaning is carried out. The hole expansion effect of the aluminum foil obtained by this method is better, and the mechanical strength of the aluminum foil has been improved, but the size and uniformity of the corrosion pits need to be further improved.
发明内容Contents of the invention
本发明的目的在于克服现有技术中存在的不足，提供一汽车电子用纳微孔结构铝电极箔制备方法，整体过程简单，能耗低，制备的阳极箔具备比容高、机械强度好、漏电流低、使用寿命长等优点，适用于汽车电子用铝电解电容器。The purpose of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing aluminum electrode foil with nanoporous structure for automotive electronics. The overall process is simple and the energy consumption is low. The prepared anode foil has high specific volume, good mechanical strength, The advantages of low leakage current and long service life are suitable for aluminum electrolytic capacitors used in automotive electronics.
本发明的技术方案为：Technical scheme of the present invention is:
一种汽车电子用纳微孔结构铝电极箔的制备方法，主要包括如下步骤：A method for preparing an aluminum electrode foil with a nanoporous structure for automotive electronics, mainly comprising the following steps:
(1)将低压用高纯电子铝光箔在磷酸溶液中进行一次前处理，再浸入盐酸和硫酸的混合液中进行二次前处理；(1) Perform a pretreatment on high-purity electronic aluminum foil for low pressure in a phosphoric acid solution, and then immerse it in a mixture of hydrochloric acid and sulfuric acid for a second pretreatment;
(2)将前处理后的阳极箔在盐酸与硫酸混合溶液中加电腐蚀，进行多级变频发孔；(2) The pretreated anode foil is galvanically corroded in a mixed solution of hydrochloric acid and sulfuric acid to perform multi-stage frequency conversion for porosity;
(3)将发孔后的阳极箔在盐酸、硫酸和草酸混合溶液中浸泡进行中处理；(3) Soak the anode foil after porosity in a mixed solution of hydrochloric acid, sulfuric acid and oxalic acid for intermediate treatment;
(4)将中处理后的阳极箔在盐酸、硫酸、草酸和磷酸混合溶液中加电腐蚀，进行多级扩孔；(4) Electrocorroding the anode foil after the intermediate treatment in a mixed solution of hydrochloric acid, sulfuric acid, oxalic acid and phosphoric acid to perform multi-stage hole expansion;
(5)将阳极箔在硝酸溶液中浸泡，除去氯离子；(5) Soak the anode foil in nitric acid solution to remove chloride ions;
(6)将阳极箔在纯水中清洗干净；(6) Clean the anode foil in pure water;
(7)将阳极箔浸泡在己二酸铵和氨水混合溶液中，进行后处理；(7) Soak the anode foil in the mixed solution of ammonium adipate and ammonia water for post-treatment;
(8)在氮气保护下，采用梯度变温热处理技术进行退火处理；(8) Under the protection of nitrogen, annealing treatment is carried out by adopting gradient variable temperature heat treatment technology;
(9)将上步所得腐蚀箔在己二酸铵溶液中进行前处理；(9) pre-treat the corroded foil obtained in the previous step in an ammonium adipate solution;
(10)在己二酸铵溶液中加电进行多级电化学阳极氧化；(10) In the ammonium adipate solution, power is applied to carry out multi-stage electrochemical anodic oxidation;
(11)将阳极箔在磷酸溶液中浸泡处理；(11) Soak the anode foil in a phosphoric acid solution;
(12)将阳极箔在己二酸铵和磷酸二氢铵混合溶液中加电氧化，进行一次修补化成；(12) The anode foil is electro-oxidized in a mixed solution of ammonium adipate and ammonium dihydrogen phosphate, and a repair is performed;
(13)对阳极箔进行退火热处理；(13) Carrying out annealing heat treatment to the anode foil;
(14)将阳极箔在磷酸二氢铵溶液中加电氧化，进行二次修补化成；(14) Electro-oxidize the anode foil in the ammonium dihydrogen phosphate solution, and carry out secondary repair and formation;
(15)对阳极箔进行干燥处理，得到汽车电子用纳微孔结构铝电极箔。(15) Drying the anode foil to obtain an aluminum electrode foil with a nanoporous structure for automotive electronics.
进一步地，步骤(1)中，一次前处理液所用磷酸溶液浓度为1-10wt％，温度为40-65℃，反应时间为1-6min；二次前处理液中盐酸浓度为1-10wt％，硫酸浓度为0.1-2wt％，温度为45-55℃，反应时间为1-6min。Further, in step (1), the concentration of phosphoric acid solution used in the primary pretreatment solution is 1-10wt%, the temperature is 40-65°C, and the reaction time is 1-6min; the concentration of hydrochloric acid in the secondary pretreatment solution is 1-10wt%. , the concentration of sulfuric acid is 0.1-2wt%, the temperature is 45-55°C, and the reaction time is 1-6min.
进一步地，步骤(5)中，所用硝酸溶液浓度为50-70wt％，温度控制在25-40℃内，反应时间60-360s。Further, in step (5), the concentration of the nitric acid solution used is 50-70wt%, the temperature is controlled within 25-40°C, and the reaction time is 60-360s.
进一步地，步骤(7)中，氨水的浓度为20wt％-28wt％，己二酸铵浓度为0.1-1％，反应时间为30-120s。Further, in step (7), the concentration of ammonia water is 20wt%-28wt%, the concentration of ammonium adipate is 0.1-1%, and the reaction time is 30-120s.
进一步地，步骤(8)中，进行梯度变温热处理时一段温度为200-300℃，保温1-3min，二段温度为300-400℃，保温1-3min，三段温度为400-550℃，保温0.5-2min。Further, in step (8), when carrying out gradient temperature heat treatment, the first stage temperature is 200-300°C, and the temperature is kept for 1-3min; the second stage temperature is 300-400°C, and the heat preservation is 1-3min; Keep warm for 0.5-2min.
进一步地，步骤(13)中，退火热处理采用微波加热法，功率为10-40KW，加热时间为60-240s。Further, in step (13), the annealing heat treatment adopts a microwave heating method, the power is 10-40KW, and the heating time is 60-240s.
相比于现有技术，本发明具有如下优点：Compared with the prior art, the present invention has the following advantages:
1.本申请公开的方案在现有工艺基础上进行改进，腐蚀阶段经过两次前处理过程后，既能确保清洗效果，更能让铝箔表面的蚀孔发生位点充分暴露，避免后续发孔和扩孔过程中产生无效孔和并孔，确保腐蚀蚀孔大小均一，分布均匀，扩面效率大幅提升，铝箔的真实比表面积大，在此基础上制备的铝电解电容器容量大，符合当今小型化、缩体化的发展需求；1. The scheme disclosed in this application is improved on the basis of the existing process. After two pretreatment processes in the corrosion stage, it can not only ensure the cleaning effect, but also fully expose the corrosion pits on the surface of the aluminum foil to avoid subsequent porosity. Ineffective holes and parallel holes are generated during the hole expansion process to ensure uniform corrosion pit size and uniform distribution, greatly improving the surface expansion efficiency, and the real specific surface area of the aluminum foil is large. The development needs of modernization and miniaturization;
2.本申请在腐蚀过程中，加入后处理这一步骤，跟热处理相结合，在腐蚀箔表面生成一 层薄的多孔三氧化二铝氧化层，既能避免腐蚀箔在贮存和运输过程中表面遭到侵蚀和污染，在后续化成过程中，还能降低能耗；2. In the corrosion process of this application, the post-treatment step is added, combined with heat treatment, to form a thin layer of porous aluminum oxide oxide layer on the surface of the corroded foil, which can avoid corrosion on the surface of the foil during storage and transportation. Being eroded and polluted, it can also reduce energy consumption in the subsequent formation process;
3.本申请在对铝箔进行扩孔处理并清洗后采用梯度变温热处理技术进行退火，梯度变温的方法可以增加铝残芯层的柔韧性，进而提高铝箔机械强度，最终增强铝电解电容器的可靠和稳定性；3. This application adopts gradient variable temperature heat treatment technology for annealing after the aluminum foil is expanded and cleaned. The gradient variable temperature method can increase the flexibility of the aluminum residual core layer, thereby improving the mechanical strength of the aluminum foil, and finally enhancing the reliability and reliability of the aluminum electrolytic capacitor. stability;
4.本申请在一修补化成和二次修补化成过程中间设计了利用微波热处理退火的步骤，该步骤可以针对氧化膜的结构特点进行选择性加热，提升结晶氧化膜的转化率，从而降低漏电流，延长产品的使用寿命，利用本申请公开方法制备的电极箔的使用寿命长达20000h，较传统工艺制备的铝电极箔而言有质的提升。4. This application designs the step of using microwave heat treatment annealing in the middle of the first repair formation and the second repair formation process. This step can selectively heat the structural characteristics of the oxide film, improve the conversion rate of the crystalline oxide film, and thereby reduce the leakage current , prolong the service life of the product, the service life of the electrode foil prepared by the method disclosed in this application is as long as 20000h, which is qualitatively improved compared with the aluminum electrode foil prepared by the traditional process.
附图说明Description of drawings
图1为实施例1制备的汽车电子用纳微孔结构铝电极箔的扫描电子显微镜图；Fig. 1 is the scanning electron micrograph of the nanoporous structure aluminum electrode foil of automotive electronics prepared in embodiment 1;
图2为实施例1制备的汽车电子用纳微孔结构铝电极箔的性能参数统计图。Fig. 2 is a statistical chart of performance parameters of the nanoporous aluminum electrode foil for automotive electronics prepared in Example 1.
具体实施方式Detailed ways
下面结合附图对本发明的技术方案作进一步的说明，但并不局限于此，凡是对本发明技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，均应涵盖在本发明的保护范围中。The technical solution of the present invention will be further described below in conjunction with the accompanying drawings, but it is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be covered by the present invention. within the scope of protection.
实施例1：汽车电子用纳微孔结构铝电极箔的制备方法Example 1: Preparation method of aluminum electrode foil with nanoporous structure for automotive electronics
(1)将低压用高纯电子铝光箔置于2wt％磷酸溶液中，55℃条件下反应3min，取出后在1wt％盐酸和0.5wt％硫酸的混合溶液中于50℃条件下反应2min；(1) Put high-purity electronic aluminum foil for low pressure in 2wt% phosphoric acid solution, react at 55°C for 3 minutes, take it out, and react it in a mixed solution of 1wt% hydrochloric acid and 0.5wt% sulfuric acid at 50°C for 2 minutes;
(2)将经前处理后的阳极箔置于5.0mol/L盐酸与0.2mol/L硫酸组成的混合溶液中，于30℃条件下加电腐蚀，进行3级变频发孔，一级发孔电流频率为60Hz，二级发孔电流频率为45Hz，三级发孔电流频率为30Hz；(2) Place the pretreated anode foil in a mixed solution composed of 5.0mol/L hydrochloric acid and 0.2mol/L sulfuric acid, and galvanically corrode at 30°C to perform three-stage frequency conversion and porosity, and one-stage porosity The frequency of the current is 60Hz, the frequency of the secondary porosity current is 45Hz, and the frequency of the tertiary porosity current is 30Hz;
(3)将发孔后的阳极箔置于6.0mol/L盐酸、0.14mol/L硫酸和0.07mol/L草酸组成的混合溶液中，于85℃条件下浸泡180s进行中处理；(3) Place the porous anode foil in a mixed solution composed of 6.0mol/L hydrochloric acid, 0.14mol/L sulfuric acid and 0.07mol/L oxalic acid, and soak for 180s at 85°C for intermediate treatment;
(4)将中处理后的阳极箔置于5.0mol/L盐酸、0.13mol/L硫酸、0.07mol/L草酸及0.05mol/L磷酸组成的混合溶液中，于30℃条件下加电腐蚀，进行5级扩孔；(4) Place the anode foil after intermediate treatment in a mixed solution composed of 5.0mol/L hydrochloric acid, 0.13mol/L sulfuric acid, 0.07mol/L oxalic acid and 0.05mol/L phosphoric acid, and conduct electro-corrosion at 30°C. Carry out 5-level reaming;
(5)将阳极箔置于26wt％硝酸溶液中，于30℃条件下浸泡100s，除去氯离子；(5) Place the anode foil in 26wt% nitric acid solution, soak for 100s at 30°C to remove chloride ions;
(6)将阳极箔在纯水中清洗干净；(6) Clean the anode foil in pure water;
(7)将阳极箔浸泡在26wt％氨水和0.2％己二酸铵溶液中45s进行后处理；(7) Soak the anode foil in 26wt% ammonia water and 0.2% ammonium adipate solution for 45s for post-treatment;
(8)将阳极箔在氮气保护下，采用梯度变温热处理技术进行退火处理，一段温度220℃，保温3min，二段温度380℃，保温1.5min，三段温度470℃，保温1min，得到汽车电子用 纳微孔结构腐蚀箔；(8) Under the protection of nitrogen, the anode foil is annealed by gradient variable temperature heat treatment technology. The temperature of the first stage is 220°C, and it is kept for 3 minutes. The temperature of the second stage is 380°C, and it is held for 1.5 minutes. Etching foils with nanoporous structures;
(9)将腐蚀箔置于1wt％己二酸铵溶液中，45℃条件下浸泡4min进行前处理；(9) Put the corroded foil in 1wt% ammonium adipate solution, soak for 4 minutes at 45°C for pretreatment;
(10)将阳极箔在8wt％己二酸铵溶液中于45℃条件下加电进行4级电化学阳极氧化；(10) Applying electricity to the anode foil in 8wt% ammonium adipate solution at 45°C to perform 4-stage electrochemical anodic oxidation;
(11)将阳极箔置于7wt％磷酸溶液中，55℃条件下浸泡处理2.5min；(11) Place the anode foil in a 7wt% phosphoric acid solution, and soak it at 55°C for 2.5 minutes;
(12)将阳极箔置于1.5wt％己二酸铵和0.25wt％磷酸二氢铵组成的混合溶液中，于75℃条件下加电4min，进行一次修补化成；(12) Place the anode foil in a mixed solution composed of 1.5wt% ammonium adipate and 0.25wt% ammonium dihydrogen phosphate, and apply electricity at 75°C for 4 minutes to perform a repairing formation;
(13)对阳极箔进行微波热处理，功率为40KW，加热时间为60s；(13) Microwave heat treatment is carried out to the anode foil, the power is 40KW, and the heating time is 60s;
(14)将阳极箔置于1wt％磷酸二氢铵溶液中，于75℃条件下加电4min，进行二次修补化成；(14) Place the anode foil in a 1wt% ammonium dihydrogen phosphate solution, apply electricity for 4 minutes at 75°C, and perform secondary repair and formation;
(15)在300℃下对阳极箔进行干燥处理，得到汽车电子用纳微孔结构铝电极箔。(15) Drying the anode foil at 300° C. to obtain an aluminum electrode foil with a nanoporous structure for automotive electronics.
所得纳微孔结构铝电极箔的扫描电子显微镜图如图1所示，从图中可以看出，所得铝电极箔上纳微孔结构规则，分布均匀，且孔径大小在100-400nm，均一性高，进而有助于提升电极箔的容量和折弯性能。The scanning electron microscope picture of the obtained aluminum electrode foil with nanoporous structure is shown in Figure 1. It can be seen from the figure that the nanoporous structure on the obtained aluminum electrode foil is regular, evenly distributed, and the pore size is 100-400nm, with uniformity. High, which in turn helps to improve the capacity and bending performance of the electrode foil.
对比例：利用原工艺制备纳微孔结构铝电极箔的方法Comparative example: the method of preparing aluminum electrode foil with nanoporous structure by using the original process
(1)将低压用高纯电子铝光箔置于5wt％氢氧化钠溶液中，45℃反应5min；(1) Put high-purity electronic aluminum foil for low pressure in 5wt% sodium hydroxide solution, and react at 45°C for 5 minutes;
(2)将经前处理后的阳极箔在5.0mol/L盐酸与0.2mol/L硫酸混合溶液中于30℃加电腐蚀，进行3级变频发孔，一级发孔电流频率为60Hz，二级发孔电流频率为45Hz，三级发孔电流频率为30Hz；(2) The pretreated anode foil is galvanically corroded in a mixed solution of 5.0mol/L hydrochloric acid and 0.2mol/L sulfuric acid at 30°C to perform three-stage frequency conversion porosity, the primary porosity current frequency is 60Hz, and the secondary The frequency of the first-level porosity current is 45Hz, and the frequency of the third-level porosity current is 30Hz;
(3)将发孔后的阳极箔置于6.0mol/L盐酸、0.14mol/L硫酸和0.07mol/L草酸的混合溶液中，85℃浸泡180s进行中处理；(3) Place the porous anode foil in a mixed solution of 6.0mol/L hydrochloric acid, 0.14mol/L sulfuric acid and 0.07mol/L oxalic acid, soak at 85°C for 180s for intermediate treatment;
(4)将中处理后的阳极箔置于5.0mol/L盐酸、0.13mol/L硫酸、0.07mol/L草酸及0.05mol/L磷酸混合的溶液中，30℃加电腐蚀，进行5级扩孔；(4) Put the anode foil after intermediate treatment in a mixed solution of 5.0mol/L hydrochloric acid, 0.13mol/L sulfuric acid, 0.07mol/L oxalic acid and 0.05mol/L phosphoric acid, and conduct galvanic corrosion at 30°C for 5-stage expansion. hole;
(5)将阳极箔在纯水中清洗干净；(5) Clean the anode foil in pure water;
(6)将阳极箔放在470℃烘箱中，退火处理7min，得到腐蚀箔；(6) Put the anode foil in an oven at 470°C and anneal for 7 minutes to obtain a corroded foil;
(7)将得到的腐蚀箔置于1wt％己二酸铵溶液中，45℃浸泡4min进行前处理；(7) Place the obtained corroded foil in 1wt% ammonium adipate solution, soak at 45°C for 4min for pretreatment;
(8)将得到的阳极箔置于8wt％己二酸铵溶液中，45℃加电进行4级电化学阳极氧化；(8) Place the obtained anode foil in 8wt% ammonium adipate solution, and apply electricity at 45° C. to perform 4-stage electrochemical anodic oxidation;
(9)将阳极箔置于7wt％磷酸溶液中，55℃浸泡处理2.5min；(9) Place the anode foil in a 7wt% phosphoric acid solution and soak at 55°C for 2.5 minutes;
(10)将阳极箔置于1.5wt％己二酸铵和0.25wt％磷酸二氢铵组成的混合溶液中，75℃加电4min，进行一次修补化成；(10) Place the anode foil in a mixed solution composed of 1.5wt% ammonium adipate and 0.25wt% ammonium dihydrogen phosphate, apply electricity at 75°C for 4 minutes, and perform a repairing formation;
(11)将阳极箔放入烘箱中，450℃退火处理2min；(11) Put the anode foil into an oven and anneal at 450°C for 2 minutes;
(12)将阳极箔置于1wt％磷酸二氢铵溶液中，75℃加电4min，进行二次修补化成；(12) Place the anode foil in 1wt% ammonium dihydrogen phosphate solution, apply electricity at 75°C for 4 minutes, and perform secondary repair and formation;
(13)在300℃下对阳极箔进行干燥处理，得到汽车电子用纳微孔结构铝电极箔。(13) Drying the anode foil at 300° C. to obtain an aluminum electrode foil with a nanoporous structure for automotive electronics.
利用实施例公开方案制备的铝电极箔与依靠现有工艺(即对比例所给出方案)制备的电极箔的性能参数对比结果如图2所示，从图中可以看出，实施例公开方案可有效提升电极箔的比电容和机械强度，并能降低漏电流，有效延长产品的使用寿命。The performance parameter comparison results of the aluminum electrode foil prepared by using the disclosed scheme of the embodiment and the electrode foil prepared by relying on the existing technology (that is, the scheme given in the comparative example) are shown in Figure 2. As can be seen from the figure, the disclosed scheme of the embodiment It can effectively improve the specific capacitance and mechanical strength of the electrode foil, reduce the leakage current, and effectively prolong the service life of the product.
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。The above is only an embodiment of the present invention, and does not limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made by using the description of the present invention and the contents of the accompanying drawings, or directly or indirectly used in other related technologies fields, all of which are equally included in the scope of patent protection of the present invention.

Claims (6)

  1. 一种汽车电子用纳微孔结构铝电极箔的制备方法，其特征在于，主要包括如下步骤：A method for preparing an aluminum electrode foil with a nanoporous structure for automotive electronics, characterized in that it mainly includes the following steps:
    (1)将低压用高纯电子铝光箔在磷酸溶液中进行一次前处理，再浸入盐酸和硫酸的混合液中进行二次前处理；(1) Perform a pretreatment on high-purity electronic aluminum foil for low pressure in a phosphoric acid solution, and then immerse it in a mixture of hydrochloric acid and sulfuric acid for a second pretreatment;
    (2)将前处理后的阳极箔在盐酸与硫酸混合溶液中加电腐蚀，进行多级变频发孔；(2) The pretreated anode foil is galvanically corroded in a mixed solution of hydrochloric acid and sulfuric acid to perform multi-stage frequency conversion for porosity;
    (3)将发孔后的阳极箔在盐酸、硫酸和草酸混合溶液中浸泡进行中处理；(3) Soak the anode foil after porosity in a mixed solution of hydrochloric acid, sulfuric acid and oxalic acid for intermediate treatment;
    (4)将中处理后的阳极箔在盐酸、硫酸、草酸和磷酸混合溶液中加电腐蚀，进行多级扩孔；(4) Electrocorroding the anode foil after the intermediate treatment in a mixed solution of hydrochloric acid, sulfuric acid, oxalic acid and phosphoric acid to perform multi-stage hole expansion;
    (5)将阳极箔在硝酸溶液中浸泡，除去氯离子；(5) Soak the anode foil in nitric acid solution to remove chloride ions;
    (6)将阳极箔在纯水中清洗干净；(6) Clean the anode foil in pure water;
    (7)将阳极箔浸泡在己二酸铵和氨水混合溶液中，进行后处理；(7) Soak the anode foil in the mixed solution of ammonium adipate and ammonia water for post-treatment;
    (8)在氮气保护下，采用梯度变温热处理技术进行退火处理；(8) Under the protection of nitrogen, annealing treatment is carried out by adopting gradient variable temperature heat treatment technology;
    (9)将上步所得腐蚀箔在己二酸铵溶液中进行前处理；(9) pre-treat the corroded foil obtained in the previous step in an ammonium adipate solution;
    (10)在己二酸铵溶液中加电进行多级电化学阳极氧化；(10) In the ammonium adipate solution, power is applied to carry out multi-stage electrochemical anodic oxidation;
    (11)将阳极箔在磷酸溶液中浸泡处理；(11) Soak the anode foil in a phosphoric acid solution;
    (12)将阳极箔在己二酸铵和磷酸二氢铵混合溶液中加电氧化，进行一次修补化成；(12) The anode foil is electro-oxidized in a mixed solution of ammonium adipate and ammonium dihydrogen phosphate, and a repair is performed;
    (13)对阳极箔进行退火热处理；(13) Carrying out annealing heat treatment to the anode foil;
    (14)将阳极箔在磷酸二氢铵溶液中加电氧化，进行二次修补化成；(14) Electro-oxidize the anode foil in the ammonium dihydrogen phosphate solution, and carry out secondary repair and formation;
    (15)对阳极箔进行干燥处理，得到汽车电子用纳微孔结构铝电极箔。(15) Drying the anode foil to obtain an aluminum electrode foil with a nanoporous structure for automotive electronics.
  2. 如权利要求1所述的一种汽车电子用纳微孔结构铝电极箔的制备方法，其特征在于，步骤(1)中，一次前处理所用磷酸溶液浓度为1-10wt％，温度为40-65℃，反应时间为1-6min；二次前处理所用盐酸浓度为1-10wt％，硫酸浓度为0.1-2wt％，温度为45-55℃，反应时间为1-6min。A kind of preparation method of nanoporous structure aluminum electrode foil for automotive electronics as claimed in claim 1, is characterized in that, in step (1), the concentration of the phosphoric acid solution used for a pretreatment is 1-10wt%, and the temperature is 40- 65°C, the reaction time is 1-6min; the hydrochloric acid concentration used for the secondary pretreatment is 1-10wt%, the sulfuric acid concentration is 0.1-2wt%, the temperature is 45-55°C, and the reaction time is 1-6min.
  3. 如权利要求1所述的一种汽车电子用纳微孔结构铝电极箔的制备方法，其特征在于，步骤(5)中，所用硝酸溶液浓度为50-70wt％，温度控制在25-40℃内，反应时间60-360s。A method for preparing an aluminum electrode foil with a nanoporous structure for automotive electronics according to claim 1, wherein in step (5), the concentration of the nitric acid solution used is 50-70wt%, and the temperature is controlled at 25-40°C Within, the response time is 60-360s.
  4. 如权利要求1所述的一种汽车电子用纳微孔结构铝电极箔的制备方法，其特 征在于，步骤(7)中，氨水的浓度为20wt％-28wt％，己二酸铵浓度为0.1-1％，反应时间为30-120s。A kind of preparation method of nanoporous structure aluminum electrode foil for automotive electronics as claimed in claim 1, is characterized in that, in step (7), the concentration of ammonia water is 20wt%-28wt%, and the concentration of ammonium adipate is 0.1 -1%, the reaction time is 30-120s.
  5. 如权利要求1所述的一种汽车电子用纳微孔结构铝电极箔的制备方法，其特征在于，步骤(8)中，进行梯度变温热处理时一段温度为200-300℃，保温1-3min，二段温度为300-400℃，保温1-3min，三段温度为400-550℃，保温0.5-2min。A method for preparing an aluminum electrode foil with a nanoporous structure for automotive electronics as claimed in claim 1, wherein in step (8), when performing gradient temperature heat treatment, the temperature is 200-300° C., and the temperature is kept for 1-3 minutes. , the temperature of the second stage is 300-400°C, keep warm for 1-3min, the temperature of the third stage is 400-550°C, keep warm for 0.5-2min.
  6. 如权利要求1所述的一种汽车电子用纳微孔结构铝电极箔的制备方法，其特征在于，步骤(13)中，退火热处理采用微波加热法，功率为10-40KW，加热时间为60-240s。The preparation method of a nano-microporous aluminum electrode foil for automotive electronics as claimed in claim 1, wherein in step (13), the annealing heat treatment adopts microwave heating method, the power is 10-40KW, and the heating time is 60 -240s.
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