WO2019166034A1 - 一种铝电解电容器用阳极箔腐蚀工艺 - Google Patents

一种铝电解电容器用阳极箔腐蚀工艺 Download PDF

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WO2019166034A1
WO2019166034A1 PCT/CN2019/085125 CN2019085125W WO2019166034A1 WO 2019166034 A1 WO2019166034 A1 WO 2019166034A1 CN 2019085125 W CN2019085125 W CN 2019085125W WO 2019166034 A1 WO2019166034 A1 WO 2019166034A1
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corrosion
salt
acid
foil
primary
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PCT/CN2019/085125
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English (en)
French (fr)
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张霞
何凤荣
曹文亮
肖远龙
向云刚
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乳源瑶族自治县东阳光化成箔有限公司
东莞东阳光科研发有限公司
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Publication of WO2019166034A1 publication Critical patent/WO2019166034A1/zh
Priority to AU2019101511A priority Critical patent/AU2019101511A4/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—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, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/055—Etched foil electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • H01G9/0032—Processes of manufacture formation of the dielectric layer

Definitions

  • the present invention relates to the field of anode foils for capacitors. Specifically, the present invention relates to an anode foil etching process for aluminum electrolytic capacitors.
  • Electrode foil is the key material for the production of aluminum electrolytic capacitors. The performance of electrode foil largely determines a number of key technical indicators such as capacity, volume, leakage current, loss and life of aluminum electrolytic capacitors.
  • the anode foil for aluminum electrolytic capacitors is generally electrochemically etched to form a tunnel hole having a certain depth and perpendicular to the surface of the aluminum foil, increasing the specific surface area, thereby increasing the electrostatic capacity of the electrode foil; and then passing through the etching process through the chemical conversion process.
  • the surface of the etched foil forms a dense oxide film whose dielectric properties determine the pressure resistance of the capacitor.
  • the winding process in the manufacture of aluminum electrolytic capacitors requires the anode foil to have a certain tensile strength and bending performance. Corrosion technology, as a key technology for the manufacture of electrode foils, largely determines the capacity and mechanical properties of the electrode foil.
  • Conventional corrosion foil manufacturing processes include pre-treatment, primary pore corrosion, secondary pore reaming, post-treatment, etc.
  • the primary pore-forming process is the core of the corrosion process and directly determines the pore density, pore distribution and pore depth.
  • the key parameters affecting the capacity and mechanical properties of the corrosion foil In the traditional electrochemical cell drilling process, the mass transfer process in the tunnel hole is slow, and the corrosion product Al 3+ is easily enriched in the tunnel hole and hydrolyzed to form a passivation film. The growth of the hole is blocked, resulting in poor hole length and uniformity of the hole diameter.
  • the taper of the etched hole is large, and a large number of lateral branch holes are generated at the same time, which eventually leads to deterioration of the mechanical properties of the corrosion foil, which is disadvantageous for the improvement of the electrode foil capacity.
  • the present invention provides an anode foil etching process for an aluminum electrolytic capacitor, which can be combined with an etching solution by adding a carboxylic acid-containing compound or a salt complexing agent to the primary pore corrosive liquid.
  • the free Al 3+ bond improves the mass transfer rate of free Al 3+ in the tunnel pores, prevents it from enriching and hydrolyzing in the tunnel pores, and forms a passivation film, which improves the consistency of corrosion foil pores and reduces lateral branch holes.
  • the present invention adopts the following technical solutions:
  • the invention provides an anode foil etching process for an aluminum electrolytic capacitor, comprising pre-treatment, primary hole corrosion, secondary hole reaming corrosion, post-treatment, adding a complexing agent to the corrosion liquid of the first-level hole corrosion,
  • the complexing agent is a carboxylic acid-containing compound or a salt thereof.
  • the kind of the salt of the carboxylic acid-containing compound is not particularly limited, and examples thereof include a sodium salt, a potassium salt, an ammonium salt, and the like.
  • carboxylic acid-containing compound is one or a combination of at least two of ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentacarboxylic acid, gluconic acid, and oxalic acid.
  • EDTA ethylenediaminetetraacetic acid
  • diethylenetriaminepentacarboxylic acid diethylenetriaminepentacarboxylic acid
  • gluconic acid gluconic acid
  • oxalic acid oxalic acid
  • the carboxylic acid-containing compound is one or a combination of at least two of ethylenediaminetetraacetic acid, gluconic acid, and oxalic acid.
  • the content of the carboxylic acid-containing compound or a salt thereof in the primary pore corrosive liquid is 0.1 to 100 mM.
  • the content of the carboxylic acid-containing compound or a salt thereof in the primary pore corrosive liquid is related to the selection of the carboxylic acid-containing compound.
  • the content in the primary corrosive etching solution is 10 to 60 mM, preferably 15 to 50 mM, for example, 15 mM, 20 mM, 24 mM, 28 mM, 32 mM, 36 mM, 40 mM, 44 mM, 48 mM or 50 mM, and the like.
  • the ethylenediaminetetraacetate is disodium edetate (EDTA-2Na).
  • the content in the primary corrosive etching solution is 4 to 55 mM, preferably 8 to 40 mM, for example, 8 mM, 11 mM, 13 mM, 15 mM, 18 mM, 22 mM, 26 mM, 30 mM, 34 mM, 38 mM or 40 mM, and the like.
  • the diethylenetriamine pentacarboxylate is pentasodium diethylenetriaminepentacarboxylate.
  • the content in the primary corrosive etching solution is 0.1 to 90 mM, preferably 0.4 to 80 mM, for example, 0.5 mM, 1 mM, 6 mM, 12 mM, 24 mM, 36 mM, 48 mM, 60 mM, 72 mM or 80 mM, and the like.
  • the gluconate is sodium gluconate.
  • the content in the primary corrosive etching solution is 0.5 to 65 mM, preferably 1 to 50 mM, for example, 1 mM, 3 mM, 5 mM, 7 mM, 9 mM, 11 mM, 13 mM, 15 mM, 18 mM, 20 mM, 30 mM, 40 mM or 50 mM, and the like.
  • the oxalate salt is sodium oxalate.
  • the primary corrosive etching corrosive solution is a mixture of two or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and a salt thereof.
  • the concentration of the mixed solution is in the range of 0.2 to 12N.
  • the concentration of hydrochloric acid is 1 to 11 wt%
  • the concentration of sulfuric acid is 40 to 63 wt%
  • the concentration of nitric acid is 1 to 18 wt%
  • the concentration of phosphoric acid is 1 to 57 wt%.
  • the etching solution is an aqueous solution of HCl and 3wt% to 30wt% of H 2 SO 4.
  • it is not limited thereto, and other etching liquids which are commonly used in the art to achieve the same effects can also be used in the present invention.
  • the first-order hole corrosion condition is: a corrosion temperature of 50 to 85 ° C, a current density of 0.1 to 2.5 A/cm 2 , and a corrosion time of 1 to 5 min.
  • the conditions for the etched pores are: a corrosion temperature of 70 ° C, a current density of 0.6 A/cm 2 , and a corrosion time of 1 min.
  • the pretreatment may be carried out by any treatment process commonly used in the art.
  • the pretreatment method is as follows: the aluminum foil is immersed in a solution of 1 to 25 wt% H 3 PO 4 for 0.5 to 3 minutes at a temperature of 50 to 70 °C.
  • the pretreatment method is as follows: After soaking the aluminum foil in the 60s 8wt% H 3 PO 4 solution was 60 deg.] C, the deionized water wash.
  • the secondary reaming corrosion can be carried out by any reaming process commonly used in the art.
  • the primary pore corrosion foil is etched in a 5-9 wt% HNO 3 solution for 5-12 min, the current density is 0.1-0.3 A/cm 2 , and the temperature is 60-80. °C.
  • the following two-stage reaming etching method is employed: the primary hole corrosion foil is etched in a 7 wt% HNO 3 solution for 500 s, the current density is 0.15 A/cm 2 , the temperature is 70 ° C, and then used. Ionized water is cleaned.
  • etching process it is preferred to further include a post-treatment step after secondary reaming etching.
  • the post treatment can be carried out using any of the processing techniques commonly used in the art.
  • the second-stage reaming corrosion foil is immersed in a 4-7 wt% HNO 3 solution at 50-75 ° C for 1 to 3 min, and then washed with pure water at 60-120 ° C. drying.
  • the following post-treatment method is adopted: the above-mentioned secondary reaming corrosion foil is immersed in a 5 wt% HNO 3 solution at 60 ° C for post-etching treatment for 80 s, then washed with pure water, and dried at 105 ° C.
  • the etching process provided by the invention is suitable for the corrugation corrosion of the anode foil of all medium voltage, high voltage and ultra high voltage voltage sections.
  • Corrosion of primary pores largely determines key parameters such as pore depth, pore diameter, and taper taper that affect the capacity and mechanical properties of the corrosion foil.
  • the present invention adds a complexing agent to the carboxylic acid in the primary pore corrosive solution.
  • the compound or its salt can significantly improve the pore morphology of the corroded foil compared with the addition of the complexing agent at other process stages (such as pretreatment, reaming corrosion);
  • the present invention adds a carboxylic acid-containing compound or a salt thereof as a complexing agent to the primary pore corrosive liquid, and combines with the free Al 3+ in the etching solution to improve the mass transfer process of Al 3+ in the tunnel pore. Preventing it from enriching and hydrolyzing in the tunnel hole to form a passivation film, effectively maintaining the activity of etched pore growth, preventing the growth rate of the etched hole from decreasing with the depth of the hole, or even stagnating growth or developing into a lateral branch hole, and significantly improving the etch hole Deep consistency, thickening of the corroded foil core layer, and significant reduction of lateral branch holes, which is beneficial to increase the capacity and bending resistance of the electrode foil;
  • the carboxylic acid-containing compound or a salt thereof added in the primary pore corrosive liquid can complex the corrosion product Al 3+ , promote the dissolution reaction of Al, and improve the growth process of the pores.
  • the number of aperture holes increases, the aperture diameter of the hole increases, and the taper of the hole decreases, preventing the capacity attenuation caused by the blockage of the small holes during the formation process.
  • Figure 1 A topographical view of the primary hole corrosion foil obtained in Comparative Example 1;
  • Figure 2 is a view showing the morphology of the primary hole corrosion foil obtained in Example 4.
  • Figure 3 Topographical view of the etched end of the primary hole corrosion foil obtained in Comparative Example 1;
  • Figure 4 is a top view of the etched hole end of the primary hole corrosion foil obtained in Example 4.
  • Fig. 6 is a view showing the pore size distribution of the primary pore corrosion foil obtained in Example 4.
  • Pre-treatment using Dongyang Sunshine high-purity aluminum foil, aluminum content ⁇ 99.99%, cubic texture >95%, after immersing aluminum foil in 60wtC 8wt% H 3 PO 4 solution for 60s, using deionized water Cleaned.
  • Pre-treatment using Dongyang Sunshine high-purity aluminum foil, aluminum content ⁇ 99.99%, cubic texture >95%, after immersing aluminum foil in 60wtC 8wt% H 3 PO 4 solution for 60s, using deionized water Cleaned.
  • Pre-treatment using Dongyang Sunshine high-purity aluminum foil, aluminum content ⁇ 99.99%, cubic texture >95%, after immersing aluminum foil in 60wtC 8wt% H 3 PO 4 solution for 60s, using deionized water Cleaned.
  • Pre-treatment using Dongyang Sunshine high-purity aluminum foil, aluminum content ⁇ 99.99%, cubic texture >95%, after immersing aluminum foil in 60wtC 8wt% H 3 PO 4 solution for 60s, using deionized water Cleaned.
  • Pre-treatment using Dongyang Sunshine high-purity aluminum foil, aluminum content ⁇ 99.99%, cubic texture >95%, after immersing aluminum foil in 60wtC 8wt% H 3 PO 4 solution for 60s, using deionized water Cleaned.
  • the primary hole corrosion foil obtained in the first step and the step (2) in the comparative example 1 was subjected to SEM test, and the pore size distribution of the pores was counted as shown in FIG. 5 and FIG.
  • the transverse branching holes of the corroded foil after the first-stage oxidized corrosion are obviously reduced, the uniformity of the etched hole depth is obviously improved, and the abnormally long etched holes are significantly reduced (see FIG. 1-4). ); the number of large apertures increases, the aperture at the end of the tunnel increases, and the taper of the holes decreases, which is beneficial to prevent specific volume attenuation caused by blockage of small apertures in subsequent formation (see Figure 3-6).

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Abstract

本发明提供一种铝电解电容器用阳极箔腐蚀工艺，包括前处理、一级发孔腐蚀、二级扩孔腐蚀、后处理，所述一级发孔腐蚀用腐蚀液中添加络合剂，所述络合剂为含羧酸类化合物或其盐。所述含羧酸类化合物或其盐类络合剂能够与腐蚀液中游离的Al 3+结合，改善隧道孔内Al 3+的传质过程，防止其在隧道孔内富集、水解生成钝化膜，明显改善腐蚀箔蚀孔孔深一致性，减少横向枝孔，提高电极箔的容量及折弯性能。

Description

一种铝电解电容器用阳极箔腐蚀工艺 技术领域
本发明涉及电容器用阳极箔技术领域，具体的，本发明涉及一种铝电解电容器用阳极箔腐蚀工艺。
技术背景
铝电解电容器广泛应用于电子节能灯、电子电源电路和运载工具等领域，近年因电子元器件集成化与高速处理化技术及移动产品小型化、高性能化技术高速发展的需求，“小尺寸、大容量、长寿命、耐高温、低阻抗”成为铝电解电容器的发展趋势。电极箔是生产铝电解电容器的关键材料，电极箔的性能在很大程度上决定着铝电解电容器的容量、体积大小、漏电流、损耗、寿命等多项关键技术指标。铝电解电容器用阳极箔一般采用电化学腐蚀的方法使铝箔表面形成一定深度、垂直于铝箔表面的隧道孔，增加比表面积，从而提高电极箔的静电容量；然后在通过化成工艺在经过腐蚀扩面的腐蚀箔表面形成一层致密的氧化膜，该氧化膜的介电性能决定了电容器的耐压性。同时铝电解电容器制造中的缠绕过程，要求阳极箔具有一定的抗拉强度和折弯性能。腐蚀技术作为制造电极箔的关键技术，很大程度上决定了电极箔的容量及力学性能。
常规的腐蚀箔制造工艺包括前处理、一级发孔腐蚀、二级扩孔腐蚀、后处理等工序，其中一级发孔工序是腐蚀工艺的核心，直接决定了孔密度、孔分布及孔深等影响腐蚀箔容量及力学性能的关键参数。传统的电化学发孔过程中，隧道孔内传质过程缓慢，腐蚀产物Al 3+易在隧道孔内富集、水解生成钝化膜，蚀孔生长受阻，导致隧道孔孔长及孔径均一性差、蚀孔锥度大，同时生成大量横向枝孔，最终导致腐蚀箔机械性能变差，不利于电极箔容量的提高。
因此，需要开发一种能够克服上述缺陷的腐蚀工艺。
发明内容
针对现有技术中的不足，本发明提供一种铝电解电容器用阳极箔腐蚀工艺，通过在一级发孔腐蚀液中添加含羧酸类化合物或其盐类络合剂，能够与腐蚀液中游离的Al 3+结合，改善隧道孔内的游离Al 3+传质速率，防止其在隧道孔内富集、水解生成钝化膜，改善腐蚀箔蚀孔孔深一致性，减少横向枝孔，明显提高电极箔的容量及折弯性能。
具体的，本发明采取如下技术方案：
本发明提供一种铝电解电容器用阳极箔腐蚀工艺，包括前处理、一级发孔腐蚀、二级扩孔腐蚀、后处理，所述一级发孔腐蚀用腐蚀液中添加络合剂，所述络合剂为含羧酸类化合物或其盐。
关于所述含羧酸类化合物的盐的种类没有特别限定，例如钠盐、钾盐，铵盐，等等。
进一步的，所述含羧酸类化合物为乙二胺四乙酸(EDTA)、二乙烯三胺五羧酸、葡萄糖酸、草酸中的一种或至少两种的组合。
更优选的，所述含羧酸类化合物为乙二胺四乙酸、葡萄糖酸、草酸中的一种或至少 两种的组合。
进一步的，所述含羧酸类化合物或其盐在一级发孔腐蚀液中的含量为0.1～100mM。
所述一级发孔腐蚀液中含羧酸类化合物或其盐的含量与含羧酸类化合物的选择有关。
当所述含羧酸类化合物为乙二胺四乙酸或其盐时，其在一级发孔腐蚀用腐蚀液中的含量为10～60mM，优选的为15～50mM，例如：15mM、20mM、24mM、28mM、32mM、36mM、40mM、44mM、48mM或50mM，等等。
优选的，所述乙二胺四乙酸盐为乙二胺四乙酸二钠(EDTA-2Na)。
当所述含羧酸类化合物为二乙烯三胺五羧酸或其盐时，其在一级发孔腐蚀用腐蚀液中的含量为4～55mM，优选的为8～40mM，例如：8mM、11mM、13mM、15mM、18mM、22mM、26mM、30mM、34mM、38mM或40mM，等等。
优选的，所述二乙烯三胺五羧酸盐为二乙烯三胺五羧酸五钠。
当所述含羧酸类化合物为葡萄糖酸或其盐时，其在一级发孔腐蚀用腐蚀液中的含量为0.1～90mM，优选的为0.4～80mM，例如：0.5mM、1mM、6mM、12mM、24mM、36mM、48mM、60mM、72mM或80mM，等等。
优选的，所述葡萄糖酸盐为葡萄糖酸钠。
当所述含羧酸类化合物为草酸或其盐时，其在一级发孔腐蚀用腐蚀液中的含量为0.5～65mM，优选的为1～50mM，例如：1mM、3mM、5mM、7mM、9mM、11mM、13mM、15mM、18mM、20mM、30mM、40mM或50mM，等等。
优选的，所述草酸盐为草酸钠。
进一步的，所述一级发孔腐蚀用腐蚀液为盐酸、硫酸、硝酸、磷酸及其所述酸的盐中的两种或两种以上的混合液。所述混合液的浓度在0.2～12N范围内。
进一步的，所述一级发孔腐蚀用腐蚀液中，盐酸的浓度为1～11wt％，硫酸的浓度为40～63wt％，硝酸的浓度为1～18wt％，磷酸的浓度为1～57wt％。
在一些实施方式中，所述腐蚀液为3wt％的HCl与30wt％的H 2SO 4的水溶液。但不限于此，其他本领域常用的可达到相同效果的腐蚀液也可用于本发明。
进一步的，所述一级发孔腐蚀的条件为：腐蚀温度为50～85℃，电流密度为0.1～2.5A/cm 2，腐蚀时间为1～5min。
在一些实施方式中，所述腐蚀发孔的条件为：腐蚀温度为70℃，电流密度为0.6A/cm 2，腐蚀时间为1min。
本发明提供的腐蚀工艺中，所述前处理可采用任何本领域常用的处理工艺进行。
优选的，采用如下的前处理方法：将铝箔在1～25wt％H 3PO 4溶液中浸泡0.5～3min，温度为50～70℃。
在一些实施方式中，采用如下的前处理方法：将铝箔在60℃的8wt％H 3PO 4溶液中浸泡60s后，用去离子水清洗干净。
本发明提供的腐蚀工艺中，所述二级扩孔腐蚀可采用任何本领域常用的扩孔工艺进行。
优选的，采用如下的二级扩孔腐蚀方法：将一级发孔腐蚀箔在5～9wt％HNO 3溶液 中腐蚀5～12min，电流密度为0.1～0.3A/cm 2，温度为60～80℃。
在一些实施方式中，采用如下的二级扩孔腐蚀方法：将一级发孔腐蚀箔在7wt％HNO 3溶液中腐蚀500s，电流密度为0.15A/cm 2，温度为70℃，然后用去离子水清洗干净。
本发明提供的腐蚀工艺中，优选的，还包括二级扩孔腐蚀之后的后处理步骤。所述后处理可采用任何本领域常用的处理工艺进行。
优选的，采用如下的后处理方法：将上述二级扩孔腐蚀箔浸入4～7wt％HNO 3溶液中50～75℃条件下进行腐蚀1～3min，然后用纯水清洗，于60～120℃烘干。
在一些实施方式中，采用如下的后处理方法：将上述二级扩孔腐蚀箔浸入5wt％HNO 3溶液中60℃条件下进行腐蚀后处理80s，然后用纯水清洗，于105℃烘干。
本发明提供的腐蚀工艺适应于所有中压、高压、超高压各电压段阳极箔的发孔腐蚀。
本发明的有益效果：
(1)一级发孔腐蚀很大程度决定了孔深、孔径、蚀孔锥度等影响腐蚀箔容量及力学性能的关键参数，本发明在一级发孔腐蚀液中添加络合剂含羧酸类化合物或其盐，与在其他工艺阶段(如前处理、扩孔腐蚀)添加络合剂相比，能够显著改善腐蚀箔的蚀孔形貌；
(2)本发明在一级发孔腐蚀液中添加含羧酸类化合物或其盐作为络合剂，与腐蚀液中游离的Al 3+结合，改善隧道孔内Al 3+的传质过程，防止其在隧道孔内富集、水解生成钝化膜，有效维持蚀孔生长的活性，防止随孔深增加蚀孔生长速率逐渐降低甚至停滞生长或发展为横向枝孔，显著提高了蚀孔孔深的一致性，腐蚀箔芯层增厚，横向枝孔明显减少，有利于提高电极箔的容量及抗折弯性能；
(3)本发明在一级发孔腐蚀液中添加的含羧酸类化合物或其盐能够络合腐蚀产物Al 3+，促进了Al的溶解反应的进行，改善了蚀孔的生长过程，大孔径蚀孔数增多，蚀孔顶端孔径增加，蚀孔锥度减小，防止小孔在化成过程中堵塞导致的容量衰减。
附图说明
图1：对比例1得到的一级发孔腐蚀箔的蚀孔形貌图；
图2：实施例4得到的一级发孔腐蚀箔的蚀孔形貌图；
图3：对比例1得到的一级发孔腐蚀箔的蚀孔末端形貌图；
图4：实施例4得到的一级发孔腐蚀箔的蚀孔末端形貌图；
图5：对比例1得到的一级发孔腐蚀箔的蚀孔孔径分布图；
图6：实施例4得到的一级发孔腐蚀箔的蚀孔孔径分布图。
具体实施方式
为使本发明解决的技术问题、采用的技术方案和达到的技术效果更加清楚，下面将结合附图对本发明实施例的技术方案作进一步的详细描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。
对比例1
(1)前处理：采用东阳光产高纯铝箔，铝含量≥99.99％，立方织构度＞95％，将铝箔在60℃的8wt％H 3PO 4溶液中浸泡60s后，用去离子水清洗干净；
(2)一级发孔腐蚀：将上述经过前处理的铝箔在3wt％HCl+30wt％H 2SO 4的水溶液中进行一级腐蚀，腐蚀时间为60s，电流密度为0.6A/cm 2，温度为70℃，腐蚀完毕用去离子水清洗干净，得到一级发孔腐蚀箔；
(3)二级扩孔腐蚀：将一级发孔腐蚀箔在7wt％HNO 3溶液中腐蚀500s，电流密度为0.15A/cm 2，温度为70℃，腐蚀完毕用去离子水清洗干净，得到二级扩孔腐蚀箔；
(4)腐蚀后处理：将上述二级扩孔腐蚀箔浸入5wt％HNO 3溶液中60℃条件下进行腐蚀80s，用纯水清洗干净后，在105℃下烘干得到腐蚀箔。
实施例1
(1)前处理：采用东阳光产高纯铝箔，铝含量≥99.99％，立方织构度＞95％，将铝箔在60℃的8wt％H 3PO 4溶液中浸泡60s后，用去离子水清洗干净。
(2)一级发孔腐蚀：将上述经过前处理的铝箔在3wt％HCl+30wt％H 2SO 4+20mM EDTA-2Na的水溶液中进行一级腐蚀，腐蚀时间为60s，电流密度为0.6A/cm 2，温度为70℃，腐蚀完毕用去离子水清洗干净，得到一级发孔腐蚀箔；
(3)二级扩孔腐蚀：将一级发孔腐蚀箔在7wt％HNO 3溶液中腐蚀500s，电流密度为0.15A/cm 2，温度为70℃，腐蚀完毕用去离子水清洗干净，得到二级扩孔腐蚀箔；
(4)腐蚀后处理：将上述二级扩孔腐蚀箔浸入5wt％HNO 3水溶液中60℃条件下进行腐蚀80s，用纯水清洗干净后，在105℃下烘干得到腐蚀箔。
实施例2
(1)前处理：采用东阳光产高纯铝箔，铝含量≥99.99％，立方织构度＞95％，将铝箔在60℃的8wt％H 3PO 4溶液中浸泡60s后，用去离子水清洗干净。
(2)一级发孔腐蚀：将上述经过前处理的铝箔在3wt％HCl+30wt％H 2SO 4+40mM EDTA-2Na水溶液中进行一级腐蚀，腐蚀时间为60s，电流密度为0.6A/cm 2，温度为70℃，腐蚀完毕用去离子水清洗干净，得到一级发孔腐蚀箔；
(3)二级扩孔腐蚀：将一级发孔腐蚀箔在7wt％HNO 3溶液中腐蚀500s，电流密度为0.15A/cm 2，温度为70℃，腐蚀完毕用去离子水清洗干净，得到二级扩孔腐蚀箔；
(4)腐蚀后处理：将上述二级扩孔腐蚀箔浸入5wt％HNO 3溶液中60℃条件下进行腐蚀80s，用纯水清洗干净后，在105℃下烘干得到腐蚀箔。
实施例3
(1)前处理：采用东阳光产高纯铝箔，铝含量≥99.99％，立方织构度＞95％，将铝箔在60℃的8wt％H 3PO 4溶液中浸泡60s后，用去离子水清洗干净。
(2)一级发孔腐蚀：将上述经过前处理的铝箔在3wt％HCl+30wt％H 2SO 4+36mM葡萄糖酸水溶液中进行一级腐蚀，腐蚀时间为60s，电流密度为0.6A/cm 2，温度为70℃，腐蚀完毕用去离子水清洗干净，得到一级发孔腐蚀箔；
(3)二级扩孔腐蚀：将一级发孔腐蚀箔在7wt％HNO 3溶液中腐蚀500s，电流密度为0.15A/cm 2，温度为70℃，腐蚀完毕用去离子水清洗干净，得到二级扩孔腐蚀箔；
(4)腐蚀后处理：将上述二级扩孔腐蚀箔浸入5wt％HNO 3溶液中60℃条件下进行腐蚀80s，用纯水清洗干净后，在105℃下烘干得到腐蚀箔。
实施例4
(1)前处理：采用东阳光产高纯铝箔，铝含量≥99.99％，立方织构度＞95％，将铝箔 在60℃的8wt％H 3PO 4溶液中浸泡60s后，用去离子水清洗干净。
(2)一级发孔腐蚀：将上述经过前处理的铝箔在3wt％HCl+30wt％H 2SO 4+72mM葡萄糖酸水溶液中进行一级腐蚀，腐蚀时间为60s，电流密度为0.6A/cm 2，温度为70℃，腐蚀完毕用去离子水清洗干净，得到一级发孔腐蚀箔；
(3)二级扩孔腐蚀：将一级发孔腐蚀箔在7wt％HNO 3溶液中腐蚀500s，电流密度为0.15A/cm 2，温度为70℃，腐蚀完毕用去离子水清洗干净，得到二级扩孔腐蚀箔；
(4)腐蚀后处理：将上述二级扩孔腐蚀箔浸入5wt％HNO 3溶液中60℃条件下进行腐蚀80s，用纯水清洗干净后，在105℃下烘干得到腐蚀箔。
实施例5
(1)前处理：采用东阳光产高纯铝箔，铝含量≥99.99％，立方织构度＞95％，将铝箔在60℃的8wt％H 3PO 4溶液中浸泡60s后，用去离子水清洗干净。
(2)一级发孔腐蚀：将上述经过前处理的铝箔在3wt％HCl+30wt％H 2SO 4+30mM草酸水溶液中进行一级腐蚀，腐蚀时间为60s，电流密度为0.6A/cm 2，温度为70℃，腐蚀完毕用去离子水清洗干净，得到一级发孔腐蚀箔；
(3)二级扩孔腐蚀：将一级发孔腐蚀箔在7wt％HNO 3溶液中腐蚀500s，电流密度为0.15A/cm 2，温度为70℃，腐蚀完毕用去离子水清洗干净，得到二级扩孔腐蚀箔；
(4)腐蚀后处理：将上述二级扩孔腐蚀箔浸入5wt％HNO 3溶液中60℃条件下进行腐蚀80s，用纯水清洗干净后，在105℃下烘干得到腐蚀箔。
性能测试
1、一级发孔腐蚀箔的蚀孔形貌与孔径分布测试
将对比例1和实施例4中步骤(2)得到的一级发孔腐蚀箔的形貌如图1-4所示。
将对比例1和实施例4中步骤(2)得到的一级发孔腐蚀箔电解抛光后进行SEM测试，统计其蚀孔孔径分布如图5和图6所示。
实施例4在一级腐蚀液中添加葡萄糖酸后，一级发孔腐蚀后的腐蚀箔横向枝孔明显减少，蚀孔孔深均匀性明显改善，异常长蚀孔明显减少(见图1-4)；大孔径蚀孔数增多，隧道孔末端孔径增加，蚀孔锥度减小，有利于防止小孔径蚀孔在后续化成时堵塞导致的比容衰减(见图3-6)。
2、折弯性能和静电容量测试
将对比例1和实施例1～5得到的腐蚀箔进行折弯次数测试，结果如表1所示。
将对比例1和实施例1～5得到的腐蚀箔进行化成后，测试其静电容量，测试结果如表1所示，化成条件为：10％硼酸，45℃，5A/dm 2，Vfe＝520V。
表1对比例1和实施例1～5得到的腐蚀箔及化成后的性能
Figure PCTCN2019085125-appb-000001
Figure PCTCN2019085125-appb-000002
由表1中的数据可知，一级发孔腐蚀液中加入羧酸类络合剂后(实施例1～5)，有利于腐蚀箔容量及折弯性能的提高，其机械性能更优。
以上结合具体实施例描述了本发明的技术原理。这些描述只是为了解释本发明的原理，而不能以任何方式解释为对本发明保护范围的限制。基于此处的解释，本领域的技术人员不需要付出创造性的劳动即可联想到本发明的其它具体实施方式，这些方式都将落入本发明的保护范围之内。

Claims (9)

  1. 一种铝电解电容器用阳极箔腐蚀工艺，包括前处理、一级发孔腐蚀、二级扩孔腐蚀、后处理，其特征在于，所述一级发孔腐蚀用腐蚀液中添加络合剂，所述络合剂为含羧酸类化合物或其盐。
  2. 根据权利要求1所述的铝电解电容器用阳极箔腐蚀工艺，其特征在于，所述含羧酸类化合物或其盐在一级发孔腐蚀用腐蚀液中的含量为0.1～100mM。
  3. 根据权利要求1或2所述的铝电解电容器用阳极箔腐蚀工艺，其特征在于，所述含羧酸类化合物或其盐为乙二胺四乙酸或其盐、二乙烯三胺五羧酸或其盐、葡萄糖酸或其盐、草酸或其盐中的一种或至少两种的组合。
  4. 根据权利要求3所述的铝电解电容器用阳极箔腐蚀工艺，其特征在于，所述乙二胺四乙酸或其盐在一级发孔腐蚀用腐蚀液中的含量为15～50mM，所述二乙烯三胺五羧酸或其盐在一级发孔腐蚀用腐蚀液中的含量为8～40mM，所述葡萄糖酸或其盐在一级发孔腐蚀用腐蚀液中的含量为0.4～80mM，所述草酸或其盐在一级发孔腐蚀用腐蚀液中的含量为1～50mM。
  5. 根据权利要求1所述的铝电解电容器用阳极箔腐蚀工艺，其特征在于，所述一级发孔腐蚀用腐蚀液为盐酸、硫酸、硝酸、磷酸及其所述酸的盐中的两种或两种以上的混合液。
  6. 根据权利要求5所述的铝电解电容器用阳极箔腐蚀工艺，其特征在于，所述一级发孔腐蚀用腐蚀液中，盐酸的浓度为1～11wt％，硫酸的浓度为40～63wt％，硝酸的浓度为1～18wt％，磷酸的浓度为1～57wt％。
  7. 根据权利要求6所述的铝电解电容器用阳极箔腐蚀工艺，其特征在于，所述一级发孔腐蚀用腐蚀液为3wt％HCl和30wt％H 2SO 4的水溶液。
  8. 根据权利要求1所述的铝电解电容器用阳极箔腐蚀工艺，其特征在于，所述一级发孔腐蚀的条件为：腐蚀温度为50～85℃，电流密度为0.1～2.5A/cm 2，腐蚀时间为1～5min。
  9. 根据权利要求8所述的铝电解电容器用阳极箔腐蚀工艺，其特征在于，所述一级发孔腐蚀的条件为：腐蚀温度为70℃，电流密度为0.6A/cm 2，腐蚀时间为1min。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113921282A (zh) * 2021-09-26 2022-01-11 内蒙古乌兰察布东阳光化成箔有限公司 一种铝电解电容器用中高压化成箔低损耗化成工艺

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108183033B (zh) * 2018-03-02 2020-07-07 东莞东阳光科研发有限公司 一种铝电解电容器用阳极箔腐蚀工艺
CN109750346A (zh) * 2018-12-17 2019-05-14 中南大学 一种中高压腐蚀箔的制作工艺
CN109727775B (zh) * 2018-12-28 2022-01-18 广西贺州市桂东电子科技有限责任公司 一种双v发孔腐蚀制备中高压阳极铝箔长短孔结构的方法
CN111472039A (zh) * 2020-03-27 2020-07-31 东莞东阳光科研发有限公司 一种铝电解电容器用中高压电极箔的制备方法
CN113628888B (zh) * 2021-10-09 2021-12-10 南通海星电子股份有限公司 一种孔长高一致性的腐蚀铝箔的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101425390A (zh) * 2008-07-29 2009-05-06 东莞市东阳光电容器有限公司 一种中高压阳极铝箔的腐蚀方法
CN101960544A (zh) * 2008-03-11 2011-01-26 日本轻金属株式会社 电解电容器用铝电极板的制造方法
CN105140039A (zh) * 2015-09-07 2015-12-09 江苏国瑞科技股份有限公司 一种铝箔腐蚀的前处理工艺
CN108183033A (zh) * 2018-03-02 2018-06-19 东莞东阳光科研发有限公司 一种铝电解电容器用阳极箔腐蚀工艺

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3185453B2 (ja) * 1993-03-19 2001-07-09 松下電器産業株式会社 アルミ電解コンデンサ用電極箔の製造方法
CN101425393B (zh) * 2008-07-29 2011-08-17 东莞市东阳光电容器有限公司 铝电解电容器用阴极箔的制造方法
CN101503801B (zh) * 2009-03-30 2010-10-20 日丰（清远）电子有限公司 一种电解电容器用铝箔腐蚀工艺
CN102426930A (zh) * 2011-08-17 2012-04-25 佛山科学技术学院 一种高压低比容阳极箔的腐蚀方法
CN103646787B (zh) * 2013-12-20 2016-09-07 严民 一种高比容高折曲电极箔腐蚀制造方法
CN103774205A (zh) * 2014-01-06 2014-05-07 广西贺州市桂东电子科技有限责任公司 中高压阳极铝箔二次纯化学侵蚀扩孔方法
CN104878441B (zh) * 2015-04-30 2017-07-04 聊城大学 一种铝电解电容器用阳极铝箔带有隧道枝孔的腐蚀工艺

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101960544A (zh) * 2008-03-11 2011-01-26 日本轻金属株式会社 电解电容器用铝电极板的制造方法
CN101425390A (zh) * 2008-07-29 2009-05-06 东莞市东阳光电容器有限公司 一种中高压阳极铝箔的腐蚀方法
CN105140039A (zh) * 2015-09-07 2015-12-09 江苏国瑞科技股份有限公司 一种铝箔腐蚀的前处理工艺
CN108183033A (zh) * 2018-03-02 2018-06-19 东莞东阳光科研发有限公司 一种铝电解电容器用阳极箔腐蚀工艺

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CN113921282A (zh) * 2021-09-26 2022-01-11 内蒙古乌兰察布东阳光化成箔有限公司 一种铝电解电容器用中高压化成箔低损耗化成工艺
CN113921282B (zh) * 2021-09-26 2023-11-17 内蒙古乌兰察布东阳光化成箔有限公司 一种铝电解电容器用中高压化成箔低损耗化成工艺

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