JP2005251884A - Method for manufacturing electrode foil for aluminum electrolytic capacitor - Google Patents
Method for manufacturing electrode foil for aluminum electrolytic capacitor Download PDFInfo
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- 239000011888 foil Substances 0.000 title claims abstract description 95
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 74
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003990 capacitor Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000005530 etching Methods 0.000 claims abstract description 98
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 230000007423 decrease Effects 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 5
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 4
- 239000001741 Ammonium adipate Substances 0.000 description 4
- 235000019293 ammonium adipate Nutrition 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000694440 Colpidium aqueous Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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Abstract
Description
本発明はアルミ電解コンデンサに使用される電極箔の製造方法に関するものである。 The present invention relates to a method for producing an electrode foil used for an aluminum electrolytic capacitor.
近年、電子機器の小型化、高信頼性化に伴い、アルミ電解コンデンサに対するユーザーからのニーズも小型化が強く要望されており、そのためにアルミ電解コンデンサに用いられる電極箔も従来以上に単位面積当たりの静電容量を高める必要が生じている。 In recent years, along with the downsizing and high reliability of electronic equipment, there has been a strong demand from users for aluminum electrolytic capacitors, and as a result, electrode foils used for aluminum electrolytic capacitors are more than per unit area. There is a need to increase the electrostatic capacity.
一般的なアルミ電解コンデンサは、アルミニウム箔をエッチング処理によって実効表面積を拡大させた表面に陽極酸化により誘電体酸化皮膜を形成した陽極箔とアルミニウム箔をエッチング処理によって実効表面積を拡大させた陰極箔とをセパレータを介して巻回することによりコンデンサ素子を形成し、このコンデンサ素子に駆動用電解液を含浸させるとともに、このコンデンサ素子を金属ケース内に封止することにより構成されている。 A general aluminum electrolytic capacitor includes an anode foil in which a dielectric oxide film is formed by anodic oxidation on a surface of which an effective surface area is expanded by etching the aluminum foil, and a cathode foil in which the effective surface area is expanded by etching the aluminum foil. The capacitor element is formed by winding the capacitor element through a separator, and the capacitor element is impregnated with a driving electrolyte, and the capacitor element is sealed in a metal case.
この種のアルミ電解コンデンサにおいて、その静電容量を高める或いは小形化を図るには、陽極箔の実効表面積を拡大し単位面積当たりの静電容量を高めることが必要不可欠になっており、陽極箔の実効表面積を拡大させるエッチング技術の開発が盛んに行われている。 In this type of aluminum electrolytic capacitor, it is essential to increase the effective surface area of the anode foil and increase the capacitance per unit area in order to increase its capacitance or reduce its size. The development of etching technology that expands the effective surface area of silicon has been actively conducted.
前記陽極箔のエッチング処理は、硫酸、硝酸、燐酸、蓚酸などの皮膜を形成する酸を添加した塩酸水溶液中で化学的あるいは電気化学的に行われているが、特に低圧用に使用される陽極箔のエッチング処理は、塩酸を主成分とする電解液中で交流電流を印加してエッチング処理する工程を数回繰り返し行うことにより、アルミニウム箔にエッチングピットを段階的に無数形成している。 The etching treatment of the anode foil is performed chemically or electrochemically in an aqueous hydrochloric acid solution to which an acid for forming a film such as sulfuric acid, nitric acid, phosphoric acid, or oxalic acid is added. In the etching process of the foil, an infinite number of etching pits are formed stepwise in the aluminum foil by repeatedly performing the etching process by applying an alternating current in an electrolyte mainly composed of hydrochloric acid several times.
この交流電流によるエッチング処理は、通常の電流波形は正弦波で、アルミニウム箔の表面にカソード電流が流れたときにアルミニウムの水和皮膜が形成され、アノード電流が流れたときに前記水和皮膜の欠陥部からエッチングピットが形成されて、この反応を繰り返されることにより無数のエッチングピットが形成されることが知られており、そのエッチング処理の電解液組成、交流電流の電流密度や周波数の条件を工夫・改善して、陽極箔の静電容量や機械的強度などの特性の向上を図っている。 In this etching process using an alternating current, the normal current waveform is a sine wave, and a hydrated film of aluminum is formed when a cathode current flows on the surface of the aluminum foil. It is known that etching pits are formed from defects and this reaction is repeated to form countless etching pits. The conditions of the electrolyte composition, the current density and frequency of the alternating current in the etching process are known. Ingenuity and improvement have been made to improve the characteristics of anode foil, such as capacitance and mechanical strength.
なお、この出願の発明に関連する先行技術文献情報としては、例えば、特許文献１、特許文献２が知られている。
しかしながら、前記塩酸を主成分とする電解液中でアルミニウム箔に交流電流を印加するエッチング処理において、一つのエッチング処理槽内では電流密度および周波数を一定値に規制してアルミニウム箔の表面積の拡大を図っているので、アルミニウム箔の表面積が過剰になると機械的強度が弱くなることから、アルミニウム箔の表面積をある領域までしか拡大することができないという課題を有している。 However, in the etching process in which an alternating current is applied to the aluminum foil in the electrolytic solution containing hydrochloric acid as a main component, the current density and frequency are restricted to a constant value in one etching treatment tank to increase the surface area of the aluminum foil. Therefore, since the mechanical strength becomes weak when the surface area of the aluminum foil becomes excessive, there is a problem that the surface area of the aluminum foil can be expanded only to a certain region.
また、前記特許文献１及び特許文献２等の技術は、種々の電流密度を変化させた交流エッチング方法が提案されているが、近年のアルミ電解コンデンサ用電極箔に対する要望に対して満足した電極箔を得ることが困難である。 Further, in the techniques of Patent Document 1 and Patent Document 2 and the like, an AC etching method in which various current densities are changed has been proposed, but the electrode foil satisfying the recent demand for electrode foils for aluminum electrolytic capacitors. Is difficult to obtain.
本発明は、前記従来の課題を解決するためのもので、アルミニウム箔の化学溶解反応、電気化学的反応、拡散現象を考慮し、緻密で高密度のエッチングピットを生成させて表面積を拡大し、静電容量を高くすることができるアルミ電解コンデンサ用電極箔の製造方法を提供するものである。 The present invention is for solving the above-mentioned conventional problems, taking into account the chemical dissolution reaction, electrochemical reaction, and diffusion phenomenon of aluminum foil, increasing the surface area by generating dense and high-density etching pits, The present invention provides a method for producing an electrode foil for an aluminum electrolytic capacitor capable of increasing the capacitance.
前記課題を解決するために、本発明は電解液中でアルミニウム箔に交流電流を印加してエッチングするエッチング処理を多段階に分けて行うアルミ電解コンデンサ用電極箔の製造方法であって、前記電解液は塩酸を主成分として硫酸、蓚酸、リン酸の少なくとも１種を添加した水溶液を用い、前記交流電流の印加する電流波形は振幅ゼロから時間ｔ１で最大振幅まで直線的に増加させ、その最大振幅から最大振幅の０．１〜０．５倍の振幅まで時間ｔ２で直線的に低下させた後振幅をゼロにする半波とした正負対称の波形からなり、始めのエッチング処理の電流波形を前記半波の時間ｔ１より時間ｔ２を長くなるようにし、後段のエッチング処理を行うにつれて始めのエッチング処理よりも半波の時間ｔ１を長くし、かつ時間ｔ２を短くなるようにしてエッチング処理を行うようにした製造方法とするものである。 In order to solve the above-mentioned problems, the present invention provides a method for producing an electrode foil for an aluminum electrolytic capacitor in which an etching process for applying an alternating current to an aluminum foil in an electrolytic solution to perform etching is performed in multiple stages, The solution is an aqueous solution containing hydrochloric acid as a main component and at least one of sulfuric acid, oxalic acid, and phosphoric acid added. The current waveform applied by the alternating current increases linearly from zero amplitude to the maximum amplitude at time t1, and the maximum It consists of a positive and negative symmetrical waveform that is a half wave in which the amplitude is reduced from zero to 0.1 to 0.5 times the maximum amplitude linearly at time t2 and then the amplitude becomes zero. The time t2 is made longer than the half-wave time t1, and as the subsequent etching process is performed, the half-wave time t1 is made longer than the first etching process, and the time t2 is shortened. Unishi Te in which a manufacturing method to perform the etching process.
本発明のアルミ電解コンデンサ用電極箔の製造方法は、電解液中でアルミニウム箔に交流電流を印加してエッチングするエッチング処理を多段階に分けて行うアルミ電解コンデンサ用電極箔の製造方法であって、前記電解液は塩酸を主成分として硫酸、蓚酸、リン酸の少なくとも１種を添加した水溶液を用い、前記交流電流の印加する電流波形は振幅ゼロから時間ｔ１で最大振幅まで直線的に増加させ、その最大振幅から最大振幅の０．１〜０．５倍の振幅まで時間ｔ２で直線的に低下させた後振幅をゼロにする半波とした正負対称の波形からなり、始めのエッチング処理の電流波形を前記半波の時間ｔ１より時間ｔ２を長くなるようにし、後段のエッチング処理を行うにつれて始めのエッチング処理よりも半波の時間ｔ１を長くし、かつ時間ｔ２を短くなるようにしてエッチング処理を行うようにした製造方法とすることにより、始めのエッチング処理では、振幅０から最大振幅までの立ち上がり部分で、均一に緻密なエッチングピットを発生させる時間ｔ１よりも次の最大振幅から最大振幅０．１〜０．５の振幅まで低下させた後振幅を０にしてエッチングピットを高密度に成長させる時間ｔ２を長くすることで、アルミニウム箔の表面から比較的浅い層に高密度のエッチングピットが形成できる。 The method for producing an electrode foil for an aluminum electrolytic capacitor according to the present invention is a method for producing an electrode foil for an aluminum electrolytic capacitor in which an etching process for applying an alternating current to an aluminum foil in an electrolytic solution to perform etching is performed in multiple stages. The electrolytic solution is an aqueous solution containing hydrochloric acid as a main component and at least one of sulfuric acid, oxalic acid, and phosphoric acid added, and the current waveform to which the alternating current is applied is linearly increased from zero amplitude to the maximum amplitude at time t1. , Consisting of a positive and negative symmetrical waveform in which the amplitude is reduced to zero to 0.5 times the maximum amplitude linearly at time t2 and then half the amplitude is made zero. The current waveform is made longer than the half-wave time t1, and the half-wave time t1 is made longer than the first etching process as the subsequent etching process is performed. By adopting a manufacturing method in which the etching process is performed such that t2 is shortened, in the first etching process, from the time t1 at which uniformly dense etching pits are generated at the rising portion from the amplitude 0 to the maximum amplitude. However, after the amplitude is reduced from the next maximum amplitude to the maximum amplitude of 0.1 to 0.5 and the time t2 for growing the etching pits at a high density is increased by setting the amplitude to 0, the surface of the aluminum foil is relatively High-density etching pits can be formed in the shallow layer.
また、後段のエッチング処理ほど電流波形の時間ｔ１を長くし、かつ時間ｔ２を短くすることにより、発生するエッチングピットはアルミニウム箔の深さ方向に進行する傾向が強まり、前半のエッチング処理工程で形成したエッチングピットをさらに高密度に数多く形成することができるので、アルミニウム箔の表面積の拡大を効率的に行い、アルミ電解コンデンサ用電極箔の静電容量を高めることができる。 In addition, by increasing the time t1 of the current waveform and shortening the time t2 in the subsequent etching process, the generated etching pits tend to travel in the depth direction of the aluminum foil, and are formed in the first half etching process. Since a large number of etched pits can be formed at a higher density, the surface area of the aluminum foil can be efficiently increased, and the capacitance of the electrode foil for aluminum electrolytic capacitors can be increased.
さらに、振幅を徐々に０にすると交流電流によるアルミニウムの溶解力が失われてしまうので、最大振幅から低下させる途中で振幅を０にすることにより、化学的な無効溶解を抑制することができる。 Further, when the amplitude is gradually reduced to 0, the dissolving power of aluminum due to the alternating current is lost. Therefore, the chemical ineffective dissolution can be suppressed by setting the amplitude to 0 in the middle of the reduction from the maximum amplitude.
以上のことから、アルミニウム箔の表面積の拡大を効率的に行い、アルミ電解コンデンサ用電極箔の静電容量を高めることができるという効果を奏するものである。 From the above, it is possible to efficiently increase the surface area of the aluminum foil and increase the capacitance of the electrode foil for an aluminum electrolytic capacitor.
（実施の形態１）
以下、実施の形態１を用いて、本発明の特に請求項１および請求項３、４に記載の発明について説明する。
(Embodiment 1)
Hereinafter, the first and third aspects of the present invention will be described using the first embodiment.
本実施の形態１におけるアルミ電解コンデンサ用電極箔の製造方法は、まず、アルミニウム箔は厚さ１００μｍ、純度９９．９８％のものを用いる。このアルミニウム箔は必要に応じて前処理を行う。 In the manufacturing method of the electrode foil for an aluminum electrolytic capacitor in the first embodiment, first, an aluminum foil having a thickness of 100 μm and a purity of 99.98% is used. This aluminum foil is pretreated as necessary.
次に、塩酸、硫酸、リン酸、硝酸等の酸性水溶液の電解液（電解液中のアルミニウム濃度を調整する）に前記アルミニウム箔を浸漬し、エッチング処理を数段階に分けて行う。最後に、硫酸の水溶液に浸漬して脱塩素処理を行い、熱処理を行って、アルミ電解コンデンサ用電極箔となるエッチング箔を作製する。 Next, the aluminum foil is immersed in an electrolytic solution (adjusting the aluminum concentration in the electrolytic solution) of an acidic aqueous solution such as hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, and etching is performed in several stages. Finally, it is immersed in an aqueous solution of sulfuric acid, dechlorinated, and heat-treated to produce an etching foil that becomes an electrode foil for an aluminum electrolytic capacitor.
前記交流電流の電流波形は図１（ａ）、（ｂ）に示すように、振幅ゼロから最大振幅Ａ１まで時間ｔ１で直線的に増加させ、その最大振幅Ａ１から最大振幅Ａ１の０．１〜０．５倍の振幅Ａ２まで時間ｔ２で直線的に低下させた後振幅をゼロにする半波からなる正負対称の波形であり、この電流波形を１段目のエッチング処理では同図（ａ）に示すように半波の時間ｔ１より時間ｔ２を長くなるようにし、後段のエッチング処理になるにつれて同図（ｂ）に示すように時間ｔ１を１段目のエッチング処理よりも長くして、かつ時間ｔ２を短くすることにより、１段目のエッチング処理工程では、振幅ゼロから最大振幅Ａ１までの立ち上がり部分で均一に緻密なエッチングピットを発生させ、次の最大振幅Ａ１から最大振幅Ａ１の０．１〜０．５倍の振幅Ａ２まで低下させた後振幅をゼロにして時間ｔ２を時間ｔ１よりも長くすることにより、エッチングピットを高密度に成長させ、アルミニウム箔の表面から比較的浅い層に高密度のエッチングピットが形成できる。 As shown in FIGS. 1A and 1B, the current waveform of the alternating current is increased linearly from time zero to maximum amplitude A1 at time t1, and from 0.1 to the maximum amplitude A1 of the maximum amplitude A1. This is a positive / negative symmetrical waveform consisting of a half wave that is reduced linearly at time t2 to 0.5 times amplitude A2 and then the amplitude becomes zero. This current waveform is shown in FIG. The time t2 is set to be longer than the half-wave time t1 as shown in FIG. 6B, and the time t1 is set longer than the first etching process as shown in FIG. By shortening the time t2, in the etching process of the first stage, uniform and dense etching pits are generated at the rising portion from the amplitude zero to the maximum amplitude A1, and the next maximum amplitude A1 to 0. 1-0. After the amplitude is reduced to twice the amplitude A2, the amplitude is made zero and the time t2 is longer than the time t1, so that the etching pits are grown at a high density, and the high density etching pits are formed from the surface of the aluminum foil to a relatively shallow layer. Can be formed.
また、後段のエッチング処理になるほど半波の時間ｔ１を長くし、かつ時間ｔ２を短くすることにより、発生するエッチングピットはアルミニウム箔の深さ方向に進行する傾向が強まり、前半のエッチング処理工程で形成したエッチングピットをさらに高密度に数多く形成することができる。 In addition, the longer the half wave time t1 and the shorter the time t2 are, the more the etching process at the later stage is, the more the etching pits that are generated tend to travel in the depth direction of the aluminum foil. Many formed etching pits can be formed with higher density.
また、前記電流波形の半波の時間（ｔ１＋ｔ２）を後段のエッチング処理になるほど長くなるようにする、或いは、前記電流波形Ａ１の最大振幅の０．１〜０．５倍の振幅Ａ２を後段のエッチング処理になるほど高くすることにより、後段のエッチング処理でのエッチングピットの密度をさらに高めることができる。 Further, the half-wave time (t1 + t2) of the current waveform is made longer as the subsequent etching process is performed, or the amplitude A2 of 0.1 to 0.5 times the maximum amplitude of the current waveform A1 is set to the subsequent stage. By making it high enough to be an etching process, the density of etching pits in the subsequent etching process can be further increased.
以下、具体的な実施例について説明する。 Specific examples will be described below.
（実施例１）
まず、厚さ１００μｍ、純度９９．９８％のアルミニウム箔を用い、リン酸濃度が１．０ｗｔ％の９０℃の水溶液に６０秒間浸漬して前処理を行う。
(Example 1)
First, an aluminum foil having a thickness of 100 μm and a purity of 99.98% is used, and pretreatment is performed by dipping in a 90 ° C. aqueous solution having a phosphoric acid concentration of 1.0 wt% for 60 seconds.
次に、塩酸５ｗｔ％、塩化アルミニウム２ｗｔ％、硫酸０．１ｗｔ％、リン酸０．５ｗｔ％、硝酸０．２ｗｔ％に調整した温度３０℃の電解液（電解液中のアルミニウム濃度を０．１ｗｔ％に調整）に前記アルミニウム箔を浸漬し、エッチング処理を４段階に分けて行った。 Next, an electrolytic solution at a temperature of 30 ° C. adjusted to 5 wt% hydrochloric acid, 2 wt% aluminum chloride, 0.1 wt% sulfuric acid, 0.5 wt% phosphoric acid, and 0.2 wt% nitric acid (the aluminum concentration in the electrolytic solution is 0.1 wt%) The aluminum foil was soaked in 4%, and the etching process was performed in four stages.
最後に、硫酸１０ｗｔ％の６０℃の水溶液で１００秒間の浸漬処理を行い、２５０℃で１２０秒間の熱処理を行って、アルミ電解コンデンサ用電極箔となるエッチング箔を作製した。 Finally, an immersion treatment was performed for 100 seconds with an aqueous solution of 10 wt% sulfuric acid at 60 ° C. and a heat treatment was performed at 250 ° C. for 120 seconds to produce an etching foil to be an electrode foil for an aluminum electrolytic capacitor.
前記交流電流の電流波形は、振幅ゼロから最大振幅Ａ１までの時間ｔ１とその最大振幅Ａ１から低下させる時間ｔ２の半波の時間を３０ｍｓとし、１段目〜４段目の時間ｔ１と時間ｔ２の値を（表１）に示す条件にした。また、最大振幅Ａ１となる電流密度を０．２０Ａ／ｃｍ2として、最大振幅Ａ１から時間ｔ２で直線的に低下させる振幅Ａ２を、最大値の０．０５倍になるようにした。 In the current waveform of the alternating current, the time t1 from the amplitude zero to the maximum amplitude A1 and the half wave time of the time t2 to be reduced from the maximum amplitude A1 are set to 30 ms, and the time t1 and time t2 in the first to fourth stages. Were set to the conditions shown in (Table 1). The current density at which the maximum amplitude A1 is reached is 0.20 A / cm 2 , and the amplitude A2 that linearly decreases from the maximum amplitude A1 at time t2 is set to 0.05 times the maximum value.
（実施例２）
前記実施例１において、最大振幅Ａ１から時間ｔ２で直線的に低下させる振幅Ａ２を、最大振幅Ａ１の０．１倍になるようにした以外は前記実施例１と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。
(Example 2)
In the first embodiment, the electrode for an aluminum electrolytic capacitor is the same as the first embodiment except that the amplitude A2 that linearly decreases from the maximum amplitude A1 at time t2 is 0.1 times the maximum amplitude A1. The etching foil used as foil was produced.
（実施例３）
前記実施例１において、最大振幅Ａ１から時間ｔ２で直線的に低下させる振幅Ａ２を、最大振幅Ａ１の０．３倍になるようにした以外は前記実施例１と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。
(Example 3)
In the first embodiment, the electrode for an aluminum electrolytic capacitor is the same as the first embodiment except that the amplitude A2 linearly decreased from the maximum amplitude A1 at time t2 is 0.3 times the maximum amplitude A1. The etching foil used as foil was produced.
（実施例４）
前記実施例１において、最大振幅Ａ１から時間ｔ２で直線的に低下させる振幅Ａ２を、最大振幅Ａ１の０．５倍になるようにした以外は前記実施例１と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。
Example 4
In the first embodiment, the electrode for an aluminum electrolytic capacitor is the same as the first embodiment except that the amplitude A2 that linearly decreases from the maximum amplitude A1 at time t2 is 0.5 times the maximum amplitude A1. The etching foil used as foil was produced.
（実施例５）
前記実施例１において、最大振幅Ａ１から時間ｔ２で直線的に低下させる振幅Ａ２を、最大振幅Ａ１の０．７倍になるようにした以外は前記実施例１と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。
(Example 5)
In the first embodiment, the electrode for an aluminum electrolytic capacitor is the same as the first embodiment except that the amplitude A2 linearly decreased from the maximum amplitude A1 at time t2 is 0.7 times the maximum amplitude A1. The etching foil used as foil was produced.
（実施例６）
前記実施例１において、最大振幅Ａ１から時間ｔ２で直線的に低下させる振幅Ａ２を、最大振幅Ａ１の１．０倍になるようにした以外は前記実施例１と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。
(Example 6)
In the first embodiment, the electrode for an aluminum electrolytic capacitor is the same as the first embodiment except that the amplitude A2 that linearly decreases from the maximum amplitude A1 at time t2 is 1.0 times the maximum amplitude A1. The etching foil used as foil was produced.
（実施例７）
前記実施例１において、電流波形を（表２）に示す条件にした以外は前記実施例１と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。
(Example 7)
An etching foil serving as an electrode foil for an aluminum electrolytic capacitor was produced in the same manner as in Example 1 except that the current waveform was changed to the conditions shown in Table 2 in Example 1.
（実施例８）
前記実施例７において、電流波形の振幅Ａ２を１段目から順にＡ１×０．２、Ａ１×０．３、Ａ１×０．４、Ａ１×０．５にした以外は前記実施例７と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。
(Example 8)
Example 7 is the same as Example 7 except that the amplitude A2 of the current waveform is set to A1 × 0.2, A1 × 0.3, A1 × 0.4, and A1 × 0.5 in order from the first stage. Thus, an etching foil to be an electrode foil for an aluminum electrolytic capacitor was produced.
（比較例１）
前記実施例１において、交流電流の電流波形を半波が３０secとなる正弦波を用いた以外は前記実施例１と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。
(Comparative Example 1)
In Example 1, an etching foil serving as an electrode foil for an aluminum electrolytic capacitor was produced in the same manner as in Example 1 except that a sine wave having a half wave of 30 seconds was used as the current waveform of the alternating current.
（比較例２）
前記実施例１において、交流電流の電流波形を振幅ゼロから最大振幅Ａ１までの時間ｔ１を１０msとし、その最大振幅Ａ１から低下させる時間ｔ２を２０msとして１段目〜４段目のエッチング処理を行った以外は前記実施例１と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。
(Comparative Example 2)
In the first embodiment, the first to fourth etching processes are performed by setting the time waveform t1 from the zero amplitude to the maximum amplitude A1 to 10 ms and the time t2 to decrease from the maximum amplitude A1 to 20 ms. Except for the above, an etching foil to be an electrode foil for an aluminum electrolytic capacitor was produced in the same manner as in Example 1.
前記実施例１〜８および比較例１と比較例２のエッチング箔を１５％アジピン酸アンモニウム水溶液中にてそれぞれ１９Ｖ、６４Ｖの電圧を印加して化成し、その静電容量を１５％アジピン酸アンモニウム水溶液中にて測定した。その結果を（表３）に示す。 The etching foils of Examples 1 to 8 and Comparative Examples 1 and 2 were formed by applying voltages of 19 V and 64 V, respectively, in a 15% ammonium adipate aqueous solution, and the capacitance was 15% ammonium adipate. Measurement was performed in an aqueous solution. The results are shown in (Table 3).
（表３）より明らかなように、電流波形の半波を振幅ゼロから最大振幅Ａ１までの時間ｔ１と最大振幅Ａ１から低下する時間ｔ２を、１段目のエッチング処理では時間ｔ１より時間ｔ２を長くするようにし、後段のエッチング処理になるにつれて時間ｔ１を１段目のエッチング処理よりも長くして時間ｔ２を短くするようにして、かつ最大振幅Ａ１から時間ｔ２後の振幅Ａ２を最大振幅Ａ１の０．１〜０．５倍にすることにより、１段目のエッチング処理でアルミニウム箔の表面から比較的浅い層に高密度のエッチングピットを形成し、２段目以降のエッチング処理で、１段目で発生させたエッチングピットをアルミニウム箔の深さ方向にさらに高密度に数多く形成することができるので、比較例１および比較例２よりも静電容量を高めることができる。 As is clear from Table 3, the time t1 from the amplitude zero to the maximum amplitude A1 and the time t2 when the half wave of the current waveform decreases from the maximum amplitude A1 are set to the time t2 from the time t1 in the first stage etching process. The time t1 is made longer than the first-stage etching process and the time t2 is shortened as the subsequent etching process is performed, and the amplitude A2 after the time t2 from the maximum amplitude A1 is set to the maximum amplitude A1. 0.1 to 0.5 times higher than that of the aluminum foil, a high-density etching pit is formed in the relatively shallow layer from the surface of the aluminum foil by the first-stage etching process, and the etching process after the second stage is 1 Since a large number of etching pits generated at the stage can be formed at a higher density in the depth direction of the aluminum foil, the capacitance can be increased more than in Comparative Example 1 and Comparative Example 2. Can.
また、実施例７のように後段のエッチング処理になるほど電流波形の半波の時間を長くすることにより、実施例２〜４で得た値よりもさらに静電容量の高いエッチング箔を得ることができる。 Moreover, the etching foil having a higher capacitance than the values obtained in Examples 2 to 4 can be obtained by increasing the half-wave time of the current waveform as the subsequent etching process is performed as in Example 7. it can.
なお、実施例１のように電流波形の振幅を徐々に低下させ、振幅Ａ２が最大振幅Ａ１の０．１倍未満にすると交流電流によるアルミニウムの溶解力が失われ、化学的な無効溶解を引き起こしてしまうので、静電容量をあまり高くすることができない。また、実施例５および実施例６のように振幅Ａ２が高くなると、エッチングピットが食いつぶされ、やはり静電容量を高くすることができない。 In addition, when the amplitude of the current waveform is gradually decreased as in Example 1 and the amplitude A2 is less than 0.1 times the maximum amplitude A1, the dissolving power of aluminum due to the alternating current is lost, causing chemical ineffective dissolution. Therefore, the electrostatic capacity cannot be increased too much. Further, when the amplitude A2 is increased as in the fifth and sixth embodiments, the etching pits are eroded and the electrostatic capacity cannot be increased.
（実施の形態２）
以下、実施の形態２を用いて、本発明の特に請求項２〜５に記載の発明について説明する。
(Embodiment 2)
The second embodiment of the present invention will be described below with reference to the second to fifth aspects of the present invention.
前記実施の形態１において、交流電流の電流波形を図２に示すように、振幅ゼロから最大振幅Ａ１まで時間ｔ１で直線的に増加させ、その最大振幅Ａ１から最大振幅Ａ１の０．６〜０．９倍の振幅Ａ３まで時間ｔ３で直線的に低下させ、さらにそこから最大振幅Ａ１の０．１〜０．５倍の振幅Ａ２まで時間ｔ２で直線的に低下させた後振幅をゼロになる半波からなる正負対称の波形を用いた以外は前記実施の形態１と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。 In the first embodiment, as shown in FIG. 2, the current waveform of the alternating current is increased linearly from time zero to maximum amplitude A1 at time t1, and 0.6 to 0 from the maximum amplitude A1 to the maximum amplitude A1. .. Decrease linearly at time t3 to 9 times amplitude A3, and further decrease linearly at time t2 from 0.1 to 0.5 times the maximum amplitude A1 to amplitude A2, and then the amplitude becomes zero An etching foil serving as an electrode foil for an aluminum electrolytic capacitor was produced in the same manner as in the first embodiment except that a positive / negative symmetrical waveform consisting of a half wave was used.
前記電流波形を最大振幅Ａ１から最大振幅Ａ１の０．６〜０．９倍の振幅Ａ３まで時間ｔ３で直線的に一旦低下させたことにより、それ以降の時間ｔ２における余分なエッチングピットの発生を防ぎ、また十分なエッチングピット成長時間を確保することで大きさの揃ったエッチングピットを形成することができるので、アルミ電解コンデンサ用電極箔の静電容量を高めることができる。 The current waveform is once decreased linearly at time t3 from the maximum amplitude A1 to the amplitude A3 which is 0.6 to 0.9 times the maximum amplitude A1, thereby generating extra etching pits at the subsequent time t2. Since the etching pits having a uniform size can be formed by preventing and securing sufficient etching pit growth time, the capacitance of the electrode foil for an aluminum electrolytic capacitor can be increased.
また、前記電流波形の半波の時間（ｔ１＋ｔ２＋ｔ３）を後段のエッチング処理になるほど長くなるようにする、或いは、前記電流波形の最大振幅Ａ１の０．１〜０．５倍の振幅Ａ２または最大振幅Ａ１の０．６〜０．９倍の振幅Ａ３を後段のエッチング処理になるほど高くすることにより、後段のエッチング処理でのエッチングピットの密度をさらに高めることができる。 Further, the half-wave time (t1 + t2 + t3) of the current waveform is increased as the subsequent etching process is performed, or the amplitude A2 or the maximum amplitude of 0.1 to 0.5 times the maximum amplitude A1 of the current waveform. By making the amplitude A3 0.6 to 0.9 times A1 higher as the subsequent etching process is performed, the density of etching pits in the subsequent etching process can be further increased.
以下、具体的な実施例について説明する。 Specific examples will be described below.
（実施例９）
前記実施例１において、交流電流の電流波形を図２に示すような波形にし、その条件を（表４）に示す。また、最大振幅Ａ１となる電流密度を０．２０Ａ／ｃｍ2として、最大振幅Ａ１から時間ｔ２で直線的に低下させる振幅Ａ２を、最大値の０．３倍になるようにした以外は前記実施例１と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。
Example 9
In the first embodiment, the alternating current waveform is as shown in FIG. 2, and the conditions are shown in Table 4. Further, the above-described implementation is performed except that the current density at which the maximum amplitude A1 is set is 0.20 A / cm 2 and the amplitude A2 that linearly decreases from the maximum amplitude A1 at time t2 is 0.3 times the maximum value. The etching foil used as the electrode foil for aluminum electrolytic capacitors was produced like Example 1. FIG.
（実施例１０）
前記実施例９において、最大振幅Ａ１から時間ｔ３で直線的に低下させる振幅Ａ３を、１段目から順にＡ１×０．６、Ａ１×０．７、Ａ１×０．８、Ａ１×０．９にした以外は前記実施例９と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。
(Example 10)
In the ninth embodiment, the amplitude A3 that linearly decreases from the maximum amplitude A1 at time t3 is set to A1 × 0.6, A1 × 0.7, A1 × 0.8, A1 × 0.9 in order from the first stage. Except for the above, an etching foil to be an electrode foil for an aluminum electrolytic capacitor was produced in the same manner as in Example 9.
（実施例１１）
前記実施例９において、電流波形の条件を（表５）に示す条件にした以外は前記実施例９と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。
(Example 11)
An etching foil serving as an electrode foil for an aluminum electrolytic capacitor was produced in the same manner as in Example 9 except that the current waveform was changed to the conditions shown in Table 5 in Example 9.
（実施例１２）
前記実施例９において、最大振幅Ａ１から時間ｔ２で直線的に低下させる振幅Ａ２を、１段目から順にＡ１×０．２、Ａ１×０．３、Ａ１×０．４、Ａ１×０．５にした以外は前記実施例９と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。
(Example 12)
In the ninth embodiment, the amplitude A2 that linearly decreases from the maximum amplitude A1 at time t2 is A1 × 0.2, A1 × 0.3, A1 × 0.4, A1 × 0.5 in order from the first stage. Except for the above, an etching foil to be an electrode foil for an aluminum electrolytic capacitor was produced in the same manner as in Example 9.
（実施例１３）
前記実施例９において、最大振幅Ａ１から時間ｔ３で直線的に低下させる振幅Ａ３を、１段目〜４段目の値をＡ１×０．５倍にした以外は前記実施例９と同様にしてアルミ電解コンデンサ用電極箔となるエッチング箔を作製した。
(Example 13)
In the ninth embodiment, the amplitude A3 that linearly decreases from the maximum amplitude A1 at time t3 is the same as the ninth embodiment except that the value of the first to fourth stages is increased by A1 × 0.5. The etching foil used as the electrode foil for aluminum electrolytic capacitors was produced.
前記実施例９〜１３のエッチング箔を１５％アジピン酸アンモニウム水溶液中にてそれぞれ１９Ｖ、６４Ｖの電圧を印加して化成し、その静電容量を１５％アジピン酸アンモニウム水溶液中にて測定した。その結果を（表６）に示す。 The etching foils of Examples 9 to 13 were formed by applying voltages of 19 V and 64 V, respectively, in a 15% ammonium adipate aqueous solution, and the capacitance was measured in a 15% ammonium adipate aqueous solution. The results are shown in (Table 6).
（表６）より明らかなように、最大振幅Ａ１から最大振幅Ａ１の０．６〜０．９倍の振幅Ａ３まで時間ｔ３で直線的に一旦低下させ、さらにそこから最大振幅Ａ１の０．１〜０．５倍の振幅Ａ２まで時間ｔ２で直線的に低下させた後振幅がゼロになる波形を用いることにより、前記実施の形態１で得られた値よりもさらに高い静電容量のものが得られる。 As is clear from (Table 6), it is once decreased linearly at time t3 from the maximum amplitude A1 to an amplitude A3 that is 0.6 to 0.9 times the maximum amplitude A1, and further from there, the maximum amplitude A1 is 0.1. By using a waveform in which the amplitude becomes zero after linearly decreasing to an amplitude A2 of .about.0.5 times at time t2, the capacitance is higher than the value obtained in the first embodiment. can get.
また、実施例１３のように最大振幅Ａ１から時間ｔ３で直線的に低下させる振幅Ａ３を、１段目〜４段目の値をＡ１×０．５にしたものは、実施例９〜実施例１２よりもエッチング箔の静電容量よりも低い値になる。 Further, as in the thirteenth embodiment, the amplitude A3 that linearly decreases from the maximum amplitude A1 at the time t3 and the values of the first to fourth steps are set to A1 × 0.5 are shown in the ninth to ninth embodiments. It becomes a value lower than the capacitance of the etching foil than 12.
なお、前記実施の形態１及び実施の形態２では半波の振幅ゼロから最大振幅Ａ１まで時間ｔ１で直線的に増加させたが、図３に示すように半波の振幅ゼロから最大振幅Ａ１まで急激に増加させた後、最大振幅Ａ１から最大振幅Ａ１の０．６〜０．９倍の振幅Ａ３まで低下させた電流波形を用いても本発明の効果を得ることができる。 In the first and second embodiments, the half wave amplitude is increased linearly from time zero to the maximum amplitude A1 at time t1, but as shown in FIG. 3, from half wave amplitude zero to the maximum amplitude A1. The effect of the present invention can also be obtained by using a current waveform that has been rapidly increased and then decreased from the maximum amplitude A1 to an amplitude A3 that is 0.6 to 0.9 times the maximum amplitude A1.
本発明は、アルミニウム箔の化学溶解反応、電気化学的反応、拡散現象を考慮し、緻密で高密度のエッチングピットを生成させて表面積を拡大し、静電容量の高い電極箔を得ることにより、その電極箔を用いたアルミ電解コンデンサの定格容量を高めることができ、電子機器の小型化や高信頼性化を図ることができる。 The present invention takes into account the chemical dissolution reaction, electrochemical reaction, and diffusion phenomenon of aluminum foil, generates dense and high-density etching pits, expands the surface area, and obtains an electrode foil with a high capacitance. The rated capacity of the aluminum electrolytic capacitor using the electrode foil can be increased, and the electronic device can be made smaller and more reliable.
ｔ１ 電流波形における振幅ゼロから最大振幅Ａ１に達するまでの時間
ｔ２ 電流波形における最大振幅Ａ１から振幅ゼロに達するまでの時間
Ａ１ 電流波形における最大振幅
Ａ２ 電流波形における最大振幅Ａ１の０．１〜０．５倍の振幅
t1 Time to reach maximum amplitude A1 from zero amplitude in current waveform t2 Time to reach amplitude zero from maximum amplitude A1 in current waveform A1 Maximum amplitude in current waveform A2 0.1 to 0 of maximum amplitude A1 in current waveform. 5 times the amplitude
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Cited By (2)
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| JP2007123552A (en) * | 2005-10-28 | 2007-05-17 | Nichicon Corp | Manufacturing method for etching foil for electrolytic capacitor |
| JP7454783B2 (en) | 2019-10-30 | 2024-03-25 | パナソニックＩｐマネジメント株式会社 | Manufacturing method of electrode foil for electrolytic capacitors |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007123552A (en) * | 2005-10-28 | 2007-05-17 | Nichicon Corp | Manufacturing method for etching foil for electrolytic capacitor |
| JP7454783B2 (en) | 2019-10-30 | 2024-03-25 | パナソニックＩｐマネジメント株式会社 | Manufacturing method of electrode foil for electrolytic capacitors |
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