JP3371362B2 - Method for producing electrode foil for aluminum electrolytic capacitor - Google Patents
Method for producing electrode foil for aluminum electrolytic capacitorInfo
- Publication number
- JP3371362B2 JP3371362B2 JP17206398A JP17206398A JP3371362B2 JP 3371362 B2 JP3371362 B2 JP 3371362B2 JP 17206398 A JP17206398 A JP 17206398A JP 17206398 A JP17206398 A JP 17206398A JP 3371362 B2 JP3371362 B2 JP 3371362B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- aqueous solution
- electrolytic capacitor
- treatment
- aluminum electrolytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- ing And Chemical Polishing (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本願発明は、アルミニウム電
解コンデンサ用電極箔、特に陰極用アルミニウム箔及び
低圧の陽極用アルミニウム箔の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an electrode foil for an aluminum electrolytic capacitor, particularly an aluminum foil for a cathode and a low voltage aluminum foil for an anode.
【0002】[0002]
【従来の技術】従来、アルミニウム電解コンデンサ用電
極箔は、塩化物を含む水溶液中で化学的又は電気化学的
エッチングによって粗面化されたエッチド箔を、これに
残存する塩素イオンを脱塩素イオン処理した後に、陰極
用アルミニウム箔の場合にはそのエッチド箔表面に安定
化皮膜を形成させる処理を、また陽極用アルミニウム箔
の場合には化成処理で酸化皮膜を形成させる処理を行う
ことによって製造されており、脱塩素イオン処理として
は、りん酸、硫酸、硝酸などの酸水溶液による化学処理
で行う方法または特公昭63−16480号公報で示さ
れるように、硝酸水溶液中で電気化学的に塩素イオンを
除去する方法が知られている。2. Description of the Related Art Conventionally, an electrode foil for an aluminum electrolytic capacitor is an etched foil roughened by chemical or electrochemical etching in an aqueous solution containing chloride, and chlorine ions remaining on the etched foil are dechlorinated. After that, in the case of the aluminum foil for the cathode, it is manufactured by performing a treatment for forming a stabilizing film on the surface of the etched foil, and for the aluminum foil for the anode, performing a treatment for forming an oxide film by chemical conversion treatment. As the dechlorination treatment, a method of performing chemical treatment with an acid aqueous solution of phosphoric acid, sulfuric acid, nitric acid or the like, or as disclosed in Japanese Patent Publication No. 63-16480, electrochemically removes chlorine ions in a nitric acid aqueous solution. Methods of removing are known.
【0003】[0003]
【発明が解決しようとする課題】しかしながら、近年ア
ルミニウム電解コンデンサの小型化にともない単位面積
当りの静電容量を増大させる必要があり、そのためエッ
チド箔はより一層粗面化され微細なエッチピット構造を
有するに至っている。このように微細に粗面化されたア
ルミニウム箔から従来の方法で残留塩素イオンを除去す
るには、脱塩素イオン処理を強く行なわなければなら
ず、その結果、微細なエッチピットを溶解してしまい、
かえって静電容量の減少をもたらすという不都合があっ
た。However, with the recent miniaturization of aluminum electrolytic capacitors, it is necessary to increase the capacitance per unit area. Therefore, the etched foil is further roughened to have a fine etch pit structure. Have come to possess. In order to remove the residual chlorine ions from the finely roughened aluminum foil by the conventional method, dechlorination treatment must be strongly performed, resulting in the dissolution of fine etch pits. ,
On the contrary, there is a disadvantage that the capacitance is reduced.
【0004】[0004]
【課題を解決するための手段】そこで本願発明は上記し
た従来の不都合を解消するために、アルミニウム箔を塩
化物を含む水溶液中で化学的又は電気化学的エッチング
により粗面化した後、脱塩素イオン処理を行う際、脱塩
素イオン処理工程を前段と後段との2段階に分け、その
前段においては、りん酸、硫酸、硝酸などの無機酸の水
溶液中に浸せきして行い、後段においては、しゅう酸、
くえん酸、酒石酸などの有機酸の水溶液中に浸せきして
行うことを特徴としたものである。In order to solve the above-mentioned conventional inconveniences, the present invention is to dechlorinate aluminum foil after roughening it by chemical or electrochemical etching in an aqueous solution containing chloride. When carrying out the ion treatment, the dechlorination treatment step is divided into two stages, a front stage and a rear stage, and in the front stage, it is immersed in an aqueous solution of an inorganic acid such as phosphoric acid, sulfuric acid or nitric acid, and in the rear stage, Oxalic acid,
It is characterized by being immersed in an aqueous solution of an organic acid such as citric acid or tartaric acid.
【0005】上記において、前段で使用するりん酸、硫
酸又は硝酸の場合の水溶液の濃度は好ましくは0.5w
t%から30wt%の範囲で、かつ水溶液の温度が20
℃から80℃の範囲であり、濃度及び温度が上記の範囲
を超えて低いと塩素イオンの除去効果は得られず、逆に
高いとアルミニウムの溶解反応が強くなり拡面倍率が低
下して静電容量の減少をもたらす。In the above, in the case of phosphoric acid, sulfuric acid or nitric acid used in the preceding stage, the concentration of the aqueous solution is preferably 0.5 w.
In the range of t% to 30 wt% and the temperature of the aqueous solution is 20
If the concentration and temperature are lower than the above range, the chlorine ion removing effect cannot be obtained. It brings about a decrease in electric capacity.
【0006】また後段で使用するしゅう酸、くえん酸又
は酒石酸の場合の水溶液中の濃度は好ましくは0.2w
t%から10wt%の範囲で、かつ水溶液の温度は30
℃から90℃の範囲であり、濃度及び温度がこの範囲を
超えて低いと塩素イオンの除去効果が得られず、逆に高
いとアルミニウムの溶解反応が強くなり拡面倍率が低下
して静電容量の減少をもたらす。In the case of oxalic acid, citric acid or tartaric acid used in the latter stage, the concentration in the aqueous solution is preferably 0.2 w.
In the range of t% to 10 wt% and the temperature of the aqueous solution is 30
It is in the range of ℃ to 90 ℃. If the concentration and temperature are lower than this range, the chlorine ion removal effect cannot be obtained. Brings capacity reduction.
【0007】[0007]
【作用】上記したように本願発明によれば、脱塩素イオ
ン処理を、酸の種類を変えて2段階で行なうものである
から、一定の無機酸水溶液中で1段階で行なう従来の脱
塩素イオン処理に比し、その無機酸水溶液による脱塩素
イオン処理で除去されなかった塩素イオンは、後段の有
機酸水溶液処理によって効果的に除去され、しかもアル
ミニウムの溶解が少ないので、静電容量の低下も少なく
することができる。As described above, according to the present invention, since the dechlorination treatment is carried out in two steps by changing the kind of acid, the conventional dechlorination treatment carried out in one step in a constant inorganic acid aqueous solution. Compared to the treatment, chlorine ions not removed by the dechlorination treatment with the inorganic acid aqueous solution are effectively removed by the subsequent organic acid aqueous solution treatment, and the aluminum is less dissolved, so the capacitance is also reduced. Can be reduced.
【0008】[0008]
【実施例】以下本願発明の実施例を詳述する。
実施例1
(1)エッチング工程
純度99.9%、厚さ90μmのアルミニウム箔を、
5.5wt%の塩素と1.5wt%のりん酸と0.5w
t%の硝酸と2.0wt%の塩化アルミニウムとを含む
水溶液から成る18℃の電解液中で10Hz、電流密度
120mA/cm2 の三角波交流電流で18分間エッチ
ングを行ない、イオン交換水で洗浄した。
(2)脱塩素イオン処理工程
60℃の5.0wt%の硫酸水溶液中で2分間前段の脱
塩素イオン処理を行なった後、50℃の1.0wt%の
しゅう酸水溶液に1分30秒間浸せきして後段の脱塩素
イオン処理を行ない、イオン交換水で洗浄した。EXAMPLES Examples of the present invention will be described in detail below. Example 1 (1) An etching process using an aluminum foil having a purity of 99.9% and a thickness of 90 μm,
5.5wt% chlorine, 1.5wt% phosphoric acid and 0.5w
Etching was carried out for 18 minutes with a triangular wave alternating current having a current density of 120 mA / cm 2 at 10 Hz in an electrolytic solution of 18 ° C. which was composed of an aqueous solution containing t% nitric acid and 2.0 wt% aluminum chloride, and washed with ion exchange water. (2) Dechlorination treatment step After performing the dechlorination treatment at 60 ° C. in a 5.0 wt% sulfuric acid aqueous solution for 2 minutes, and then immersing in a 1.0 wt% oxalic acid aqueous solution at 50 ° C. for 1 minute 30 seconds. Then, the subsequent dechlorination treatment was performed and the product was washed with ion-exchanged water.
【0009】実施例2
(1)エッチング工程
実施例1と同じ
(2)脱塩素イオン処理工程
40℃の5.0wt%のりん酸水溶液中で2分間前段の
脱塩素イオン処理を行なった後、75℃の2.0wt%
のくえん酸水溶液中に5分間浸せきして後段の脱塩素イ
オン処理を行ない、イオン交換水で洗浄した。Example 2 (1) Etching step The same as in Example 1 (2) Dechlorination ion treatment step After the dechlorination ion treatment of the previous stage was performed in a 5.0 wt% phosphoric acid aqueous solution at 40 ° C. for 2 minutes, 2.0 wt% at 75 ° C
It was immersed in an aqueous citric acid solution for 5 minutes to carry out dechlorination ion treatment in the latter stage, and washed with ion-exchanged water.
【0010】実施例3
(1)エッチング工程
実施例1と同じ
(2)脱塩素イオン処理工程
60℃の5.0wt%の硝酸水溶液中で1分30秒間前
段の脱塩素イオン処理を行なった後、85℃の2.0w
t%の酒石酸水溶液中に5分間浸せきして後段の脱塩素
イオン処理を行ない、イオン交換水で洗浄した。Example 3 (1) Etching process Same as in Example 1 (2) Dechlorination ion treatment process After the dechlorination ion treatment of the previous stage was performed for 1 minute 30 seconds in a 5.0 wt% nitric acid aqueous solution at 60 ° C. , 85 ° C 2.0w
It was dipped in a t% tartaric acid aqueous solution for 5 minutes, subjected to dechlorination ion treatment in the latter stage, and washed with ion-exchanged water.
【0011】比較例1
(1)エッチング工程
実施例1と同じ
(2)脱塩素イオン処理工程
60℃の5.0wt%の硫酸水溶液中に2分間及び3分
間浸せきした後、イオン交換水で洗浄した。Comparative Example 1 (1) Etching Step Same as Example 1 (2) Dechlorination Ion Treatment Step After immersion in a 5.0 wt% sulfuric acid aqueous solution at 60 ° C. for 2 minutes and 3 minutes, washing with ion-exchanged water did.
【0012】比較例2
(1)エッチング工程
実施例1と同じ
(2)脱塩素イオン処理工程
40℃の5.0wt%のりん酸水溶液中に2分間及び3
分間浸せきした後、イオン交換水で洗浄した。Comparative Example 2 (1) Etching Step Same as Example 1 (2) Dechlorination Treatment Step 2 minutes and 3 in a 5.0 wt% phosphoric acid aqueous solution at 40 ° C.
After soaking for a minute, it was washed with ion-exchanged water.
【0013】比較例3
(1)エッチング工程
実施例1と同じ
(2)脱塩素イオン処理工程
60℃の5.0wt%の硝酸水溶液中に1分30秒間及
び2分間浸せきした後、イオン交換水で洗浄した。Comparative Example 3 (1) Etching Step Same as Example 1 (2) Dechlorination Ionizing Step After immersion in a 5.0 wt% nitric acid aqueous solution at 60 ° C. for 1 minute 30 seconds and 2 minutes, ion-exchanged water Washed with.
【0014】しかして、上記実施例1から3及び比較例
1から3によってそれぞれ得られたエッチド箔の表面に
残留する塩素イオン量を硝酸銀比濁法にて測定した。ま
た同一箔を一般的に行なわれているアジピン酸アンモニ
ウム水溶液中で20V化成を行ない、その静電容量を測
定し、その結果を表で示した。The amounts of chlorine ions remaining on the surfaces of the etched foils obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured by the silver nitrate nephelometry. Further, the same foil was subjected to 20 V chemical formation in a commonly used aqueous solution of ammonium adipate, the electrostatic capacity was measured, and the results are shown in the table.
【0015】[0015]
【表1】 [Table 1]
【0016】表1から明らかなように、実施例1から3
で得られたエッチド箔の残留イオン量は、それぞれ1.
0mg/m2 、1.2mg/m2 及び1.0mg/m2
であり、そのいづれも比較例1から3で得られたエッチ
ド箔の残留塩素イオン量に比し大幅な減少を示した。As is apparent from Table 1, Examples 1 to 3
The amount of residual ions in the etched foil obtained in 1. was 1.
0 mg / m2, 1.2 mg / m2 and 1.0 mg / m2
And each of them showed a significant decrease as compared to the residual chlorine ion amount of the etched foils obtained in Comparative Examples 1 to 3.
【0017】また比較例1から3に示す1段階の脱塩素
イオン処理を行なった場合、酸水溶液中への浸せき時間
を長くすると残留塩素イオン量は低下するが静電容量も
減少し、しかも残留塩素イオン量の低下は僅少で依然と
して高い値を示している。When the one-step dechlorination treatment shown in Comparative Examples 1 to 3 is performed, when the immersion time in the acid aqueous solution is prolonged, the amount of residual chlorine ions is reduced but the electrostatic capacity is also reduced, and The decrease in the amount of chlorine ions is small and still high.
【0018】[0018]
【発明の効果】以上のように本願発明によれば、エッチ
ド箔に残存する塩素イオンを効果的に減少できて、容量
が同一であるにも拘らず残留塩素イオン量の少ない電極
箔を製造することができる。また脱塩素イオン処理に特
別な設備を必要とせず容易に達成することができる。As described above, according to the present invention, the chlorine ions remaining in the etched foil can be effectively reduced, and an electrode foil having a small amount of residual chlorine ions despite having the same capacity can be manufactured. be able to. In addition, dechlorination treatment can be easily achieved without requiring special equipment.
【0019】また本願発明は後段で有機酸水溶液中に浸
せきして脱塩素イオン処理を行なっているので、前段で
使用したりん酸、硫酸または硝酸などの無機酸イオンが
エッチド箔表面から除去され、また後段で使用するしゅ
う酸、くえん酸または酒石酸は、250℃以下の比較的
低い温度の加熱処理で容易に分解されるので、エッチド
箔表面から不要な酸イオンを容易に除去することができ
る等の利点を有する。Further, in the present invention, since the latter step is soaked in an organic acid aqueous solution for dechlorination treatment, the inorganic acid ions such as phosphoric acid, sulfuric acid or nitric acid used in the previous step are removed from the surface of the etched foil, Further, oxalic acid, citric acid or tartaric acid used in the subsequent stage is easily decomposed by heat treatment at a relatively low temperature of 250 ° C. or lower, so that unnecessary acid ions can be easily removed from the surface of the etched foil. Have the advantage of.
Claims (3)
で化学的又は電気化学的エッチングにより粗面化した
後、脱塩素イオン処理を行う際、脱塩素イオン処理工程
を前段と後段との2段階に分け、その前段においては、
りん酸、硫酸、硝酸などの無機酸の水溶液中に浸せきし
て行い、後段においては、しゅう酸、くえん酸、酒石酸
などの有機酸の水溶液中に浸せきして行うことを特徴と
したアルミニウム電解コンデンサ用電極箔の製造方法。1. When the aluminum foil is roughened by chemical or electrochemical etching in an aqueous solution containing chloride and then subjected to dechlorinating ion treatment, the dechlorinating ion treatment step is performed in two stages, a first stage and a second stage. And in the previous stage,
An aluminum electrolytic capacitor characterized by being dipped in an aqueous solution of an inorganic acid such as phosphoric acid, sulfuric acid, nitric acid, and in the latter step by being dipped in an aqueous solution of an organic acid such as oxalic acid, citric acid, tartaric acid. Of manufacturing electrode foil for automobile.
のりん酸、硫酸又は硝酸の濃度が0.5wt%から30
wt%の範囲であり、その水溶液温度が20℃から80
℃の範囲である請求項1記載のアルミニウム電解コンデ
ンサ用電極箔の製造方法。2. The concentration of phosphoric acid, sulfuric acid or nitric acid in an aqueous solution of phosphoric acid, sulfuric acid or nitric acid is 0.5 wt% to 30.
It is in the range of wt% and the temperature of the aqueous solution is 20 ° C to 80
The method for producing an electrode foil for an aluminum electrolytic capacitor according to claim 1, which is in the range of ° C.
水溶液中のしゅう酸、くえん酸又は酒石酸の濃度が0.
2wt%から10wt%であり、その水溶液温度が30
℃から90℃の範囲である請求項1または2記載のアル
ミニウム電解コンデンサ用電極箔の製造方法。3. The concentration of oxalic acid, citric acid or tartaric acid in an aqueous solution of oxalic acid, citric acid or tartaric acid is 0.
2 wt% to 10 wt% and the temperature of the aqueous solution is 30
The method for producing an electrode foil for an aluminum electrolytic capacitor according to claim 1 or 2, wherein the temperature is in the range of ℃ to 90 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17206398A JP3371362B2 (en) | 1998-06-05 | 1998-06-05 | Method for producing electrode foil for aluminum electrolytic capacitor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17206398A JP3371362B2 (en) | 1998-06-05 | 1998-06-05 | Method for producing electrode foil for aluminum electrolytic capacitor |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH11354387A JPH11354387A (en) | 1999-12-24 |
JP3371362B2 true JP3371362B2 (en) | 2003-01-27 |
Family
ID=15934855
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17206398A Expired - Fee Related JP3371362B2 (en) | 1998-06-05 | 1998-06-05 | Method for producing electrode foil for aluminum electrolytic capacitor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3371362B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7768773B2 (en) * | 2008-01-22 | 2010-08-03 | Avx Corporation | Sintered anode pellet etched with an organic acid for use in an electrolytic capacitor |
KR101539860B1 (en) * | 2013-10-30 | 2015-07-27 | 인하대학교 산학협력단 | Method of manufacturing capacitor |
-
1998
- 1998-06-05 JP JP17206398A patent/JP3371362B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH11354387A (en) | 1999-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2007103798A (en) | Method of forming aluminum electrode foil for electrolytic capacitor | |
JP3371362B2 (en) | Method for producing electrode foil for aluminum electrolytic capacitor | |
JPS6229519B2 (en) | ||
JP3084330B2 (en) | Method of manufacturing aluminum material for electrolytic capacitor electrode having reduced etching layer | |
JPH11307400A (en) | Manufacture of electrode foil for solid electrolytic capacitor | |
JPH043409A (en) | Method of etching aluminum foil for electrolytic capacitor | |
JPS5825218A (en) | Method of producing low voltage electrolytic condenser electrode foil | |
JP3582451B2 (en) | Manufacturing method of anode foil for aluminum electrolytic capacitor | |
JP3248251B2 (en) | Method for producing electrode foil for aluminum electrolytic capacitor | |
JPH08241832A (en) | Manufacture of electrode foil for aluminum electrolytic capacitor | |
JP4163022B2 (en) | Manufacturing method of etching foil for electrolytic capacitor | |
JPH03270117A (en) | Manufacture of aluminum foil for electrolytic capacitor | |
JP3480164B2 (en) | Manufacturing method of electrode foil for aluminum electrolytic capacitor | |
JP3295839B2 (en) | Method for removing copper from foil surface of aluminum foil for electrolytic capacitors | |
JP3460418B2 (en) | Manufacturing method of electrode foil for aluminum electrolytic capacitor | |
JP3728964B2 (en) | Manufacturing method of electrode foil for aluminum electrolytic capacitor | |
JP2638038B2 (en) | Manufacturing method of electrode foil for aluminum electrolytic capacitor | |
JP2004193339A (en) | Manufacturing method of electrode foil for electrolytic capacitor | |
JP3496465B2 (en) | Manufacturing method of electrode foil for aluminum electrolytic capacitor | |
JP4308556B2 (en) | Aluminum material for electrolytic capacitor electrode, method for producing electrolytic capacitor electrode material, and electrolytic capacitor | |
JP2583802B2 (en) | Etching method of aluminum foil for electrolytic capacitor | |
JP2523654B2 (en) | Method for manufacturing electrode foil for aluminum electrolytic capacitors | |
JPH07272983A (en) | Electrode foil for aluminum electrolytic capacitor and its manufacturing method | |
JPH0653084A (en) | Manufacture of electrode foil for aluminum electrolytic capacitor | |
JPH03101213A (en) | Etching of aluminium foil for electrolytic capacitor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081122 Year of fee payment: 6 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081122 Year of fee payment: 6 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091122 Year of fee payment: 7 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101122 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101122 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111122 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111122 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121122 Year of fee payment: 10 |
|
LAPS | Cancellation because of no payment of annual fees |