JPH0637715B2 - Method for manufacturing electrode foil for aluminum electrolytic capacitor - Google Patents
Method for manufacturing electrode foil for aluminum electrolytic capacitorInfo
- Publication number
- JPH0637715B2 JPH0637715B2 JP1065193A JP6519389A JPH0637715B2 JP H0637715 B2 JPH0637715 B2 JP H0637715B2 JP 1065193 A JP1065193 A JP 1065193A JP 6519389 A JP6519389 A JP 6519389A JP H0637715 B2 JPH0637715 B2 JP H0637715B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic capacitor
- electrode foil
- diaphragm
- aluminum electrolytic
- fluororesin
- 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 - Lifetime
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- ing And Chemical Polishing (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明はアルミニウム電解コンデンサ用電極箔の製造
方法に関する。The present invention relates to a method for manufacturing an electrode foil for an aluminum electrolytic capacitor.
アルミニウム電解コンデンサ用電極箔のエッチング法と
しては、塩酸、硫酸、蓚酸、塩化ナトリウムなどの水溶
液中で、アルミニウム箔と陰極間に直流電流を流す直流
エッチング法と、交流電流を流す交流エッチング法とが
広く使用されている。As a method for etching an electrode foil for an aluminum electrolytic capacitor, there are a direct current etching method in which a direct current is applied between an aluminum foil and a cathode in an aqueous solution of hydrochloric acid, sulfuric acid, oxalic acid, sodium chloride or the like, and an alternating current etching method in which an alternating current is applied. Widely used.
なお、直流エッチングの一形態として直流パルス波ある
いは三角波を使用する方法も提案されている。A method of using a DC pulse wave or a triangular wave has also been proposed as one form of DC etching.
電解エッチングを工業的に実施する場合は、連続的に箔
を移動させてエッチングを行なう方法が採用されている
が、直流エッチングを行なうにあたり、高い倍率を達成
するには、偶発的な電解の中断や電解開始点での緩慢な
電流の立上がりおよび意図しない濃度勾配の発生等を抑
止することが肝要である。When performing electrolytic etching industrially, a method of continuously moving the foil to perform etching is adopted, but in performing direct current etching, in order to achieve a high magnification, accidental interruption of electrolysis is required. It is important to suppress the slow rise of the current at the electrolysis start point and the occurrence of an unintended concentration gradient.
しかしながら、工業槽ではアルミニウムと陰極から発生
するガスが気液界面に滞溜するため電流分布が不均一に
なったり、電流の立上がりが緩慢になったりして高い倍
率が達成しがたいという問題があった。However, in industrial tanks, the gas generated from aluminum and the cathode accumulates at the gas-liquid interface, resulting in non-uniform current distribution and slow current rise, making it difficult to achieve high magnification. there were.
この問題点を解決するための方法として、一般に、アル
ミニウムと陰極の間隔を大きく広げることが行なわれて
いるが、これによるとスペースや電力コストがかさむば
かりでなく、ガスの影響を除去できないという欠点があ
る。As a method for solving this problem, generally, the distance between the aluminum and the cathode is widely widened, but this not only increases the space and power cost, but also has the drawback that the influence of gas cannot be removed. There is.
また、特開昭62-219610号公報、特開昭64-8299号公報、
特開昭64-8300号公報、特開昭64-9612号公報に示される
ように、電槽下部より電解を開始する方法も提案されて
いる。しかしながら、構造が複雑で制御しにくく、また
摺動部が磨耗し、安定性が乏しいなどの難点があった。Further, JP-A-62-219610, JP-A-64-8299,
As disclosed in JP-A-64-8300 and JP-A-64-9612, there has been proposed a method of starting electrolysis from the lower part of a battery case. However, there are problems that the structure is complicated and difficult to control, the sliding portion is worn, and the stability is poor.
他方、電槽上部に補助陰極を設けて電流の立上がりを改
良する提案（特開昭61-244013号公報）もあるが、この
ものにおいても電槽構造、電解電源等が複雑であるとい
う点は解決されない。On the other hand, there is also a proposal (Japanese Patent Laid-Open No. 61-244013) to provide an auxiliary cathode on the upper part of the battery case to improve the rise of the current, but the point that the battery container structure, the electrolytic power source, etc. are also complicated in this proposal. Not resolved.
この発明は、上記問題点を解決するもので、発生ガスの
約85％以上が陰極から発生する水素ガスであることに着
目し、エッチング開始と同時に電流が急峻に立上がり、
アルミニウム箔表面での発生ガスの遮蔽と滞溜によるエ
ッチングの瞬断を防止するようにしたものである。This invention solves the above problems, paying attention to that about 85% or more of the generated gas is hydrogen gas generated from the cathode, and the current sharply rises at the same time as the start of etching,
This is to prevent the generation of gas on the surface of the aluminum foil and to prevent instantaneous interruption of etching due to retention.
上記従来の問題点を解決するため、この発明において
は、アルミニウム箔を陽極として直流エッチングにより
電解するにあたり、同陽極と陰極との間に親水性フッ素
樹脂製隔膜を設けたことを特徴とする。In order to solve the above-mentioned conventional problems, the present invention is characterized in that a hydrophilic fluororesin diaphragm is provided between the anode and the cathode during electrolysis by direct current etching using an aluminum foil as the anode.
陰極で多量に発生する水素ガスを陽極表面に到達しない
ようにするための隔膜としては種々の多孔膜やイオン交
換膜が候補としてあげられるが、高温、高濃度の酸性
で、かつ、一部酸化性のある電解液に耐えられる隔膜と
して鋭意検討の結果、親水性フッ素樹脂製多孔膜あるい
はフッ素樹脂製カチオン交換膜が格別に信頼性が高く、
隔膜のオーム損が低いことが判明した。Various porous membranes and ion exchange membranes are candidates for the diaphragm to prevent hydrogen gas, which is generated in large quantities at the cathode, from reaching the surface of the anode. As a result of diligent studies as a diaphragm that can withstand a strong electrolytic solution, a hydrophilic fluororesin porous membrane or fluororesin cation exchange membrane is exceptionally reliable,
It was found that the ohmic loss of the diaphragm was low.
親水性フッ素樹脂製多孔膜としては、フッ素樹脂微多孔
膜を親水性フッ素樹脂ポリマーでポア表面をコーティン
グしたものが特に電解液の濡れ性が良好であるととも
に、隔膜の抵抗値が低く、かつ、ガスが付着しにくいの
で好適である。この多孔膜の基体ポリマーとしては、ポ
リテトラフルオロエチレン、パーフルオロアルキルビニ
ルエーテル重合体、テトラフルオロエチレンとエチレン
の共重合体などが用いられる。As the hydrophilic fluororesin porous film, a fluororesin microporous film having a pore surface coated with a hydrophilic fluororesin polymer has particularly good wettability of the electrolytic solution, and the resistance value of the diaphragm is low, and It is suitable because it is difficult for gas to adhere. As the base polymer of this porous film, polytetrafluoroethylene, a perfluoroalkyl vinyl ether polymer, a copolymer of tetrafluoroethylene and ethylene, or the like is used.
また、フッ素樹脂製カチオン交換膜は、式（Ｉ） で表されるポリマーが好ましい。The cation exchange membrane made of fluororesin has the formula (I) Polymers represented by are preferred.
式（Ｉ）においてｍは０または１、ｎは１〜５の整数、
ＲはＣＯ2Ｘ，ＳＯ3Ｘ，ＰＯ3Ｘ（ＸはＨ，Ｎａ，Ｋ，
ＮＨ4，Ｌi，第４級アンモニウム基またはホスホニウム
基）のいずれかである。In the formula (I), m is 0 or 1, n is an integer of 1 to 5,
R is CO 2 X, SO 3 X, PO 3 X (X is H, Na, K,
NH 4, L i, is either a quaternary ammonium group or phosphonium group).
イオン交換体のイオン交換容量は0.5〜2.0meq／g乾燥樹
脂、特に0.6〜1.5meq／g乾燥樹脂が好ましい。The ion exchange capacity of the ion exchanger is preferably 0.5 to 2.0 meq / g dry resin, more preferably 0.6 to 1.5 meq / g dry resin.
Ｒは、ＳＯ3Ｘが特に酸解離定数が大きく酸性電解液中
で電導度を高くできるので好ましい。なお、ＲはＳＯ3
Ｘ単独またはＳＯ3ＸとＣＯＯＸとの混酸または２層膜
でもよい。イオン交換膜は、その引裂強度を高めたり寸
法変化を抑えるために、フッ素樹脂製の布、不織布等が
用いられることがある。R 3 is preferably SO 3 X because it has a particularly large acid dissociation constant and can increase the conductivity in an acidic electrolyte. In addition, R is SO 3
X alone or a mixed acid of SO 3 X and COOX or a two-layer film may be used. For the ion exchange membrane, a fluororesin cloth, a non-woven cloth, or the like may be used in order to increase the tear strength or suppress the dimensional change.
フッ素樹脂多孔膜あるいはイオン交換膜の厚みは50〜70
0μｍが多用される。フッ素樹脂多孔膜またはイオン交
換膜は両極の間に隔膜として設置されるが、必要により
陰極をヒートシール法により袋状膜でシールして隔離を
する場合もある。The thickness of fluororesin porous membrane or ion exchange membrane is 50-70
0 μm is often used. The fluororesin porous membrane or ion exchange membrane is installed as a diaphragm between both electrodes, but if necessary, the cathode may be sealed with a bag-like membrane by a heat sealing method for isolation.
イオン交換膜およびフッ素樹脂多孔膜は、表面が親水性
ポリマーで被覆されているが、ガスが表面に付着する場
合がある。このような場合には、隔膜表面に１〜10μｍ
の親水性無機物（例えば、ＳｉＣ，Ａｌ2Ｏ3，Ｔｉ
Ｏ2，ＺｒＯ2，ＴａＮＯ5Ｎｂ2Ｏ5）粒子をコーティン
グすることにより、親水性がさらに向上し、電解電圧を
下げることができる。フッ素樹脂カチオン交換膜は、旭
硝子株式会社よりFlemion(商品名)として市販されてい
る。The surface of the ion exchange membrane and the fluororesin porous membrane is coated with a hydrophilic polymer, but gas may adhere to the surface. In such a case, 1 to 10 μm on the surface of the diaphragm.
Hydrophilic inorganic substances (eg, SiC, Al 2 O 3 , Ti
By coating with O 2 , ZrO 2 , TaNO 5 Nb 2 O 5 ) particles, the hydrophilicity is further improved and the electrolysis voltage can be lowered. The fluororesin cation exchange membrane is commercially available from Asahi Glass Co., Ltd. as Flemion (trade name).
なお、既述のフッ素樹脂多孔膜を親水性することは、式
（Ｉ）からなるパーフルオロカチオン樹脂を溶媒に溶か
して多孔体表面を被覆し、乾燥することにより達成され
る。溶媒としては、Ｎ-メチルピロリドトン、アセト
ン、アルコール類などが使用される。The hydrophilicity of the fluororesin porous membrane described above can be achieved by dissolving the perfluorocationic resin represented by the formula (I) in a solvent to coat the surface of the porous body and drying. As the solvent, N-methylpyrrolidone, acetone, alcohols, etc. are used.
《実施例１》 第１図にこの実施例に使用した電槽の概略的な構成図が
示されている。この図において、１はアルミニウム箔、
２はフッ素樹脂カチオン交換膜、３は陰極、４は給電ロ
ーラ、５はエッチング液である。<< Example 1 >> FIG. 1 shows a schematic configuration diagram of a battery case used in this example. In this figure, 1 is aluminum foil,
Reference numeral 2 is a fluororesin cation exchange membrane, 3 is a cathode, 4 is a power supply roller, and 5 is an etching solution.
アルミニウム箔１の幅は500mm、その送り速度１ｍ／
分、塩酸を主体とし硫酸を添加した15％、70℃のエッチ
ング液５を用い、直流パルスエッチングを行なった。電
流は5000Ａ、アルミニウム箔１と陰極３との間の距離は
15mm、陰極３の有効深さは1000mmであった。Aluminum foil 1 has a width of 500 mm and its feed rate is 1 m /
For 15 minutes, DC pulse etching was performed using an etching solution 5 containing hydrochloric acid as a main component and sulfuric acid added at 15% and 70 ° C. The current is 5000A, the distance between the aluminum foil 1 and the cathode 3 is
The effective depth of the cathode 3 was 15 mm and 1000 mm.
フッ素樹脂カチオン交換膜２は、膜厚410μｍで、その
イオン交換容量は0.92meq／g乾燥樹脂であり、ポリテト
ラフルオロエチレン織布を補強材に用いている。The fluororesin cation exchange membrane 2 has a film thickness of 410 μm, its ion exchange capacity is 0.92 meq / g dry resin, and polytetrafluoroethylene woven fabric is used as a reinforcing material.
ポリマー構造式は である。The polymer structural formula is Is.
このイオン交換膜表面には、両面に粒径１〜５μｍのＺ
ｒＯ2粒子がコーティングされている。直流パルスエッ
チングに供するアルミニウム箔は、予め塩酸中で交流連
続エッチングをしたものを用いた。On the surface of this ion exchange membrane, Z with a particle size of 1 to 5 μm is formed on both sides.
The rO 2 particles are coated. The aluminum foil used for the direct current pulse etching was one that was previously subjected to alternating current continuous etching in hydrochloric acid.
直流パルスエッチングの後、アジピン酸水溶液中で化成
電圧33Ｖにて化成し、静電容量を求めたところ、隔膜を
用いないときの静電容量を100とした場合、静電容量は1
40であった。なお、隔膜を入れることによる電圧上昇は
わずか0.15Ｖであった。After DC pulse etching, formation was performed in an aqueous solution of adipic acid at a formation voltage of 33 V, and the capacitance was calculated. The capacitance was 1 when the capacitance without a diaphragm was 100.
It was 40. The voltage increase by inserting the diaphragm was only 0.15V.
《実施例２》 厚み180μｍ、平均孔径７μｍのポリテトラフルオロエ
チレン製多孔膜で、 からなるイオン交換容量1.9meq／g乾燥樹脂のポリマー
を、20倍量のＮメチルピロリドンに溶解した溶液で多孔
体の表面処理を行ない加水分解することにより親水性フ
ッ素樹脂多孔膜を得た。Example 2 A porous film made of polytetrafluoroethylene having a thickness of 180 μm and an average pore diameter of 7 μm, A hydrophilic fluororesin porous membrane was obtained by subjecting a porous polymer to a surface treatment with a solution prepared by dissolving a polymer of an ion exchange capacity of 1.9 meq / g of a dry resin in 20 times the amount of N-methylpyrrolidone and hydrolyzing it.
この多孔膜を実施例１のイオン交換膜の代りに用いたほ
かは、実施例１と同様な試験を行なった。隔膜を用いな
いときの静電容量を100とした場合、静電容量は138であ
った。隔膜を入れることによる電圧上昇はわずか0.20Ｖ
であった。この場合、多孔質の表面に実施例１と同様に
粒径１〜５μｍのＺｒＯ2粒子をコーティングするとさ
らに効果がある。The same test as in Example 1 was conducted except that this porous membrane was used in place of the ion exchange membrane in Example 1. The capacitance was 138 when the capacitance without a diaphragm was 100. Only 0.20V increase due to the diaphragm
Met. In this case, it is more effective to coat the porous surface with ZrO 2 particles having a particle size of 1 to 5 μm as in Example 1.
以上説明したように、この発明によれば、アルミニウム
箔の陽極と陰極との間にフッ素樹脂製親水性隔膜を設け
たことにより、エッチング開始と同時に電流が急峻に立
上がり、アルミニウム箔表面での発生ガスの遮蔽と滞溜
によるエッチングの瞬断を防止することができる。As described above, according to the present invention, by providing the fluororesin hydrophilic partition film between the anode and the cathode of the aluminum foil, the current sharply rises at the same time as the etching starts, and the generation on the aluminum foil surface occurs. It is possible to prevent instantaneous interruption of etching due to gas shielding and retention.
第１図はこの発明の実施例に使用した電槽の構成を概略
的に示した断面図である。 図中、１はアルミニウム箔、２は交換膜、３は陰極、４
は給電ローラ、５はエッチング液である。FIG. 1 is a sectional view schematically showing the structure of a battery case used in an embodiment of the present invention. In the figure, 1 is an aluminum foil, 2 is an exchange membrane, 3 is a cathode, 4
Is a power supply roller, and 5 is an etching solution.
フロントページの続き (72)発明者 藤原 秀二 神奈川県藤沢市辻堂新町２丁目２番１号 エルナー株式会社内 (72)発明者 鈴木 公二 神奈川県横浜市神奈川区栗田谷62番地 (56)参考文献 特開 昭50−102537（ＪＰ，Ａ) 実開 昭62−112135（ＪＰ，Ｕ) 実公 昭59−35586（ＪＰ，Ｙ２)Front page continuation (72) Inventor Shuji Fujiwara 2-2-1 Tsujido Shinmachi, Fujisawa-shi, Kanagawa Elner Co., Ltd. Reference Japanese Unexamined Patent Publication No. 50-102537 (JP, A) Actual development 62-112135 (JP, U) Actual public 59-35586 (JP, Y2)
Claims (5)
との間に直流電圧を印加して電解エッチングを行なうに
あたり、上記陽極と陰極との間にフッ素樹脂製親水性隔
膜を設けたことを特徴とするアルミニウム電解コンデン
サ用電極箔の製造方法。1. When an aluminum foil is used as an anode and a direct current voltage is applied between the anode and the cathode for electrolytic etching, a hydrophilic fluororesin membrane is provided between the anode and the cathode. A method of manufacturing an electrode foil for a characteristic aluminum electrolytic capacitor.
らなる請求項１に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 method for producing an electrode foil for an aluminum electrolytic capacitor according to claim 1, wherein the diaphragm is a cation exchange membrane made of fluororesin.
乾燥樹脂からなる請求項１に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 diaphragm has an ion exchange capacity of 0.6 to 1.5 meq / g.
The method for producing an electrode foil for an aluminum electrolytic capacitor according to claim 1, which is made of a dry resin.
ィングされている請求項２に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。4. The method for producing an electrode foil for an aluminum electrolytic capacitor according to claim 2, wherein the surface of the diaphragm is coated with a hydrophilic inorganic substance.
なる請求項１に記載のアルミ電解コンデンサ用電極箔の
製造方法。5. The method for producing an electrode foil for an aluminum electrolytic capacitor according to claim 1, wherein the diaphragm is a hydrophilic fluororesin porous film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1065193A JPH0637715B2 (en) | 1989-03-17 | 1989-03-17 | Method for manufacturing electrode foil for aluminum electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1065193A JPH0637715B2 (en) | 1989-03-17 | 1989-03-17 | Method for manufacturing electrode foil for aluminum electrolytic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02244705A JPH02244705A (en) | 1990-09-28 |
| JPH0637715B2 true JPH0637715B2 (en) | 1994-05-18 |
Family
ID=13279841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1065193A Expired - Lifetime JPH0637715B2 (en) | 1989-03-17 | 1989-03-17 | Method for manufacturing electrode foil for aluminum electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0637715B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107731535A (en) * | 2017-11-20 | 2018-02-23 | 湖北富奕达电子科技有限公司 | A kind of aluminium foil corrosion line hanger |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100257807B1 (en) * | 1991-05-30 | 2000-06-01 | 엔.프럼 | Electrode chamber for an electrolytic cell, use thereof and method for electrolytically depositing or removing a metal layer |
| CN116479513B (en) * | 2023-05-05 | 2023-12-08 | 江苏荣生电子有限公司 | Corrosion device for electrode foil processing |
-
1989
- 1989-03-17 JP JP1065193A patent/JPH0637715B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107731535A (en) * | 2017-11-20 | 2018-02-23 | 湖北富奕达电子科技有限公司 | A kind of aluminium foil corrosion line hanger |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02244705A (en) | 1990-09-28 |
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