JP4289717B2 - Aluminum electrolytic capacitor and method for producing cathode foil for aluminum electrolytic capacitor - Google Patents
Aluminum electrolytic capacitor and method for producing cathode foil for aluminum electrolytic capacitor Download PDFInfo
- Publication number
- JP4289717B2 JP4289717B2 JP10873699A JP10873699A JP4289717B2 JP 4289717 B2 JP4289717 B2 JP 4289717B2 JP 10873699 A JP10873699 A JP 10873699A JP 10873699 A JP10873699 A JP 10873699A JP 4289717 B2 JP4289717 B2 JP 4289717B2
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- Prior art keywords
- electrolytic capacitor
- cathode foil
- aluminum electrolytic
- acid
- foil
- 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.)
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- 239000011888 foil Substances 0.000 title claims description 39
- 229910052782 aluminium Inorganic materials 0.000 title claims description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 26
- 239000003990 capacitor Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 12
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001771 vacuum deposition Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Treatment Of Metals (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、アルミニウム電解コンデンサおよびアルミニウム電解コンデンサ用陰極箔の製造方法に関するものである。
【０００２】
【従来の技術】
近年の電機・電子機器の小型化、軽量化により、アルミニウム電解コンデンサにおいても、小型化の要求が更に強くなっている。
アルミニウム電解コンデンサの小型化を図るためには、使用する電極箔の単位面積当たりの静電容量を上げる必要があり、このため種々のエッチング方法の検討が行われているが、表面拡大の際には既エッチング部の溶解も起こるため、単位面積当たりの静電容量の向上を図ることには限度があった。
したがって、単位面積当たりの静電容量が高く、製品化した際の静電容量変化が小さい電極箔が要求されていた。
【０００３】
【発明が解決しようとする課題】
上記課題を解決するため、Ａｌより誘電率の高い元素をドライプロセスにて表面にコーティングすることで、単位面積当たりの静電容量を上げた陰極箔が採用されているが、製品化したときの静電容量の減少が大きいという欠点があり、静電容量変化が少ない陰極箔の開発が望まれていた。
【０００４】
【課題を解決するための手段】
本発明は、上記課題を解決するため種々検討を行った結果、見出されたものであり、単位面積当たりの静電容量が高く、かつ、製品での静電容量減少も少ない、アルミニウム電解コンデンサ用陰極箔に関するものである。すなわち、アルミニウム箔にＴｉ、Ｚｒ、Ｈｆ、Ｎｂの金属またはその酸化物若しくは窒化物を蒸着してなる陰極箔にリン酸、亜リン酸、次亜リン酸またはその塩を付着させ、該陰極箔に付着させたリン酸、亜リン酸、次亜リン酸またはその塩を電解液中に溶出させることを特徴とするアルミニウム電解コンデンサである。また、上記陰極箔が電気化学的または化学的手法により表面を粗面化したアルミニウムエッチング箔であることを特徴とするアルミニウム電解コンデンサである。そして、アルミニウム箔にＴｉ、Ｚｒ、Ｈｆ、Ｎｂの金属またはその酸化物若しくは窒化物を蒸着してなる陰極箔をリン酸、亜リン酸、次亜リン酸またはその塩を含む溶液に浸漬した後、１００〜５００℃の熱処理温度で熱処理し、電解液中で溶出するようにリン酸、亜リン酸、次亜リン酸またはその塩を前記陰極箔に付着させることを特徴とするアルミニウム電解コンデンサ用陰極箔の製造方法である。
【０００５】
【発明の実施の形態】
製品化したときの静電容量減少の一因として、陰極箔界面のｐＨの上昇があげられる。そこで、あらかじめ、リン酸、亜リン酸、次亜リン酸、またはそれらの塩を陰極箔に付着させておけば、これらの酸が電解液中に徐々に溶解し、陰極箔界面のｐＨ上昇が緩衝され、静電容量の減少が抑えられる。
【０００６】
【実施例】
以下、実施例を従来例と比較して詳細に説明する。
[実施例１]
電気化学的にエッチングしたアルミニウム箔に、真空蒸着法によりＴｉを蒸着した後、７５ｗｔ％リン酸１ｃｃ／Ｌの水溶液に浸漬し、２５０℃にて熱処理して陰極箔とし、定格１０Ｖ−３３０μＦの電解コンデンサを作製した。
[実施例２]
電気化学的にエッチングしたアルミニウム箔に、真空蒸着法によりＴｉを蒸着した後、リン酸二水素アンモニウム３ｇ／Ｌの水溶液に浸漬し、１５０℃にて熱処理して陰極箔とし、実施例１と同じ定格の電解コンデンサを作製した。
[実施例３]
電気化学的にエッチングしたアルミニウム箔に、真空蒸着法によりＴｉを蒸着した後、亜リン酸１ｇ／Ｌの水溶液に浸漬し、３５０℃にて熱処理して陰極箔とし、実施例１と同じ定格の電解コンデンサを作製した。
[実施例４]
電気化学的にエッチングしたアルミニウム箔に、真空蒸着法によりＴｉを蒸着した後、次亜リン酸１ｇ／Ｌの水溶液に浸漬し、４５０℃にて熱処理して陰極箔とし、実施例１と同じ定格の電解コンデンサを作製した。
[従来例]
リン酸、亜リン酸または次亜リン酸系水溶液への浸漬処理、および熱処理を行わないＴｉ蒸着したアルミニウムエッチング箔を陰極箔に用いて実施例１〜４と同じ定格の電解コンデンサを作製した。
これらの電解コンデンサ試料を、１０５℃中にて、１０Ｖの電圧を５０００時間連続印加した後の静電容量変化を、表１に示す。
【０００７】
【表１】
実施例１〜４においては、従来例に比較し、高温寿命試験における静電容量変化が小さく、信頼性が著しく改善されている。
【０００９】
なお、熱処理温度は、１００℃を下回ると、付着したリン酸、亜リン酸または次亜リン酸が、短時間で溶出してしまい、また、５００℃を超えると、溶出しにくくなるため、１００〜５００℃の範囲が好ましい。
【００１０】
【発明の効果】
本発明によるアルミニウム電解コンデンサおよびアルミニウム電解コンデンサ用陰極箔は、製品寿命試験における静電容量変化を大幅に低減させることができ、信頼性を著しく改善することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aluminum electrolytic capacitor and a method for producing a cathode foil for an aluminum electrolytic capacitor.
[0002]
[Prior art]
Due to the recent reduction in size and weight of electric and electronic devices, there is an increasing demand for miniaturization of aluminum electrolytic capacitors.
In order to reduce the size of the aluminum electrolytic capacitor, it is necessary to increase the capacitance per unit area of the electrode foil to be used. For this reason, various etching methods have been studied. However, there is a limit in improving the capacitance per unit area because the already-etched portion also melts.
Accordingly, there has been a demand for an electrode foil that has a high capacitance per unit area and a small change in capacitance when manufactured.
[0003]
[Problems to be solved by the invention]
In order to solve the above problems, a cathode foil having a higher capacitance per unit area by coating an element having a dielectric constant higher than that of Al by a dry process is employed. There has been a drawback that the reduction in capacitance is large, and the development of a cathode foil with little change in capacitance has been desired.
[0004]
[Means for Solving the Problems]
The present invention has been found as a result of various studies to solve the above-mentioned problems, and has been found, and an aluminum electrolytic capacitor having a high capacitance per unit area and a small reduction in capacitance in a product. The present invention relates to a cathode foil for use. That is, phosphoric acid, phosphorous acid, hypophosphorous acid, or a salt thereof is adhered to a cathode foil formed by depositing a metal of Ti, Zr, Hf, Nb or an oxide or nitride thereof on an aluminum foil, and the cathode foil The aluminum electrolytic capacitor is characterized by eluting phosphoric acid, phosphorous acid, hypophosphorous acid or a salt thereof adhering to the electrolyte. The aluminum electrolytic capacitor is characterized in that the cathode foil is an aluminum etching foil whose surface is roughened by an electrochemical or chemical method. And after immersing the cathode foil formed by vapor-depositing a metal of Ti, Zr, Hf, Nb or an oxide or nitride thereof on an aluminum foil in a solution containing phosphoric acid, phosphorous acid, hypophosphorous acid or a salt thereof For aluminum electrolytic capacitors, characterized in that phosphoric acid, phosphorous acid, hypophosphorous acid or a salt thereof is attached to the cathode foil so as to be eluted at a heat treatment temperature of 100 to 500 ° C. It is a manufacturing method of cathode foil.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
One cause of the decrease in capacitance when commercialized is an increase in pH at the cathode foil interface. Therefore, if phosphoric acid, phosphorous acid, hypophosphorous acid, or a salt thereof is attached to the cathode foil in advance, these acids are gradually dissolved in the electrolyte, and the pH at the cathode foil interface is increased. It is buffered and the decrease in capacitance is suppressed.
[0006]
【Example】
Hereinafter, examples will be described in detail in comparison with conventional examples.
[Example 1]
After Ti is deposited on an electrochemically etched aluminum foil by vacuum deposition, it is immersed in an aqueous solution of 1 cc / L of 75 wt% phosphoric acid and heat-treated at 250 ° C. to form a cathode foil. A capacitor was produced.
[Example 2]
After Ti was deposited on an electrochemically etched aluminum foil by vacuum deposition, it was immersed in an aqueous solution of 3 g / L ammonium dihydrogen phosphate and heat-treated at 150 ° C. to obtain a cathode foil, the same as in Example 1. A rated electrolytic capacitor was produced.
[Example 3]
After Ti was deposited on the electrochemically etched aluminum foil by vacuum deposition, it was immersed in an aqueous solution of 1 g / L phosphorous acid and heat treated at 350 ° C. to form a cathode foil, which had the same rating as in Example 1. An electrolytic capacitor was produced.
[Example 4]
After Ti was deposited on an electrochemically etched aluminum foil by vacuum deposition, it was immersed in an aqueous solution of 1 g / L hypophosphorous acid and heat treated at 450 ° C. to form a cathode foil. The same rating as in Example 1 An electrolytic capacitor was prepared.
[Conventional example]
An electrolytic capacitor having the same rating as that of Examples 1 to 4 was prepared by using, as a cathode foil, a Ti-deposited aluminum etching foil that was not immersed in phosphoric acid, phosphorous acid, or a hypophosphorous acid aqueous solution, and was not subjected to heat treatment.
Table 1 shows the change in capacitance after applying a voltage of 10 V to these electrolytic capacitor samples at 105 ° C. for 5000 hours continuously.
[0007]
[Table 1]
In Examples 1 to 4, compared to the conventional example, the capacitance change in the high-temperature life test is small, and the reliability is remarkably improved.
[0009]
When the heat treatment temperature is below 100 ° C., the adhering phosphoric acid, phosphorous acid or hypophosphorous acid is eluted in a short time, and when it exceeds 500 ° C., it is difficult to elute. A range of ˜500 ° C. is preferred.
[0010]
【The invention's effect】
The aluminum electrolytic capacitor and the cathode foil for an aluminum electrolytic capacitor according to the present invention can significantly reduce the capacitance change in the product life test, and can significantly improve the reliability.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10873699A JP4289717B2 (en) | 1999-04-16 | 1999-04-16 | Aluminum electrolytic capacitor and method for producing cathode foil for aluminum electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10873699A JP4289717B2 (en) | 1999-04-16 | 1999-04-16 | Aluminum electrolytic capacitor and method for producing cathode foil for aluminum electrolytic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000299257A JP2000299257A (en) | 2000-10-24 |
| JP4289717B2 true JP4289717B2 (en) | 2009-07-01 |
Family
ID=14492233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10873699A Expired - Fee Related JP4289717B2 (en) | 1999-04-16 | 1999-04-16 | Aluminum electrolytic capacitor and method for producing cathode foil for aluminum electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4289717B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1580772B1 (en) * | 2002-11-08 | 2015-03-11 | Nippon Chemi-Con Corporation | Electrolytic capacitor |
| CN1310262C (en) * | 2003-07-08 | 2007-04-11 | 深圳市东阳光化成箔股份有限公司 | Methof for manufacturing foil of cathode of electrolytic capacitor |
| JP4867462B2 (en) * | 2006-05-08 | 2012-02-01 | パナソニック株式会社 | Aluminum electrolytic capacitor and cathode foil for aluminum electrolytic capacitor |
| JP2008010490A (en) * | 2006-06-27 | 2008-01-17 | Nichicon Corp | Manufacturing method of electrode for electrolytic capacitor |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5343864A (en) * | 1976-10-01 | 1978-04-20 | Hitachi Denkaihaku Kenkyusho | Method of stabilizing treatment of aluminum negative electrode foil for electrolytic capacitor |
| JPH01319924A (en) * | 1988-06-22 | 1989-12-26 | Matsushita Electric Ind Co Ltd | Manufacture of aluminum cathode foil for electrolytic capacitor |
| JP2745875B2 (en) * | 1991-06-29 | 1998-04-28 | 日本ケミコン株式会社 | Cathode materials for electrolytic capacitors |
| JPH1167606A (en) * | 1997-08-11 | 1999-03-09 | Nippon Chemicon Corp | Electrolytic capacitor |
-
1999
- 1999-04-16 JP JP10873699A patent/JP4289717B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000299257A (en) | 2000-10-24 |
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