JP3657664B2 - Electrolytic solution for electrolytic capacitor drive - Google Patents
Electrolytic solution for electrolytic capacitor drive Download PDFInfo
- Publication number
- JP3657664B2 JP3657664B2 JP26005195A JP26005195A JP3657664B2 JP 3657664 B2 JP3657664 B2 JP 3657664B2 JP 26005195 A JP26005195 A JP 26005195A JP 26005195 A JP26005195 A JP 26005195A JP 3657664 B2 JP3657664 B2 JP 3657664B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic
- electrolytic solution
- electrolytic capacitor
- acid
- sodium
- 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
- 239000003990 capacitor Substances 0.000 title claims description 20
- 239000008151 electrolyte solution Substances 0.000 title claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 150000003863 ammonium salts Chemical class 0.000 claims description 9
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims description 7
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 7
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 7
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 7
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229940005740 hexametaphosphate Drugs 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、中高圧用電解コンデンサの駆動用電解液に関するものである。
【０００２】
【従来の技術】
従来より電解コンデンサの駆動用電解液（以下電解液という）には、酸化皮膜形成能を有し、アルミ箔の耐水性を向上させ、かつ皮膜劣化の抑制を目的としたオルトリン酸またはそのアンモニウム塩等のリン酸化合物の添加が検討されている。
【０００３】
【発明が解決しようとする課題】
オルトリン酸またはそのアンモニウム塩は酸化皮膜形成時に消費されるため電解液中の濃度は経時的に低下し、長期に及ぶ電解コンデンサの高温負荷試験や高温無負荷試験においてアルミ箔の酸化皮膜の劣化により静電容量の低下や、漏れ電流の増大を招く。そこでオルトリン酸またはそのアンモニウム塩の添加量を過剰に増加させると、アルミ箔および酸化皮膜に対して溶解性が増大し腐食を生じさせるので好ましくない。さらに、オルトリン酸またはそのアンモニウム塩は熱的安定性に乏しく、高温領域では上述の酸化皮膜の劣化を抑制する効果が減少するなどの欠点をもっていた。
本発明は以上の欠点を改善し、電解コンデンサの特性を長時間にわたって安定化し、高温下において皮膜劣化抑制効果を示す電解コンデンサの駆動用電解液を提供することを目的とする。
【０００４】
【課題を解決するための手段】
エチレングリコールを主成分とする溶媒に、高級二塩基酸またはそのアンモニウム塩及びホウ酸またはそのアンモニウム塩を溶解した電解コンデンサ用電解液に、メタリン酸またはメタリン酸ナトリウム、あるいはヘキサメタリン酸ナトリウムを溶解させた電解液であり、上記メタリン酸またはメタリン酸ナトリウムを電解液全体に対して０．０１〜０．４５重量％溶解するか、あるいは上記ヘキサメタリン酸ナトリウムを電解液全体に対して０．０１〜０．０９重量％溶解した電解液を用いることで、長期にわたって安定した特性を示す電解コンデンサを提供できることを見いだした。
【０００５】
【作用】
メタリン酸は水溶液中において水和反応によりオルトリン酸に変化するが、水分の少ない電解コンデンサ用電解液中ではその反応が緩やかに進行し、徐々にオルトリン酸が電解液中に供給されるため、オルトリン酸のもつアルミ箔の耐水性、酸化皮膜形成能を低下させず維持できることから、電解コンデンサの静電容量の低下や、漏れ電流の増大を防止できる。
また、分子量の大きいヘキサメタリン酸ナトリウムはその構造から熱的安定性に優れるため高温領域においても電解コンデンサの特性の長期安定化が可能である。
【０００６】
【実施例】
以下、実施例の具体的内容について説明する。溶媒には、エチレングリコール等の多価アルコールを用いる。溶質には７−ビニル−９−ヘキサデセン−１−１６−ジカルボン酸またはそのアンモニウム塩を用いる。添加剤としてはホウ酸、マンニットを用いる。表１、表２に実施例の組成および測定結果を示す。但し、比抵抗は３０℃、火花電圧は８５℃において測定した。表１、表２から明らかなように、従来例及び実施例ともに比抵抗は７１０Ω・ｃｍ程度であったが、従来例において火花電圧は４３０Ｖであったのに対し実施例１〜９では４４０〜４５０Ｖとなる。すなわち比抵抗はほぼ同等で、火花電圧は実施例１〜９の方が２．０〜５．０％高い値を示した。
【０００７】
【表１】
【表２】
また、表１、表２に示す従来例及び実施例１〜９の電解液を用いた定格４００Ｖ、１０μＦの電解コンデンサによる高温負荷試験及び高温無負荷試験を行った。高温負荷試験条件は、温度１０５℃、印加電圧４００Ｖ、放置時間２０００ｈとし、高温無負荷試験条件は、温度１０５℃、放置時間２０００ｈとし、電解コンデンサ試料数は各電解液、各試験１０個とした。測定結果を表３及び表４に示す。
【００１０】
【表３】
【表４】
表３、表４より明らかなように、初期において、実施例１〜６は従来例と顕著な差はみられないが、実施例７〜９については、従来例と比較するとｔａｎδ、漏れ電流で若干改善されている。
高温負荷試験２０００ｈ後においては、表３より明らかなように従来例と実施例の差はより顕著にみられ、特に実施例７〜９では従来例に対して、静電容量変化率、ｔａｎδ、漏れ電流のいずれにおいても大幅に改善されている。
【００１３】
表４に示されているように、高温負荷試験２０００ｈ後と同様、高温無負荷試験２０００ｈ後の測定結果においても従来例に比べ実施例では各特性において改善されている。このことから、メタリン酸、メタリン酸ナトリウム、ヘキサメタリン酸ナトリウムはコンデンサ特性を向上させ、特にヘキサメタリン酸ナトリウムは高温領域でも改善効果が顕著であることがわかる。メタリン酸、メタリン酸ナトリウムおよびヘキサメタリン酸ナトリウムにおいて添加量が０．０１％未満では、顕著な効果がみられず、メタリン酸およびメタリン酸ナトリウムは添加量が０．５％以上、ヘキサメタリン酸ナトリウムは添加量が０．１％以上では、溶解に時間を要し、また溶質の析出を招き、さらに火花電圧が低下するので好ましくない。
【００１４】
【発明の効果】
上述の通り、本発明は、従来の電解液に比べ、静電容量、ｔａｎδ、漏れ電流等の電解コンデンサの諸特性を向上させ、高温下で長時間にわたって安定な電解コンデンサを実現できる電解液の提供が可能である。[0001]
[Industrial application fields]
The present invention relates to an electrolyte for driving a medium-high voltage electrolytic capacitor.
[0002]
[Prior art]
Conventionally, an electrolytic solution for driving an electrolytic capacitor (hereinafter referred to as an electrolytic solution) is orthophosphoric acid or an ammonium salt thereof having an oxide film forming ability, improving water resistance of an aluminum foil, and suppressing film deterioration. The addition of phosphoric acid compounds such as these has been studied.
[0003]
[Problems to be solved by the invention]
Since orthophosphoric acid or its ammonium salt is consumed during the formation of the oxide film, the concentration in the electrolyte decreases with time, and due to deterioration of the oxide film on the aluminum foil in long-term high-temperature load tests and high-temperature no-load tests of electrolytic capacitors. It causes a decrease in capacitance and an increase in leakage current. Therefore, if the amount of orthophosphoric acid or its ammonium salt added is excessively increased, the solubility in the aluminum foil and the oxide film is increased, which causes corrosion. Furthermore, orthophosphoric acid or its ammonium salt has poor thermal stability, and has the disadvantage that the effect of suppressing the deterioration of the above-described oxide film is reduced at high temperatures.
An object of the present invention is to provide an electrolytic solution for driving an electrolytic capacitor that improves the above drawbacks, stabilizes the characteristics of the electrolytic capacitor over a long period of time, and exhibits an effect of suppressing film deterioration at high temperatures.
[0004]
[Means for Solving the Problems]
Metaphosphoric acid or sodium metaphosphate or sodium hexametaphosphate was dissolved in an electrolytic solution for an electrolytic capacitor in which a higher dibasic acid or its ammonium salt and boric acid or its ammonium salt were dissolved in a solvent containing ethylene glycol as a main component. an electrolyte solution, 0.01 to 0 the metaphosphate or sodium metaphosphate for the entire electrolyte. 45 or wt% dissolved, or sodium the hexametaphosphate for the entire electrolytic solution from 0.01 to 0. It has been found that an electrolytic capacitor exhibiting stable characteristics over a long period of time can be provided by using an electrolytic solution in which 09 % by weight is dissolved.
[0005]
[Action]
Metaphosphoric acid changes to orthophosphoric acid in an aqueous solution due to a hydration reaction, but the reaction proceeds slowly in an electrolytic solution for electrolytic capacitors with little moisture, and orthophosphoric acid is gradually supplied into the electrolytic solution. Since the water resistance of the aluminum foil with acid and the ability to form an oxide film can be maintained without lowering, the capacitance of the electrolytic capacitor can be prevented from decreasing and the leakage current can be prevented from increasing.
In addition, sodium hexametaphosphate having a large molecular weight is excellent in thermal stability due to its structure, and therefore, the characteristics of the electrolytic capacitor can be stabilized for a long time even in a high temperature region.
[0006]
【Example】
Hereinafter, specific contents of the embodiment will be described. A polyhydric alcohol such as ethylene glycol is used as the solvent. As the solute, 7-vinyl-9-hexadecene-1-16-dicarboxylic acid or an ammonium salt thereof is used. As the additive, boric acid or mannitol is used. Tables 1 and 2 show the compositions and measurement results of the examples. However, the specific resistance was measured at 30 ° C., and the spark voltage was measured at 85 ° C. As is clear from Tables 1 and 2, the specific resistance was about 710 Ω · cm in both the conventional example and the example. However, in the conventional example, the spark voltage was 430 V, whereas in Examples 1 to 9, the specific voltage was 440 V. 450V. That is, the specific resistance was almost the same, and the spark voltage was 2.0 to 5.0% higher in Examples 1 to 9.
[0007]
[Table 1]
[Table 2]
In addition, a high temperature load test and a high temperature no load test were performed using an electrolytic capacitor having a rating of 400 V and a 10 μF using the conventional examples shown in Tables 1 and 2 and the electrolytes of Examples 1 to 9. The high-temperature load test conditions were a temperature of 105 ° C., an applied voltage of 400 V, and a standing time of 2000 h. The high-temperature no-load test conditions were a temperature of 105 ° C. and a standing time of 2000 h, and the number of electrolytic capacitor samples was 10 for each electrolyte and each test. . The measurement results are shown in Tables 3 and 4.
[0010]
[Table 3]
[Table 4]
As is apparent from Tables 3 and 4, in the initial stage, Examples 1 to 6 are not significantly different from the conventional example, but Examples 7 to 9 are tan δ and leakage current as compared with the conventional example. Slightly improved.
After the high temperature load test 2000 h, as clearly shown in Table 3, the difference between the conventional example and the example is more noticeable. In particular, in Examples 7 to 9, the capacitance change rate, tan δ, There is a significant improvement in both leakage currents.
[0013]
As shown in Table 4, as in the case after the high temperature load test 2000 h, the measurement results after the high temperature no load test 2000 h are improved in the respective characteristics in the embodiment as compared with the conventional example. From this, it can be seen that metaphosphoric acid, sodium metaphosphate, and sodium hexametaphosphate improve the capacitor characteristics. In particular, sodium hexametaphosphate has a remarkable improvement effect even in a high temperature region. When the addition amount is less than 0.01% in metaphosphoric acid, sodium metaphosphate, and sodium hexametaphosphate, there is no significant effect. Addition amount of metaphosphoric acid and sodium metaphosphate is 0.5% or more, and sodium hexametaphosphate is added. If the amount is 0.1% or more, it takes a long time to dissolve, causes solute precipitation, and further reduces the spark voltage, which is not preferable.
[0014]
【The invention's effect】
As described above, the present invention improves the various characteristics of the electrolytic capacitor such as capacitance, tan δ, leakage current, etc., compared with the conventional electrolytic solution, and realizes a stable electrolytic capacitor for a long time at high temperature. Can be provided.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26005195A JP3657664B2 (en) | 1995-10-06 | 1995-10-06 | Electrolytic solution for electrolytic capacitor drive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26005195A JP3657664B2 (en) | 1995-10-06 | 1995-10-06 | Electrolytic solution for electrolytic capacitor drive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09102439A JPH09102439A (en) | 1997-04-15 |
| JP3657664B2 true JP3657664B2 (en) | 2005-06-08 |
Family
ID=17342630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26005195A Expired - Fee Related JP3657664B2 (en) | 1995-10-06 | 1995-10-06 | Electrolytic solution for electrolytic capacitor drive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3657664B2 (en) |
-
1995
- 1995-10-06 JP JP26005195A patent/JP3657664B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09102439A (en) | 1997-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3657664B2 (en) | Electrolytic solution for electrolytic capacitor drive | |
| JP3254981B2 (en) | Electrolyte for electrolytic capacitors | |
| JPH11340097A (en) | Electrolytic solution for driving electrolytic capacitor | |
| JP2921363B2 (en) | Electrolyte for electrolytic capacitors | |
| JP2529300B2 (en) | Electrolytic solution for driving electrolytic capacitors | |
| JP3254983B2 (en) | Electrolyte for electrolytic capacitors | |
| KR0137998B1 (en) | Electrolytic Solution for Aluminum Electrolytic Capacitors | |
| JP2532457B2 (en) | Electrolytic solution for driving electrolytic capacitors | |
| JP3494464B2 (en) | Electrolyte for driving electrolytic capacitors | |
| JP2624710B2 (en) | Electrolytic capacitor | |
| JPH0719731B2 (en) | Electrolytic solution for electrolytic capacitors | |
| JPH03225908A (en) | Electrolyte for electrolytic capacitor | |
| JP2625464B2 (en) | Electrolyte for driving electrolytic capacitors | |
| JP2765875B2 (en) | Electrolyte for electrolytic capacitors | |
| JPH04290418A (en) | Electrolyte for driving electrolytic capacitor and electrolytic capacitor using the electrolyte | |
| KR970008556B1 (en) | Electrolyte of aluminium electrolytic condenser | |
| JPS6263416A (en) | Electrolyte for driving aluminum electrolytic condenser | |
| JPH01103820A (en) | Electrolyte for driving electrolytic capacitor | |
| JPH0376007B2 (en) | ||
| JPH04364015A (en) | Electrolytic capacitor driving electrolytic solution | |
| JPS63261822A (en) | Electrolyte for driving electrolytic capacitor | |
| JPH0410514A (en) | Electrolyte for electrolytic capacitor | |
| JPH0485807A (en) | Electrolyte for electrolytic capacitor | |
| JPH0775214B2 (en) | Aluminum electrolytic capacitor electrolyte | |
| JPS6269607A (en) | Electrolyte for driving aluminum electrolytic condenser |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20041122 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20041129 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050128 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20050307 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20050310 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090318 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100318 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110318 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110318 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120318 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130318 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140318 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |