JP2004193408A - Electrolyte for driving electrolytic capacitor - Google Patents
Electrolyte for driving electrolytic capacitor Download PDFInfo
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- JP2004193408A JP2004193408A JP2002360767A JP2002360767A JP2004193408A JP 2004193408 A JP2004193408 A JP 2004193408A JP 2002360767 A JP2002360767 A JP 2002360767A JP 2002360767 A JP2002360767 A JP 2002360767A JP 2004193408 A JP2004193408 A JP 2004193408A
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- Prior art keywords
- salt
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- electrolyte
- ammonium
- electrolytic capacitor
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Abstract
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の駆動用電解液(以下、電解液と称す)の改良に関するものであり、詳しくは、電解液の熱的安定性の向上技術に関するものである。
【0002】
【従来の技術】
従来、電解コンデンサの中高圧用電解液は、エチレングリコールを主成分とする溶媒に、アゼライン酸、セバシン酸、デカンジカルボン酸等の直鎖のカルボン酸または上記のカルボン酸に側鎖基としてアルキル基およびアルキレン基等を置換させたカルボン酸を溶解させた電解液が使用されてきた(例えば、特許文献1、2参照)。
【0003】
【特許文献1】
特公平7−48460号公報(第2頁、表)
【特許文献2】
特公平7−63047号公報(第3頁、表1)
【0004】
【発明が解決しようとする課題】
しかし、上記カルボン酸はエチレングリコールに対しての溶解度が低く、また、エチレングリコールとエステル化しやすいため、熱的安定性が低いという欠点があった。この改善策として、側鎖基にアルキル基及びアルキレン基等を置換させたカルボン酸が使用されているが、更に高温度化が進む電解コンデンサにおいての使用は困難であるという問題があった。
【0005】
本発明の課題は、上記の問題を解決するもので、高温における安定性を向上させた電解コンデンサの駆動用電解液を提供することにある。
【0006】
【課題を解決するための手段】
本発明は、上記の課題を解決するために各種検討した結果、見出されたものであり、カルボキシル基の隣接位置に置換基としてスルホ基を導入することにより、エチレングリコールとのエステル化を立体的に抑制させる効果、エチレングリコール等の溶媒に対する溶解性を向上させる効果、電導度を向上させる効果を利用した電解液である。
【0007】
すなわち、本発明の電解コンデンサの駆動用電解液では、エチレングリコールを含む溶媒に対して、以下の化学式で表されるスルホジカルボン酸またはその塩を溶解したことを特徴とする。
【0008】
【化2】
【0009】
本発明において、上記スルホジカルボン酸の塩としては、アンモニウム塩の他、メチルアミン、エチルアミン、t−ブチルアミン等の一級アミン塩、ジメチルアミン、エチルメチルアミン、ジエチルアミン等の二級アミン塩、トリメチルアミン、ジエチルメチルアミン、エチルジメチルアミン、トリエチルアミン等の三級アミン塩、テトラメチルアンモニウム、トリエチルメチルアンモニウム、テトラエチルアンモニウム等の四級アンモニウム塩、イミダゾリニウム塩等を例示することができる。
【0010】
溶媒としては、エチレングリコールの他、プロピレングリコール等のグリコール類、γ−ブチロラクトン、N−メチル−2−ピロリドン等のラクトン類、N−メチルホルムアミド、N,N−ジメチルホルムアミド、N−エチルホルムアミド、N,N−ジエチルホルムアミド、N−メチルアセトアミド、N,N−ジメチルアセトアミド、N−エチルアセトアミド、N,N−ジエチルアセトアミド、ヘキサメチルホスホリックアミド等のアミド類、エチレンカーボネート、プロピレンカーボネート、イソブチレンカーボネート等の炭酸類、アセトニトリル等のニトリル類、ジメチルスルホキシド等のオキシド類、エーテル類、ケトン類、エステル類、水等を例示することができる。
【0011】
本発明において、上記スルホジカルボン酸またはその塩の溶解量は、電解質の種類および溶媒の種類により異なるが、電解液全体に対して1.0〜20.0wt%であることが好ましい。また、1.0wt%未満では十分な効果が得られず、20.0wt%を超えると、析出する傾向にある。
【0012】
上記の電解液には、漏れ電流の低減、ガス吸収等の目的で種々の添加剤を加えることができる。添加剤の例として、リン酸化合物、ニトロ化合物等が挙げられる。
【0013】
【発明の実施の形態】
本発明に係る電解液では、エチレングリコール等の溶媒に対して、スルホジカルボン酸またはその塩を溶解する。ここで、前記スルホジカルボン酸またはその塩の溶解量は、電解液全体に対して1.0〜20.0wt%である。
【0014】
このような電解液では、エチレングリコールを主成分とする溶媒にスルホジカルボン酸またはそれらの塩を溶解することで、電解液の熱的安定性を向上させることができる。
【0015】
【実施例】
以下、本発明を実施例に基づき具体的に説明する。
【0016】
まず、表1に示す組成の電解液について、30℃における比抵抗、並びに火花電圧を測定した結果を表1に示す。
【0017】
【表1】
【0018】
また、上記の各電解液を用いて、250V−68μF(φ16×25L)のアルミニウム電解コンデンサを製作し、105℃、1000時間経過した後、電解液を絞り出して、その比抵抗並びに火花電圧を測定した結果を表1に示す。
【0019】
表1に示すように、スルホジカルボン酸を溶解させた本発明の実施例に係る電解液は、従来の直鎖のカルボン酸を溶解させた従来例の電解液と比較して1000時間後の比抵抗上昇、並びに火花電圧低下が抑えられている。
【0020】
また、スルホカルボン酸はエチレングリコールを主成分とする溶媒に対して溶解度が低いが、実施例の如く直鎖のカルボン酸を組み合わせることによって、上記の効果は得られている。
【0021】
なお、スルホカルボン酸を溶解させた効果は、実施例に限定されるものではなく、各種化合物を単独または複数溶解させた電解液に用いても実施例と同様の効果があった。
【0022】
【発明の効果】
上記の通り、本発明に係る電解液では、エチレングリコールを主成分とする溶媒にスルホカルボン酸またはその塩を溶解したので、電解液の熱的安定性の改善を図ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an improvement in a driving electrolyte (hereinafter, referred to as an electrolyte) for an aluminum electrolytic capacitor, and more particularly to a technique for improving the thermal stability of the electrolyte.
[0002]
[Prior art]
Conventionally, a medium-to-high pressure electrolytic solution of an electrolytic capacitor has a solvent mainly composed of ethylene glycol, a linear carboxylic acid such as azelaic acid, sebacic acid, decanedicarboxylic acid, or an alkyl group as a side group in the above carboxylic acid. And an electrolytic solution in which a carboxylic acid substituted with an alkylene group or the like is dissolved (for example, see Patent Documents 1 and 2).
[0003]
[Patent Document 1]
Japanese Patent Publication No. 7-48460 (page 2, table)
[Patent Document 2]
Japanese Patent Publication No. 7-63047 (page 3, table 1)
[0004]
[Problems to be solved by the invention]
However, the above-mentioned carboxylic acids have low solubility in ethylene glycol, and are liable to be esterified with ethylene glycol, so that they have low thermal stability. As a remedy, a carboxylic acid in which an alkyl group, an alkylene group, or the like is substituted for a side chain group is used, but there is a problem that it is difficult to use an electrolytic capacitor in which the temperature is further increased.
[0005]
An object of the present invention is to solve the above problems and to provide an electrolytic solution for driving an electrolytic capacitor with improved stability at high temperatures.
[0006]
[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 to introduce esterification with ethylene glycol by introducing a sulfo group as a substituent at a position adjacent to a carboxyl group. It is an electrolytic solution that utilizes the effect of reducing the concentration, the effect of improving the solubility in solvents such as ethylene glycol, and the effect of improving the conductivity.
[0007]
That is, the electrolytic solution for driving an electrolytic capacitor of the present invention is characterized in that a sulfodicarboxylic acid represented by the following chemical formula or a salt thereof is dissolved in a solvent containing ethylene glycol.
[0008]
Embedded image
[0009]
In the present invention, as the salt of the sulfodicarboxylic acid, in addition to ammonium salts, primary amine salts such as methylamine, ethylamine and t-butylamine, secondary amine salts such as dimethylamine, ethylmethylamine and diethylamine, trimethylamine and diethylamine Examples include tertiary amine salts such as methylamine, ethyldimethylamine, and triethylamine; quaternary ammonium salts such as tetramethylammonium, triethylmethylammonium, and tetraethylammonium; and imidazolinium salts.
[0010]
Examples of the solvent include, in addition to ethylene glycol, glycols such as propylene glycol, lactones such as γ-butyrolactone, N-methyl-2-pyrrolidone, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N-ethylformamide, Amides such as N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, hexamethylphosphoramide, ethylene carbonate, propylene carbonate, isobutylene carbonate, etc. Examples thereof include carbonates, nitriles such as acetonitrile, oxides such as dimethyl sulfoxide, ethers, ketones, esters, and water.
[0011]
In the present invention, the amount of the sulfodicarboxylic acid or salt thereof to be dissolved varies depending on the type of the electrolyte and the type of the solvent, but is preferably 1.0 to 20.0 wt% with respect to the entire electrolytic solution. On the other hand, if the content is less than 1.0 wt%, a sufficient effect cannot be obtained, and if it exceeds 20.0 wt%, there is a tendency for precipitation.
[0012]
Various additives can be added to the electrolyte for the purpose of reducing leakage current, absorbing gas, and the like. Examples of the additive include a phosphoric acid compound and a nitro compound.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
In the electrolytic solution according to the present invention, sulfodicarboxylic acid or a salt thereof is dissolved in a solvent such as ethylene glycol. Here, the dissolution amount of the sulfodicarboxylic acid or a salt thereof is 1.0 to 20.0 wt% with respect to the entire electrolytic solution.
[0014]
In such an electrolytic solution, the thermal stability of the electrolytic solution can be improved by dissolving the sulfodicarboxylic acid or a salt thereof in a solvent containing ethylene glycol as a main component.
[0015]
【Example】
Hereinafter, the present invention will be specifically described based on examples.
[0016]
First, the results of measuring the specific resistance at 30 ° C. and the spark voltage of the electrolytic solution having the composition shown in Table 1 are shown in Table 1.
[0017]
[Table 1]
[0018]
Also, an aluminum electrolytic capacitor of 250 V-68 μF (φ16 × 25 L) was manufactured using each of the above electrolytes, and after 105 hours at 105 ° C., the electrolyte was squeezed out and its specific resistance and spark voltage were measured. Table 1 shows the results.
[0019]
As shown in Table 1, the electrolyte solution according to the example of the present invention in which the sulfodicarboxylic acid was dissolved was compared with the conventional electrolyte solution in which the conventional linear carboxylic acid was dissolved, in a ratio after 1000 hours. Resistance rise and spark voltage drop are suppressed.
[0020]
Although the sulfocarboxylic acid has low solubility in a solvent containing ethylene glycol as a main component, the above-mentioned effects are obtained by combining a linear carboxylic acid as in the examples.
[0021]
In addition, the effect of dissolving the sulfocarboxylic acid is not limited to the examples, and the same effects as those of the examples were obtained even when various compounds were used singly or in an electrolytic solution in which a plurality of compounds were dissolved.
[0022]
【The invention's effect】
As described above, in the electrolytic solution according to the present invention, since the sulfocarboxylic acid or a salt thereof is dissolved in the solvent containing ethylene glycol as a main component, the thermal stability of the electrolytic solution can be improved.
Claims (2)
Priority Applications (1)
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JP2002360767A JP4020775B2 (en) | 2002-12-12 | 2002-12-12 | Electrolytic solution for electrolytic capacitor drive |
Applications Claiming Priority (1)
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JP2002360767A JP4020775B2 (en) | 2002-12-12 | 2002-12-12 | Electrolytic solution for electrolytic capacitor drive |
Publications (2)
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JP2004193408A true JP2004193408A (en) | 2004-07-08 |
JP4020775B2 JP4020775B2 (en) | 2007-12-12 |
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JP2002360767A Expired - Fee Related JP4020775B2 (en) | 2002-12-12 | 2002-12-12 | Electrolytic solution for electrolytic capacitor drive |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8227116B2 (en) | 2003-12-15 | 2012-07-24 | Nec Corporation | Secondary battery |
US8357471B2 (en) | 2003-12-15 | 2013-01-22 | Nec Corporation | Secondary battery using an electrolyte solution |
-
2002
- 2002-12-12 JP JP2002360767A patent/JP4020775B2/en not_active Expired - Fee Related
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8227116B2 (en) | 2003-12-15 | 2012-07-24 | Nec Corporation | Secondary battery |
US8357471B2 (en) | 2003-12-15 | 2013-01-22 | Nec Corporation | Secondary battery using an electrolyte solution |
US8445144B2 (en) * | 2003-12-15 | 2013-05-21 | Nec Corporation | Additive for an electrolyte solution for an electrochemical device |
US9012071B2 (en) | 2003-12-15 | 2015-04-21 | Nec Corporation | Electrolyte solution for a secondary battery |
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