JPH0810663B2 - Electrolytic solution for electrolytic capacitors - Google Patents
Electrolytic solution for electrolytic capacitorsInfo
- Publication number
- JPH0810663B2 JPH0810663B2 JP62051885A JP5188587A JPH0810663B2 JP H0810663 B2 JPH0810663 B2 JP H0810663B2 JP 62051885 A JP62051885 A JP 62051885A JP 5188587 A JP5188587 A JP 5188587A JP H0810663 B2 JPH0810663 B2 JP H0810663B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- electrolytic
- electrolytic solution
- electrolytic capacitor
- conductivity
- 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
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、ピロリジニウム化合物、又はピペリジニウ
ム化合物のカルボン酸塩を電解質として含む高電導度の
電解コンデンサ用電解液に関するものである。TECHNICAL FIELD The present invention relates to an electrolytic solution for a high-conductivity electrolytic capacitor, which contains a carboxylate of a pyrrolidinium compound or a piperidinium compound as an electrolyte.
従来、電解コンデンサ用電解液として、アジピン酸な
どの有機酸又はその塩をエチレングリコールなどの多価
アルコール類を溶解したものが用いられている。Conventionally, as an electrolytic solution for an electrolytic capacitor, an organic acid such as adipic acid or a salt thereof in which a polyhydric alcohol such as ethylene glycol is dissolved is used.
電解液は電解コンデンサの陽極電極の誘電体層と集電
陰極との間に介在して、電解コンデンサの直列抵抗を構
成し、このため電解液の電導度が低いと、電解コンデン
サの内部の等価直列抵抗分を増大させ、高周波特性や損
失特性が悪くなる。近年ますます高度の電気的特性の電
解コンデンサが求められており、現状の電解液の電導度
では十分とは言えない。特に、現状の電解液の場合、溶
質の濃度を十分に高めても所望の電導度が得られない場
合が多く、そのためやむをえず意図的に水を添加して電
導度の向上を図ることが行われている。水の添加は製品
コンデンサの高温での安定性を劣化させる別の問題を提
起する。従って、電導度と安定性の高い電解液の要望が
高い。The electrolytic solution is interposed between the dielectric layer of the anode electrode of the electrolytic capacitor and the collecting cathode to form a series resistance of the electrolytic capacitor. Therefore, if the electrical conductivity of the electrolytic solution is low, the internal equivalent of the electrolytic capacitor The series resistance increases, and the high frequency characteristics and loss characteristics deteriorate. In recent years, electrolytic capacitors having more and more advanced electrical characteristics have been demanded, and it cannot be said that the current conductivity of the electrolytic solution is sufficient. In particular, in the case of the current electrolytic solution, the desired conductivity is often not obtained even if the concentration of the solute is sufficiently increased, so that it is unavoidable to intentionally add water to improve the conductivity. It is being appreciated. The addition of water poses another problem that degrades the high temperature stability of the product capacitor. Therefore, there is a strong demand for an electrolytic solution having high conductivity and stability.
それ故、本発明の目的は、非水系、もしくは可及的に
非水系の高電導度の電解液を提供することにより、電解
コンデンサの電気的特性を向上させ、かつ安定した特性
を長期間維持することによって、電解コンデンサの信頼
性を向上させることを目的としている。Therefore, an object of the present invention is to improve the electrical characteristics of an electrolytic capacitor and to maintain stable characteristics for a long period of time by providing a non-aqueous or, as far as possible, non-aqueous electrolyte having high conductivity. By doing so, it is intended to improve the reliability of the electrolytic capacitor.
本発明に係る電解コンデンサ用電解液は、非プロトン
溶媒、又は非プロトン溶媒を主とした多価アルコール類
との混合溶媒中に、一般式 （式中R1、R2は炭素原子数１〜６個のアルキル基、又は
フェニル基、R3は水素原子又は炭素数１〜６個のアルキ
ル基、Ｂはフタル酸又は脂肪族オキシカルボン酸のアニ
オン、ｎは４又は５）で表されるピロリジニウム化合
物、又はピペリジニウム化合物、又はピペリジニウム化
合物のカルボン酸塩を電解質として含むことを特徴とす
る。The electrolytic solution for an electrolytic capacitor according to the present invention has a general formula in an aprotic solvent or a mixed solvent with a polyhydric alcohol mainly containing an aprotic solvent. (Wherein R 1 and R 2 are an alkyl group having 1 to 6 carbon atoms or a phenyl group, R 3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, B is a phthalic acid or an aliphatic oxycarboxylic acid) The anion, and n is a pyrrolidinium compound represented by 4 or 5), a piperidinium compound, or a carboxylic acid salt of a piperidinium compound is contained as an electrolyte.
本発明の対象となるピロリジニウム化合物としては、
Ｎ、Ｎ−ジメチルピロリジニウム、Ｎ、Ｎ−ジエチルピ
ロリジニウム、Ｎ、Ｎ−メチルエチルピロリジニウム、
Ｎ、Ｎ−メチルフエニルピロリジニウム、Ｎ、Ｎ−ジメ
チル−２−メチルピロリジニウム、Ｎ、Ｎ−ジメチル−
３−メチルピロリジニウム、などが挙げられ、ピペリジ
ニウム化合物としては、Ｎ、Ｎ−ジメチルピペリジニウ
ム、Ｎ、Ｎ−メチルエチルピペリジニウム、Ｎ、Ｎ−ジ
エチルピペリジニウム、Ｎ、Ｎ−メチルフエニルピペリ
ジニウム、Ｎ、Ｎ−ジメチル−２−メチルピペリジニウ
ム、Ｎ、Ｎ−ジメチル−３−メチルピペリジニウムなど
が挙げられる。The pyrrolidinium compound which is the object of the present invention,
N, N-dimethylpyrrolidinium, N, N-diethylpyrrolidinium, N, N-methylethylpyrrolidinium,
N, N-methylphenylpyrrolidinium, N, N-dimethyl-2-methylpyrrolidinium, N, N-dimethyl-
3-methylpyrrolidinium, and the like, and the piperidinium compound includes N, N-dimethylpiperidinium, N, N-methylethylpiperidinium, N, N-diethylpiperidinium, N, N-methyl. Examples thereof include phenylpiperidinium, N, N-dimethyl-2-methylpiperidinium, N, N-dimethyl-3-methylpiperidinium and the like.
本発明の対象となるカルボン酸としては、フタル酸又
は脂肪族オキシカルボン酸、例えばグリコール酸、乳
酸、リンゴ酸、クエン酸及び酒石酸が挙げられる。Carboxylic acids covered by the present invention include phthalic acid or aliphatic oxycarboxylic acids such as glycolic acid, lactic acid, malic acid, citric acid and tartaric acid.
本発明で使用される非プロトン系溶媒としては、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、γ−ブチロラクトン、Ｎ−メチル−２−ピ
ロリドン、エチレンカーボネイト、プロピレンカーボネ
ート、ジメチルスルホオキシド、アセトニトリル又はこ
られの混合物の群より選択されるが、これらに限定され
るものではない。The aprotic solvent used in the present invention includes N-
Methylformamide, N, N-dimethylformamide,
N-ethylformamide, NN-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, γ-butyrolactone, N-methyl-2-pyrrolidone, ethylene carbonate , Propylene carbonate, dimethyl sulfoxide, acetonitrile or a mixture of these, but not limited to.
本発明で使用される多価アルコール類としては、エチ
レングリコロール、プロピレングリコール、ジエチレン
グリコール、ヘキシレングリコール、フェニールグリコ
ール、グリセリン、エリスリトール、ヘキシトール又は
これらの混合物の群より選択されるが、これらに限定さ
れるものでない。これらの多価アルコール類は、非プロ
トン溶媒単独で得られない所望の高電導度電解液を得る
場合に、最小限の使用料で添加され、一般に電解液に対
し約30重量％まで使用される。The polyhydric alcohol used in the present invention is selected from the group of ethylene glycolol, propylene glycol, diethylene glycol, hexylene glycol, phenyl glycol, glycerin, erythritol, hexitol or a mixture thereof, but is not limited thereto. Not something. These polyhydric alcohols are added with a minimum amount of charge when obtaining a desired high conductivity electrolyte which cannot be obtained by aprotic solvent alone, and are generally used up to about 30% by weight based on the electrolyte. .
本発明に係る電解コンデンサ用電解液は、一般的に、
硫酸水素ピロリジニウム類又は硫酸水素ピペリジニウム
類を酢酸メチルまたは塩化メチルなどの溶媒に溶かし、
目的カルボン酸を当量添加し、次に２当量の水酸化アル
カリ金属を添加反応させて、析出物を除去した後、減圧
乾燥させて無水塩を得、これを所定溶媒に所望の電導度
が得られる濃度に溶解して調製する。The electrolytic solution for an electrolytic capacitor according to the present invention is generally
Pyrrolidinium hydrogensulfate or piperidinium hydrogensulfate is dissolved in a solvent such as methyl acetate or methyl chloride,
The target carboxylic acid is added in an equivalent amount, and then 2 equivalents of an alkali metal hydroxide is added and reacted to remove the precipitate, followed by drying under reduced pressure to obtain an anhydrous salt, which is used in a predetermined solvent to obtain a desired conductivity. Prepare by dissolving it to the required concentration.
以下、本発明に係る電解コンデンサ用電解液の実施例
につき、各種ピロリジニウム化合物又はピペリジニウム
化合物のカルボン酸塩の各種溶媒に対する15重量％溶液
を、前記一般調製方法に準じて調製し、この電導度を第
１表に示す。なお、比較例として、従来の標準的電解液
（エチレングリコール78重量％、水10重量％、アジピン
酸アンモニウム12重量％）をも示してある。Hereinafter, for the examples of the electrolytic solution for an electrolytic capacitor according to the present invention, a 15 wt% solution of various pyrrolidinium compounds or various salts of carboxylic acid salts of piperidinium compounds with respect to various solvents was prepared according to the general preparation method, and its conductivity was It is shown in Table 1. As a comparative example, a conventional standard electrolytic solution (78 wt% ethylene glycol, 10 wt% water, 12 wt% ammonium adipate) is also shown.
以上の結果から分かるように、本発明に係る電解液
は、従来のものに比べ高い電導度を示し、広い範囲の電
導度が選択可能とされる。 As can be seen from the above results, the electrolytic solution according to the present invention exhibits higher conductivity than the conventional one, and a wide range of conductivity can be selected.
次に、これらの電解液を使用して、電解コンデンサを
作製し、その特性の比較を行った。Next, using these electrolytic solutions, electrolytic capacitors were produced and their characteristics were compared.
作製した電解コンデンサは、アルミニウム箔を陽極並
びに陰極に使用し、セパレータ紙を挟んで重ね合わせて
巻回し、円筒状のコンデンサ素子としたものに、各実施
例の電解液を含浸して外装ケースに収納し、密封したも
のである。The produced electrolytic capacitor was manufactured by using aluminum foil for the anode and the cathode, and stacking and winding with a separator paper sandwiched between them to form a cylindrical capacitor element, which was impregnated with the electrolytic solution of each example to form an outer case. It is stored and sealed.
いずれも同一のコンデンサ素子を使用しており、定格
電圧16V、定格容量47μＦで、各10回測定した平均値で
ある。All of them use the same capacitor element, and are the average values measured 10 times each with a rated voltage of 16 V and a rated capacity of 47 μF.
以下の第２表は、これら電解コンデンサの初期値並び
に110℃で定格電圧を印加して1000時間経過後の静電容
量値（CAP）、損失角の正接（tanδ）、漏れ電流値（L
C）（２分値）を表している。The following Table 2 shows the initial values of these electrolytic capacitors as well as the capacitance value (CAP), loss tangent (tan δ), and leakage current value (L) after 1000 hours of application of the rated voltage at 110 ° C.
C) (2 minutes value).
この試験の結果からも明らかなように、本発明に係る
電解コンデンサ用電解液は、電導度が高い為に、従来の
ものに比較して損失、即ちtanδの値が低くなる。 As is clear from the results of this test, the electrolytic solution for an electrolytic capacitor according to the present invention has a high electric conductivity, so that the loss, that is, the value of tan δ is lower than that of the conventional one.
また、エチレングリコールが溶媒として使用される
が、電解液に対し30重量％程度の使用は、高温負荷状態
に置いても、内圧上昇による外観異常や静電容量の減少
等がなく、初期値と1000時間後の特性値の比較において
も、本発明のものは極めて変化が少ない。Although ethylene glycol is used as a solvent, using about 30% by weight with respect to the electrolyte does not cause abnormal appearance or decrease in capacitance due to increase in internal pressure even when placed in a high temperature load state. Even when the characteristic values after 1000 hours are compared, those of the present invention show very little change.
本発明に係る電解コンデンサ用電解液によると、低い
損失値と、高温で長時間使用しても安定した特性が維持
できるので、高い周波数で使用され、かつ高効率が求め
られるスイッチングレギュレータなどの電源装置や、高
温度で長期間使用される各種電気機器等に好適に使用で
きる。According to the electrolytic solution for an electrolytic capacitor of the present invention, a low loss value and stable characteristics can be maintained even when used at high temperature for a long time, so a power supply for a switching regulator or the like that is used at a high frequency and is required to have high efficiency. It can be suitably used for devices and various electric devices used at high temperatures for a long time.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 篠崎 郁彦 東京都青梅市東青梅１丁目167番地の１ 日本ケミコン株式会社内 (72)発明者 横山 豊 東京都青梅市東青梅１丁目167番地の１ 日本ケミコン株式会社内 (56)参考文献 特開 昭62−145713（ＪＰ，Ａ) 特開 昭62−145714（ＪＰ，Ａ) 特開 昭62−145715（ＪＰ，Ａ) 特開 昭62−145716（ＪＰ，Ａ) 特開 昭62−248216（ＪＰ，Ａ) 特開 昭62−248217（ＪＰ，Ａ) 特開 昭62−254415（ＪＰ，Ａ) 特開 昭62−254416（ＪＰ，Ａ) 特開 昭63−181413（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ikuhiko Shinozaki 1-1, Higashi-Ome, Ome, Tokyo 1-167 Japan Chemi-Con Co., Ltd. (72) Inventor Yutaka Yokoyama 1-167, Higashi-Ome, Ome-shi, Tokyo 1 (56) References JP 62-145713 (JP, A) JP 62-145714 (JP, A) JP 62-145715 (JP, A) JP 62-145716 (JP, A) A) JP 62-248216 (JP, A) JP 62-248217 (JP, A) JP 62-254415 (JP, A) JP 62-254416 (JP, A) JP 63 -181413 (JP, A)
Claims (2)
とした多価アルコール類との混合溶媒中に、 一般式 （式中、R1、R2は炭素原子数１〜６個のアルキル基、又
はフェニル基、R3は水素原子又は炭素数１〜６個のアル
キル基、Ｂはフタル酸又は脂肪族オキシカルボン酸のア
ニオン、ｎは４又は５）で表されるピロリジニウム化合
物、又はピペリジニウム化合物のカルボン酸塩を電解質
として含む電解コンデンサ用電解液。1. A general formula in an aprotic solvent or a mixed solvent with a polyhydric alcohol mainly containing an aprotic solvent (In the formula, R 1 and R 2 are alkyl groups having 1 to 6 carbon atoms or a phenyl group, R 3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, B is phthalic acid or an aliphatic oxycarboxylic acid. An electrolytic solution for an electrolytic capacitor, comprising an anion of an acid, n is a pyrrolidinium compound represented by 4 or 5), or a carboxylate of a piperidinium compound as an electrolyte.
乳酸、リンゴ酸、クエン酸及び酒石酸よりなる群から選
択される特許請求の範囲第１項記載の電解コンデンサ用
電解液。2. The aliphatic oxycarboxylic acid is glycolic acid,
The electrolytic solution for an electrolytic capacitor according to claim 1, which is selected from the group consisting of lactic acid, malic acid, citric acid and tartaric acid.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62051885A JPH0810663B2 (en) | 1987-03-09 | 1987-03-09 | Electrolytic solution for electrolytic capacitors |
| EP88103589A EP0281994A1 (en) | 1987-03-09 | 1988-03-08 | An electrolyte for electrolytic capacitor |
| KR1019880002447A KR970004299B1 (en) | 1987-03-09 | 1988-03-09 | Electrolyte for condenser |
| US07/725,344 US5202042A (en) | 1987-03-09 | 1991-07-03 | Heterocyclic electrolyte salts for electrolytic capacitors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62051885A JPH0810663B2 (en) | 1987-03-09 | 1987-03-09 | Electrolytic solution for electrolytic capacitors |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63219116A JPS63219116A (en) | 1988-09-12 |
| JPH0810663B2 true JPH0810663B2 (en) | 1996-01-31 |
Family
ID=12899338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62051885A Expired - Fee Related JPH0810663B2 (en) | 1987-03-09 | 1987-03-09 | Electrolytic solution for electrolytic capacitors |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0810663B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8951664B2 (en) | 2011-06-03 | 2015-02-10 | Semiconductor Energy Laboratory Co., Ltd. | Ionic liquid and power storage device including the same |
| JP2017178792A (en) * | 2016-03-28 | 2017-10-05 | Tdk株式会社 | Ammonium salt, electrolyte for lithium secondary battery, and lithium secondary battery using them |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62145715A (en) * | 1985-12-20 | 1987-06-29 | 三菱油化株式会社 | Electrolyte for electrolytic capacitor |
| JPH0797541B2 (en) * | 1986-04-28 | 1995-10-18 | 三菱化学株式会社 | Electrolytic solution for electrolytic capacitors |
| JPS62145714A (en) * | 1985-12-20 | 1987-06-29 | 三菱油化株式会社 | Electrolyte for electrolytic capacitor |
| JPS62145713A (en) * | 1985-12-20 | 1987-06-29 | 三菱油化株式会社 | Electrolyte for electrolytic capacitor |
| JPS62248217A (en) * | 1986-04-21 | 1987-10-29 | 三菱油化株式会社 | Electrolyte for electrolytic capacitor |
| JPS62248216A (en) * | 1986-04-21 | 1987-10-29 | 三菱油化株式会社 | Electrolyte for electrolytic capacitor |
| JPS62254415A (en) * | 1986-04-28 | 1987-11-06 | 三菱油化株式会社 | Electrolyte for electrolytic capacitor |
| JPS63181413A (en) * | 1987-01-23 | 1988-07-26 | 三菱油化株式会社 | Electrolyte for electrolytic capacitor |
-
1987
- 1987-03-09 JP JP62051885A patent/JPH0810663B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63219116A (en) | 1988-09-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |