JPH08321440A - Electrolytic solution and electrochemical element using the same - Google Patents
Electrolytic solution and electrochemical element using the sameInfo
- Publication number
- JPH08321440A JPH08321440A JP7127841A JP12784195A JPH08321440A JP H08321440 A JPH08321440 A JP H08321440A JP 7127841 A JP7127841 A JP 7127841A JP 12784195 A JP12784195 A JP 12784195A JP H08321440 A JPH08321440 A JP H08321440A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- electrolytic solution
- alkyl group
- carbon atoms
- salt
- 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.)
- Granted
Links
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
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電解コンデンサや電気
二重層コンデンサ、イオンの電荷移動による充電／放電
機構を有する電池、エレクトロクロミック表示素子など
に使用する電解液およびそれを用いた電気化学素子に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic solution, an electric double layer capacitor, a battery having a charge / discharge mechanism by charge transfer of ions, an electrolytic solution used for an electrochromic display element, and an electrochemical element using the electrolytic solution. It is about.
【０００２】[0002]
【従来の技術】従来、電解コンデンサ等の電解液として
は、芳香族カルボン酸（フタル酸等）の第４級アンモニ
ウム塩を電解質としたもの（特開昭６２−１４５７１５
号）、マレイン酸の第４級アンモニウム塩を電解質とし
たもの（特開昭６２−１４５７１３号）、脂肪族飽和モ
ノカルボン酸（蟻酸等）の第４級アンモニウム塩を電解
質としたもの（特開昭６２−２２６６１４号）、脂肪族
飽和ジカルボン酸（マロン酸等）の第４級アンモニウム
塩を電解質としたもの（特開昭６２−２４８２１７号）
などが知られている。2. Description of the Related Art Conventionally, as an electrolytic solution for an electrolytic capacitor or the like, a quaternary ammonium salt of an aromatic carboxylic acid (phthalic acid or the like) has been used as an electrolyte (JP-A-62-145715).
No.), a quaternary ammonium salt of maleic acid as an electrolyte (JP-A-62-145713), and a quaternary ammonium salt of an aliphatic saturated monocarboxylic acid (formic acid, etc.) as an electrolyte (JP-A No. JP-A-62-226614), using a quaternary ammonium salt of an aliphatic saturated dicarboxylic acid (malonic acid, etc.) as an electrolyte (JP-A-62-248217).
Etc. are known.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、フタル
酸の第４級アンモニウム塩を電解質としたものは電導度
が不十分であり、またマレイン酸、蟻酸、マロン酸等の
第４級アンモニウム塩を電解質としたものは高温での安
定性が不十分であった。However, the use of a quaternary ammonium salt of phthalic acid as an electrolyte has insufficient electric conductivity, and a quaternary ammonium salt of maleic acid, formic acid, malonic acid or the like is used as an electrolyte. The above-mentioned products had insufficient stability at high temperatures.
【０００４】そしてまた、第４級アンモニウム塩を電解
質とした電解液は、第４級アンモニウムの電気化学的な
変質により、コンデンサを構成する材料である樹脂やゴ
ム、金属を劣化させたり、腐食させる等の不具合があっ
た。Further, the electrolytic solution using a quaternary ammonium salt as an electrolyte deteriorates or corrodes the resin, rubber, and metal which are the materials constituting the capacitor due to the electrochemical alteration of the quaternary ammonium. There was a problem such as.
【０００５】本発明は上記従来の問題点を解決するもの
で、電導度が高く、電気化学的な変質時にも樹脂やゴ
ム、金属を劣化させたり、腐食させたりすることなく、
熱的にも安定性の高い電解液およびそれを用いた電気化
学素子を提供することを目的とするものである。The present invention solves the above-mentioned conventional problems and has a high electric conductivity, and does not deteriorate or corrode the resin, rubber or metal even when it is electrochemically deteriorated.
It is an object of the present invention to provide an electrolytic solution having high thermal stability and an electrochemical device using the electrolytic solution.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
に本発明の電解液は、（化３）で示されるイミダゾリン
化合物を陽イオン成分とする塩を電解質としたもので、
さらに本発明の電気化学素子は前記電解液を用いるよう
にしたものである。In order to achieve the above object, the electrolytic solution of the present invention comprises a salt containing an imidazoline compound represented by (Chemical Formula 3) as a cation component as an electrolyte.
Furthermore, the electrochemical device of the present invention uses the electrolytic solution.
【０００７】[0007]
【化３】 Embedded image
【０００８】（式中、Ｒ1、Ｒ2、Ｒ3は炭素数１〜３の
アルキル基であり、Ｒ1、Ｒ2、Ｒ3の２つ以上が同じ炭
素数のアルキル基でも良い。Ｒ4は炭素数１〜３のアル
キル基または水素であり、炭素数１〜３のアルキル基の
場合、Ｒ4はＲ1、Ｒ2、Ｒ3のいずれかと同じ炭素数のア
ルキル基でも良い。）(In the formula, R 1 , R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms, and two or more of R 1 , R 2 and R 3 may be alkyl groups having the same carbon number. 4 is an alkyl group having 1 to 3 carbon atoms or hydrogen, and in the case of an alkyl group having 1 to 3 carbon atoms, R 4 may be an alkyl group having the same carbon number as any one of R 1 , R 2 and R 3. )
【０００９】[0009]
【作用】通常のアミン塩およびその４級化アンモニウム
場と異なり、本発明のイミダゾリン化合物を陽イオン成
分とする塩は非局在化したＮ−Ｃ−Ｎのアミジン基が４
級化されているため、陽イオンが共鳴安定化してイオン
解離が促進され、高い電導度が得られる。In contrast to the usual amine salt and its quaternized ammonium field, the salt containing the imidazoline compound of the present invention as a cation component has a delocalized N—C—N amidine group of 4 or more.
Since it is graded, the cations are resonance-stabilized to promote ionic dissociation, and high conductivity is obtained.
【００１０】また、イミダゾリン環の２位や４位にアル
キル基を導入することにより、イミダゾリン環の熱的な
安定性が向上することになるため、ガス発生も少ない。Further, the introduction of an alkyl group at the 2-position or 4-position of the imidazoline ring improves the thermal stability of the imidazoline ring, so that less gas is generated.
【００１１】さらには、電解液中で電気化学反応により
水酸化物イオンが生じた場合にも、水酸化物イオンとＮ
−Ｃ−Ｎのアミジン基との反応、分解開環により速やか
に電解生成物が消失するため、コンデンサを構成する材
料である樹脂やゴム、金属を劣化させたり、腐食させる
ことはなくなる。Further, even when hydroxide ions are generated by an electrochemical reaction in the electrolytic solution, the hydroxide ions and N
Since the electrolytic product disappears promptly by the reaction with the amidine group of —C—N and the decomposition ring-opening, the resin, rubber, and metal that are the materials constituting the capacitor are not deteriorated or corroded.
【００１２】[0012]
【実施例】以下、本発明の実施例について説明する。Embodiments of the present invention will be described below.
【００１３】本発明の基本は、（化４）で示されるイミ
ダゾリン化合物を陽イオン成分とする塩を電解質とした
電解液である。The basis of the present invention is an electrolytic solution in which a salt containing an imidazoline compound represented by the chemical formula 4 as a cation component is used as an electrolyte.
【００１４】[0014]
【化４】 [Chemical 4]
【００１５】（式中、Ｒ1、Ｒ2、Ｒ3は炭素数１〜３の
アルキル基であり、Ｒ1、Ｒ2、Ｒ3の２つ以上が同じ炭
素数のアルキル基でも良い。Ｒ4は炭素数１〜３のアル
キル基または水素であり、炭素数１〜３のアルキル基の
場合、Ｒ4はＲ1、Ｒ2、Ｒ3のいずれかと同じ炭素数のア
ルキル基でも良い。） 本発明の電解液に用いるイミダゾリン化合物の陽イオン
の例としては、１，２，３，４−テトラメチルイミダゾ
リニウム、１，３，４−トリメチル−２−エチルイミダ
ゾリニウム、１，３−ジメチル−２，４−ジエチルイミ
ダゾリニウム、１，２−ジメチル−３，４−ジエチルイ
ミダゾリニウム、１−メチル−２，３，４−トリエチル
イミダゾリニウム、１，２，３，４−テトラエチルイミ
ダゾリニウム、１，２，３−トリメチルイミダゾリニウ
ム、１，３−ジメチル−２−エチルイミダゾリニウム、
１，２−ジメチル−３−エチルイミダゾリニウム、１，
２，３−トリエチルイミダゾリニウムなどが挙げられ
る。(In the formula, R 1 , R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms, and two or more of R 1 , R 2 and R 3 may be alkyl groups having the same carbon number. 4 is an alkyl group having 1 to 3 carbon atoms or hydrogen, and in the case of an alkyl group having 1 to 3 carbon atoms, R 4 may be an alkyl group having the same carbon number as any one of R 1 , R 2 and R 3. ) Examples of the cation of the imidazoline compound used in the electrolytic solution of the present invention include 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium and 1,3- Dimethyl-2,4-diethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1-methyl-2,3,4-triethylimidazolinium, 1,2,3,4-tetraethyl Imidazolinium, 1,2,3-trimethylimi Zoriniumu, 1,3-dimethyl-2-ethyl imidazolinium,
1,2-dimethyl-3-ethylimidazolinium, 1,
2,3-triethyl imidazolinium etc. are mentioned.
【００１６】これらのうちで好ましいのは導電度が高い
１，２，３，４−テトラメチルイミダゾリニウム、１，
３，４−トリメチル−２−エチルイミダゾリニウムであ
る。Of these, preferred are 1,2,3,4-tetramethylimidazolinium having a high conductivity, 1,
It is 3,4-trimethyl-2-ethylimidazolinium.
【００１７】本発明の電解液に用いる酸の例としては、
ポリカルボン酸（２〜４価）：脂肪族ポリカルボン酸
［飽和ポリカルボン酸、例えばシュウ酸，マロン酸，コ
ハク酸，グルタル酸，アジピン酸，ピメリン酸，スベリ
ン酸，アゼライン酸，セバチン酸，１，６−デカンジカ
ルボン酸，５，６−デカンジカルボン酸：不飽和ポリカ
ルボン酸、例えばマレイン酸，フマル酸，イコタン
酸］；芳香族ポリカルボン酸、例えばフタル酸，イソフ
タル酸，テレフタル酸，トリメリット酸，ピロメリット
酸；脂環式ポリカルボン酸、例えばテトロヒドロフタル
酸（シクロヘキサン−１，２−ジカルボン酸等），ヘキ
サヒドロフタル酸；これらのポリカルボン酸のアルキル
（炭素数１〜３）もしくはニトロ置換体、例えばシトコ
ラン酸，ジメチルマレイン酸，ニトロフタル酸（３−ニ
トロフタル酸，４−ニトロフタル酸）；および硫黄含有
ポリカルボン酸、例えばチオプロピオン酸；モノカルボ
ン酸；脂肪族モノカルボン酸（炭素数１〜３０）［飽和
モノカルボン酸、例えばギ酸，酢酸，プロピオン酸，酪
酸，イソ酪酸，吉草酸，カプロン酸，エナント酸，カプ
リル酸，ペラルゴン酸，ラウリン酸，ミリスチン酸，ス
テアリン酸，ベヘン酸：不飽和モノカルボン酸、例えば
アクリル酸，メタクリル酸，オレイン酸］；芳香族モノ
カルボン酸、例えば安息香酸，ｏ−ニトロ安息香酸、ｐ
−ニトロ安息香酸、ケイ皮酸，ナフトエ酸；オキシカル
ボン酸、例えばサリチル酸，マンデル酸，レゾルシル酸 無機酸；リン酸、ホウ酸、ホウフッ酸、４フッ化ホウ
酸、過塩素酸、６フッ化リン酸、６フッ化アンチモン
酸、６フッ化ヒ素酸、などが例として挙げられる。Examples of the acid used in the electrolytic solution of the present invention include:
Polycarboxylic acid (2 to 4 valent): Aliphatic polycarboxylic acid [Saturated polycarboxylic acid such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1 , 6-decanedicarboxylic acid, 5,6-decanedicarboxylic acid: unsaturated polycarboxylic acids such as maleic acid, fumaric acid, icotanic acid]; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitate Acid, pyromellitic acid; alicyclic polycarboxylic acid such as tetrohydrophthalic acid (cyclohexane-1,2-dicarboxylic acid etc.), hexahydrophthalic acid; alkyl of these polycarboxylic acids (having 1 to 3 carbon atoms) or Nitro-substituted compounds such as cytocholanic acid, dimethyl maleic acid, nitrophthalic acid (3-nitrophthalic acid, 4-nit Phthalic acid); and sulfur-containing polycarboxylic acids such as thiopropionic acid; monocarboxylic acids; aliphatic monocarboxylic acids (having 1 to 30 carbon atoms) [saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid , Valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, lauric acid, myristic acid, stearic acid, behenic acid: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, oleic acid]; aromatic monocarboxylic acids , Benzoic acid, o-nitrobenzoic acid, p
-Nitrobenzoic acid, cinnamic acid, naphthoic acid; oxycarboxylic acids such as salicylic acid, mandelic acid, resorcylic acid inorganic acids; phosphoric acid, boric acid, borofluoric acid, tetrafluoroboric acid, perchloric acid, phosphorus hexafluoride Examples thereof include acid, antimony hexafluoride, and arsenic hexafluoride.
【００１８】これらのうちで好ましいのは、電導度が高
く熱的にも安定な、マレイン酸，フタル酸，アジピン
酸，安息香酸である。Of these, maleic acid, phthalic acid, adipic acid and benzoic acid, which have a high electric conductivity and are stable thermally, are preferable.
【００１９】電解液を構成する酸と１，２，３，４−テ
トラアルキルイミダゾリニウムとの割合は、電解液のｐ
Ｈにして、通常４〜１１、好ましくは６〜９である。こ
の範囲外では、電解液の火花電圧が低下する。The ratio of the acid constituting the electrolytic solution and 1,2,3,4-tetraalkylimidazolinium is p of the electrolytic solution.
H is usually 4 to 11, preferably 6 to 9. Outside this range, the spark voltage of the electrolytic solution decreases.
【００２０】本発明の電解液に用いる溶媒の例として
は、アルコール類［１価アルコール（ブチルアルコー
ル、ジアセトンアルコール、ベンジルアルコール、アミ
ノアルコールなど）；２価アルコール（エチレングリコ
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、フェニルグリコールなど）；３
価アルコール（グリセリン、３−メチルペンタン−１，
３，５−トリオールなど）；ヘキシトールなど］、エー
テル類［モノエーテル（エチレングリコールモノメチル
エーテル、ジエチレングリコールモノメチルエーテル、
ジエチレングリコールモノエチルエーテル、エチレング
リコールモノフェニルエーテルなど）；ジエーテル（エ
チレングリコールジメチルエーテル、エチレングリコー
ルジエチルエーテル、ジエチレングリコールジメチルエ
ーテル、ジエチレングリコールジエチルエーテルなど）
など］、アミド類［ホルムアミド類（Ｎ−メチルホルム
アミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエ
チルホルムアミドなど）；アセトアミド類（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な
ど）；プロピオンアミド類（Ｎ，Ｎ−ジメチルプロピオ
ンアミドなど）；ヘキサメチルホスホリルアミドな
ど］、オキサゾリジノン類（１，３−ジメチル−２−イ
ミダゾリジノン、３−メチルオキサゾリジン−２−オン
など）、ジメチルスルホキシド、γ−ブチロラクトンお
よびこれら２種以上の混合物が挙げられる。Examples of the solvent used in the electrolytic solution of the present invention include alcohols [monohydric alcohol (butyl alcohol, diacetone alcohol, benzyl alcohol, amino alcohol, etc.); dihydric alcohol (ethylene glycol, propylene glycol, diethylene glycol,
Hexylene glycol, phenyl glycol, etc.); 3
Polyhydric alcohol (glycerin, 3-methylpentane-1,
3,5-triol, etc.); hexitol, etc.], ethers [monoether (ethylene glycol monomethyl ether, diethylene glycol monomethyl ether,
Diethylene glycol monoethyl ether, ethylene glycol monophenyl ether, etc.); Diether (ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc.)
Etc.], amides [formamides (N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, etc.); acetamides (N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, etc.); propionamides (N, N-dimethylpropionamide, etc.); hexamethylphosphorylamide, etc.], oxazolidinones (1,3-dimethyl-2-imidazolidinone, 3-methyloxazolidine- 2-one), dimethylsulfoxide, γ-butyrolactone, and mixtures of two or more thereof.
【００２１】これらのうちで好ましいのは、電導度が高
く熱的にも安定な、エチレングリコール、１，３−ジメ
チル−２−イミダゾリジノン、３−メチルオキサゾリジ
ン−２−オン、γ−ブチロラクトン単独およびこれらの
群より選ばれる２種以上との混合溶媒である。そしてこ
の中でも特に好ましいのは、γ−ブチロラクトン単独、
またはγ−ブチロラクトンとエチレングリコールとの混
合溶媒であり、そのときのγ−ブチロラクトンの含有量
は、溶媒の重量に基づいて５０〜１００％が好ましい。
なお、γ−ブチロラクトンの含有量が５０％未満では電
導度が著しく低下するものである。Of these, preferred are ethylene glycol, 1,3-dimethyl-2-imidazolidinone, 3-methyloxazolidin-2-one, and γ-butyrolactone alone, which have high electric conductivity and are thermally stable. And a mixed solvent of two or more selected from these groups. And among these, particularly preferred is γ-butyrolactone alone,
Alternatively, it is a mixed solvent of γ-butyrolactone and ethylene glycol, and the content of γ-butyrolactone at that time is preferably 50 to 100% based on the weight of the solvent.
In addition, when the content of γ-butyrolactone is less than 50%, the electric conductivity is remarkably reduced.
【００２２】本発明の電解液には、必要により水を含有
させることもできる。その含有量は電解液の重量に基づ
いて通常１０％未満である。水の含有量が１０％以上で
はガス発生が大きくなり、電解コンデンサの特性を著し
く劣化させる。If desired, the electrolytic solution of the present invention may contain water. Its content is usually less than 10% based on the weight of the electrolyte. When the water content is 10% or more, gas generation becomes large and the characteristics of the electrolytic capacitor are significantly deteriorated.
【００２３】また本発明の電解液は、必要により種々の
添加剤を混合しても良い。添加剤としては、リン系化合
物［リン酸、リン酸エステルなど］、ホウ酸系化合物
［ホウ酸、ホウ酸と多糖類（マンニット、ソルビット、
など）との錯化合物、ホウ酸と多価アルコール（エチレ
ングリコール、グリセリン、など）］との錯化合物、ニ
トロ化合物［ｐ−ニトロ安息香酸、ｐ−ニトロフェノー
ル、など］が挙げられる。If desired, the electrolytic solution of the present invention may contain various additives. As additives, phosphorus compounds [phosphoric acid, phosphoric acid ester, etc.], boric acid compounds [boric acid, boric acid and polysaccharides (mannite, sorbit,
Etc.), a complex compound of boric acid and a polyhydric alcohol (ethylene glycol, glycerin, etc.)], and a nitro compound [p-nitrobenzoic acid, p-nitrophenol, etc.].
【００２４】本発明の電解液における電解質の含有量
は、電解液の重量に基づいて通常１〜７０重量％、好ま
しくは５〜４０重量％である。この範囲外では電導度が
著しく低下する。The content of the electrolyte in the electrolytic solution of the present invention is usually 1 to 70% by weight, preferably 5 to 40% by weight based on the weight of the electrolytic solution. Outside this range, the electrical conductivity will be significantly reduced.
【００２５】次に、本発明の具体的な実施例について説
明するが、本発明はこれに限定されるものではない。以
下、部はすべて重量部を示す。Next, specific examples of the present invention will be described, but the present invention is not limited thereto. Hereinafter, all parts are parts by weight.
【００２６】（表１）は本発明の実施例１〜３および従
来例１〜２の電解液組成と３０℃で測定した電導度とこ
れらの電解液に熱処理（１０５℃、５００時間）を施し
た後、３０℃で測定した電導度を示したものである。Table 1 shows the compositions of the electrolytic solutions of Examples 1 to 3 and Conventional Examples 1 and 2 of the present invention, the conductivity measured at 30 ° C., and the heat treatment (105 ° C., 500 hours) to these electrolytic solutions. And shows the electrical conductivity measured at 30 ° C.
【００２７】[0027]
【表１】 [Table 1]
【００２８】（表１）から明らかなように本発明の実施
例１〜３の電解液は、従来例１の電解液と比較して電導
度が高い。また、本発明の実施例１〜３の電解液は、従
来例２の電解液と比較して電導度の熱的な安定性も高
い。As is clear from (Table 1), the electrolytic solutions of Examples 1 to 3 of the present invention have higher conductivity than the electrolytic solution of Conventional Example 1. Further, the electrolytic solutions of Examples 1 to 3 of the present invention have higher thermal stability of electric conductivity than the electrolytic solution of Conventional Example 2.
【００２９】次に、本発明の実施例１〜３および従来例
１〜２の電解液を使用して巻き取り形のアルミ電解コン
デンサ（定格電圧３５Ｖ−静電容量２２００μＦ、サイ
ズ；φ１６ｍｍ×Ｌ３５ｍｍ）を作成した。アルミ引き
出しリードには両極共に陽極酸化処理を施し、封口ゴム
には硫黄加硫のブチルゴムを使用した。このアルミ電解
コンデンサに逆電圧−２．０Ｖを印加して、１２５℃の
恒温槽中で劣化させ、封口部の外観を経時的に観察し
た。その結果を（表２）に示す。Next, a roll-up type aluminum electrolytic capacitor using the electrolytic solutions of Examples 1 to 3 and Conventional Examples 1 and 2 of the present invention (rated voltage 35V-capacitance 2200 μF, size; φ16 mm × L35 mm) It was created. Both electrodes were anodized on the aluminum lead, and sulfur-vulcanized butyl rubber was used as the sealing rubber. A reverse voltage of −2.0 V was applied to this aluminum electrolytic capacitor to deteriorate it in a constant temperature bath at 125 ° C., and the appearance of the sealing portion was observed with time. The results are shown in (Table 2).
【００３０】[0030]
【表２】 [Table 2]
【００３１】（表２）から明らかなように、本発明の実
施例１〜３の電解液は、１０００時間経過した時点でも
封口ゴムの劣化による液漏れ等の異常は観察されなかっ
た。As is clear from (Table 2), no abnormality such as liquid leakage due to deterioration of the sealing rubber was observed in the electrolytic solutions of Examples 1 to 3 of the present invention even after 1000 hours.
【００３２】[0032]
【発明の効果】以上のように本発明の電解液は、高い電
導度を示し、かつその熱的な安定性にも優れ、また電気
化学的な変質時においても、樹脂やゴム、金属を劣化さ
せたり、腐食させる等の不具合もないもので、この本発
明の電解液を電解コンデンサに使用した場合は、低損失
で、かつ高温でも電気的特性の安定した、長寿命で信頼
性の高い電解コンデンサを得ることができる。INDUSTRIAL APPLICABILITY As described above, the electrolytic solution of the present invention exhibits high electric conductivity and is excellent in thermal stability, and also deteriorates resin, rubber, and metal even during electrochemical alteration. When using the electrolytic solution of the present invention for an electrolytic capacitor, there is no problem such as causing or corroding, low loss, stable electrical characteristics even at high temperature, long life and highly reliable electrolysis. Capacitor can be obtained.
【００３３】また、電解コンデンサや電気二重層コンデ
ンサ、イオンの電荷移動による充電／放電機構を有する
電池、エレクトロクロミック表示素子などに使用した場
合は、電解液と接触する樹脂やゴム、金属を劣化させた
り、腐食させる等の不具合もないため、信頼性の高い電
気化学素子を構成できるものである。When it is used in an electrolytic capacitor, an electric double layer capacitor, a battery having a charge / discharge mechanism by charge transfer of ions, an electrochromic display element, etc., it deteriorates the resin, rubber, and metal that come into contact with the electrolytic solution. Since there is no problem such as corrosion or corrosion, a highly reliable electrochemical element can be constructed.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 塩野 和司 京都府京都市東山区一橋野本町11番地の１ 三洋化成工業株式会社内 (72)発明者 中野 智治 京都府京都市東山区一橋野本町11番地の１ 三洋化成工業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazushio Shino 1 1-11, Hitotsubashi-honmachi, Higashiyama-ku, Kyoto-shi, Kyoto 1 Sanyo Chemical Industry Co., Ltd. No. 1 Sanyo Chemical Industry Co., Ltd.
Claims (7)
を陽イオン成分とする塩を電解質とした電解液。 【化１】 （式中、Ｒ1、Ｒ2、Ｒ3は炭素数１〜３のアルキル基で
あり、Ｒ1、Ｒ2、Ｒ3の２つ以上が同じ炭素数のアルキ
ル基でも良い。Ｒ4は炭素数１〜３のアルキル基または
水素であり、炭素数１〜３のアルキル基の場合、Ｒ4は
Ｒ1、Ｒ2、Ｒ3のいずれかと同じ炭素数のアルキル基で
も良い。）1. An electrolytic solution comprising a salt having a cation component of an imidazoline compound represented by Chemical formula 1 as an electrolyte. Embedded image (In the formula, R 1 , R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms, and two or more of R 1 , R 2 and R 3 may be alkyl groups having the same carbon number. R 4 is carbon In the case of an alkyl group having 1 to 3 carbon atoms or hydrogen, and in the case of an alkyl group having 1 to 3 carbon atoms, R 4 may be an alkyl group having the same carbon number as any one of R 1 , R 2 and R 3. )
テトラメチルイミダゾリニウム、１，３，４−トリメチ
ル−２−エチルイミダゾリニウム、１，３−ジメチル−
２，４−ジエチルイミダゾリニウム、１，２−ジメチル
−３，４−ジエチルイミダゾリニウム、１−メチル−
２，３，４−トリエチルイミダゾリニウム、１，２，
３，４−テトラエチルイミダゾリニウム、１，２，３−
トリメチルイミダゾリニウム、１，３−ジメチル−２−
エチルイミダゾリニウム、１，２−ジメチル−３−エチ
ルイミダゾリニウム、１，２，３−トリエチルイミダゾ
リニウムから選ばれる１種以上である請求項１記載の電
解液。2. The imidazoline compound is 1,2,3,4-
Tetramethyl imidazolinium, 1,3,4-trimethyl-2-ethyl imidazolinium, 1,3-dimethyl-
2,4-diethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1-methyl-
2,3,4-triethylimidazolinium, 1,2,
3,4-tetraethylimidazolinium, 1,2,3-
Trimethylimidazolinium, 1,3-dimethyl-2-
The electrolytic solution according to claim 1, which is one or more selected from ethylimidazolinium, 1,2-dimethyl-3-ethylimidazolinium, and 1,2,3-triethylimidazolinium.
る塩を構成する酸がカルボン酸、リン酸、モノまたはジ
アルキルリン酸エステル、無機酸からなる群から選ばれ
る１種以上である請求項１または２記載の電解液。3. The acid constituting the salt having an imidazoline compound as a cation component is one or more selected from the group consisting of carboxylic acid, phosphoric acid, mono- or dialkyl phosphate ester, and inorganic acid. The electrolytic solution described.
る塩を構成する酸がフタル酸および／またはマレイン酸
である請求項１〜３のいずれかに記載の電解液。4. The electrolytic solution according to claim 1, wherein the acid constituting the salt having an imidazoline compound as a cation component is phthalic acid and / or maleic acid.
またはエチレングリコールを含有する請求項１〜４のい
ずれかに記載の電解液。5. As solvent, γ-butyrolactone and / or
Alternatively, the electrolytic solution according to claim 1, which contains ethylene glycol.
を陽イオン成分とする塩を電解質とした電解液を用いて
なる電気化学素子。 【化２】 （式中、Ｒ1、Ｒ2、Ｒ3は炭素数１〜３のアルキル基で
あり、Ｒ1、Ｒ2、Ｒ3の２つ以上が同じ炭素数のアルキ
ル基でも良い。Ｒ4は炭素数１〜３のアルキル基または
水素であり、炭素数１〜３のアルキル基の場合、Ｒ4は
Ｒ1、Ｒ2、Ｒ3のいずれかと同じ炭素数のアルキル基で
も良い。）6. An electrochemical device comprising an electrolytic solution using a salt containing a cation component of the imidazoline compound represented by the chemical formula 2 as an electrolyte. Embedded image (In the formula, R 1 , R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms, and two or more of R 1 , R 2 and R 3 may be alkyl groups having the same carbon number. R 4 is carbon In the case of an alkyl group having 1 to 3 carbon atoms or hydrogen, and in the case of an alkyl group having 1 to 3 carbon atoms, R 4 may be an alkyl group having the same carbon number as any one of R 1 , R 2 and R 3. )
求項６記載の電気化学素子。7. The electrochemical device according to claim 6, wherein the electrochemical device is an electrolytic capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07127841A JP3130228B2 (en) | 1995-05-26 | 1995-05-26 | Electrolytic solution and electrochemical device using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07127841A JP3130228B2 (en) | 1995-05-26 | 1995-05-26 | Electrolytic solution and electrochemical device using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08321440A true JPH08321440A (en) | 1996-12-03 |
| JP3130228B2 JP3130228B2 (en) | 2001-01-31 |
Family
ID=14969995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07127841A Expired - Lifetime JP3130228B2 (en) | 1995-05-26 | 1995-05-26 | Electrolytic solution and electrochemical device using the same |
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| Country | Link |
|---|---|
| JP (1) | JP3130228B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11219866A (en) * | 1998-02-03 | 1999-08-10 | Nippon Chemicon Corp | Electrolytic capacitor electrolyte and electrolytic capacitor provided therewith |
| JPH11233380A (en) * | 1998-02-18 | 1999-08-27 | Nippon Chemicon Corp | Electrolytic capacitor electrolyte and electrolytic capacitor provided therewith |
| JPH11243037A (en) * | 1997-12-25 | 1999-09-07 | Nippon Chemicon Corp | Electrolyte solution for electrolytic capacitor and electrolytic capacitor using the electrolyte solution |
| JP2000124074A (en) * | 1998-10-21 | 2000-04-28 | Nichicon Corp | Aluminum electrolytic capacitor |
| WO2003007416A1 (en) * | 2001-07-10 | 2003-01-23 | Mitsubishi Chemical Corporation | Non-aqueous electrolyte and secondary cell using the same |
| JP2010034301A (en) * | 2008-07-29 | 2010-02-12 | Sanyo Chem Ind Ltd | Electrolyte for aluminum electrolytic capacitor and aluminum electrolytic capacitor using the same |
| US8817355B2 (en) | 2011-01-07 | 2014-08-26 | Samsung Electronics Co., Ltd. | Electrochromic device |
| CN112582179A (en) * | 2019-09-30 | 2021-03-30 | 深圳新宙邦科技股份有限公司 | Electrolytic capacitor |
-
1995
- 1995-05-26 JP JP07127841A patent/JP3130228B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11243037A (en) * | 1997-12-25 | 1999-09-07 | Nippon Chemicon Corp | Electrolyte solution for electrolytic capacitor and electrolytic capacitor using the electrolyte solution |
| JPH11219866A (en) * | 1998-02-03 | 1999-08-10 | Nippon Chemicon Corp | Electrolytic capacitor electrolyte and electrolytic capacitor provided therewith |
| JPH11233380A (en) * | 1998-02-18 | 1999-08-27 | Nippon Chemicon Corp | Electrolytic capacitor electrolyte and electrolytic capacitor provided therewith |
| JP2000124074A (en) * | 1998-10-21 | 2000-04-28 | Nichicon Corp | Aluminum electrolytic capacitor |
| WO2003007416A1 (en) * | 2001-07-10 | 2003-01-23 | Mitsubishi Chemical Corporation | Non-aqueous electrolyte and secondary cell using the same |
| US6942948B2 (en) | 2001-07-10 | 2005-09-13 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte solution and secondary battery employing the same |
| JP2010034301A (en) * | 2008-07-29 | 2010-02-12 | Sanyo Chem Ind Ltd | Electrolyte for aluminum electrolytic capacitor and aluminum electrolytic capacitor using the same |
| US8817355B2 (en) | 2011-01-07 | 2014-08-26 | Samsung Electronics Co., Ltd. | Electrochromic device |
| CN112582179A (en) * | 2019-09-30 | 2021-03-30 | 深圳新宙邦科技股份有限公司 | Electrolytic capacitor |
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| Publication number | Publication date |
|---|---|
| JP3130228B2 (en) | 2001-01-31 |
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