JPH07283083A - Electrochemical element and driving electrolyte therefor - Google Patents
Electrochemical element and driving electrolyte thereforInfo
- Publication number
- JPH07283083A JPH07283083A JP6075830A JP7583094A JPH07283083A JP H07283083 A JPH07283083 A JP H07283083A JP 6075830 A JP6075830 A JP 6075830A JP 7583094 A JP7583094 A JP 7583094A JP H07283083 A JPH07283083 A JP H07283083A
- Authority
- JP
- Japan
- Prior art keywords
- driving
- electrolytic solution
- acid
- electrochemical device
- butyrolactone
- 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
Landscapes
- Secondary Cells (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アルミ電解コンデン
サ、電気二重層コンデンサ、電池、ＥＬ素子等の電気化
学素子を駆動するために用いられる電気化学素子駆動用
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 for driving an electrochemical device used for driving an electrochemical device such as an aluminum electrolytic capacitor, an electric double layer capacitor, a battery and an EL device, and an electrochemical using the same. It is related to the element.
【０００２】[0002]
【従来の技術】従来の電気化学素子駆動用電解液は、主
溶媒として、γ−ブチロラクトン、エチレングリコー
ル、Ｎ，Ｎ−ジメチルホルムアミド、プロピレンカーボ
ネイト、エチレンカーボネイトのいずれか一種を用い、
そしてこれに支持電解質として無機酸塩または有機酸塩
を加え、さらに場合によってはリン酸化合物、芳香族ニ
トロ化合物、糖類等を添加剤として加えたものが主流で
あった。特に主溶媒としてのγ−ブチロラクトンは、毒
性も低く、かつ温度特性も他のグリコール系またはカー
ボネイト系の溶媒より良好であるため、アルミ電解コン
デンサ、電気二重層コンデンサ、電池等の電気化学素子
駆動用電解液の溶媒として広く使われている。2. Description of the Related Art A conventional electrolyte for driving an electrochemical device uses, as a main solvent, one of γ-butyrolactone, ethylene glycol, N, N-dimethylformamide, propylene carbonate and ethylene carbonate.
In addition, an inorganic acid salt or an organic acid salt was added to this as a supporting electrolyte, and in some cases, a phosphoric acid compound, an aromatic nitro compound, a saccharide or the like was added as an additive, which was the mainstream. In particular, γ-butyrolactone as the main solvent has low toxicity and has better temperature characteristics than other glycol-based or carbonate-based solvents, so it is used for driving electrochemical elements such as aluminum electrolytic capacitors, electric double-layer capacitors and batteries. Widely used as a solvent for electrolytes.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、主溶媒
としてγ−ブチロラクトンを用いた電気化学素子駆動用
電解液においては、極微量の水が存在するだけでラクト
ン環の−ＣＯＯ−部分が加水分解を起こし、そしてこれ
により、駆動用電解液の特性劣化が促進されたり、駆動
用電解液の酸化側分解電位が低下するという問題点を有
していた。However, in the electrolyte for driving an electrochemical device using γ-butyrolactone as the main solvent, the -COO- moiety of the lactone ring is not hydrolyzed even if only a trace amount of water is present. Then, the characteristics of the driving electrolyte are deteriorated, and the decomposition potential on the oxidation side of the driving electrolyte is lowered.
【０００４】本発明は上記従来の問題点を解決するもの
で、ラクトン環の−ＣＯＯ−部分の加水分解反応を抑制
して駆動用電解液の特性劣化が促進されるのを防止する
ことができるとともに、駆動用電解液の酸化側分解電位
も高めることができ、しかもこの駆動用電解液を使用し
た製品においては、高耐電圧化および長寿命化が図れる
電気化学素子駆動用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 can suppress the hydrolysis reaction of the -COO- moiety of the lactone ring and prevent the deterioration of the characteristics of the driving electrolyte solution from being promoted. At the same time, the oxidation side decomposition potential of the driving electrolyte can be increased, and in products using this driving electrolyte, an electrochemical element driving electrolyte that can achieve high withstand voltage and long life The purpose is to provide an electrochemical device used.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するため
に本発明の電気化学素子駆動用電解液は、溶媒と溶質と
を有し、前記溶媒として（化３）におけるＲ1〜Ｒ6の少
なくとも一つ以上が電子吸引性置換基を有する化合物を
少なくとも含んでなるものを用いたものである。In order to achieve the above object, the electrolytic solution for driving an electrochemical device of the present invention has a solvent and a solute, and the solvent of R 1 to R 6 in the chemical formula 3 is used as the solvent. At least one of them contains at least a compound having an electron-withdrawing substituent.
【０００６】[0006]
【化３】 [Chemical 3]
【０００７】[0007]
【作用】上記構成の電気化学素子駆動用電解液によれ
ば、溶媒として（化３）におけるＲ1〜Ｒ6の少なくとも
一つ以上が電子吸引性置換基を有する化合物を少なくと
も含んでなるものを用いているため、ラクトン環の−Ｃ
ＯＯ−部分の加水分解反応を抑制して駆動用電解液の特
性劣化が促進されるのを防止することができるととも
に、駆動用電解液の酸化側分解電位も高めることがで
き、しかもこの駆動用電解液を用いた電気化学素子にお
いては、高耐電圧化および長寿命化が図れるものであ
る。According to the electrochemical element driving electrolytic solution having the above structure, at least one of R 1 to R 6 in Chemical formula 3 contains at least a compound having an electron-withdrawing group as a solvent. Since it is used, -C of the lactone ring
It is possible to suppress the hydrolysis reaction of the OO- portion to prevent the deterioration of the characteristics of the driving electrolyte solution, and to increase the oxidation side decomposition potential of the driving electrolyte solution. An electrochemical device using an electrolytic solution can have a high withstand voltage and a long life.
【０００８】[0008]
【実施例】以下、本発明の実施例を説明する。EXAMPLES Examples of the present invention will be described below.
【０００９】本発明の電気化学素子駆動用電解液の基本
は、溶媒と溶質とを有し、前記溶媒として（化３）にお
けるＲ1〜Ｒ6の少なくとも一つ以上が電子吸引性置換基
を有する化合物を少なくとも含んでなるものを用いたも
のである。The basis of the electrolytic solution for driving an electrochemical device of the present invention is that it has a solvent and a solute, and at least one of R 1 to R 6 in the chemical formula 3 is an electron-withdrawing substituent. The thing using at least the compound which has is used.
【００１０】本発明の対象物となる化合物としては、以
下のものが挙げられるが、これに限定されるものではな
い。The compounds which are the object of the present invention include, but are not limited to, the followings.
【００１１】α−ビニル−γ−ブチロラクトン、β−ビ
ニル−γ−ブチロラクトン、γ−ビニル−γ−ブチロラ
クトン、α−アリル−γ−ブチロラクトン、β−アリル
−γ−ブチロラクトン、γ−アリル−γ−ブチロラクト
ン、α−フェニル−γ−ブチロラクトン、β−フェニル
−γ−ブチロラクトン、γ−フェニル−γ−ブチロラク
トン、α−メトキシ−γ−ブチロラクトン、β−メトキ
シ−γ−ブチロラクトン、γ−メトキシ−γ−ブチロラ
クトン、α−エトキシ−γ−ブチロラクトン、β−エト
キシ−γ−ブチロラクトン、γ−エトキシ−γ−ブチロ
ラクトン、α−プロポキシ−γ−ブチロラクトン、β−
プロポキシ−γ−ブチロラクトン、γ−プロポキシ−γ
−ブチロラクトン、α−ペンチロキシ−γ−ブチロラク
トン、β−ペンチロキシ−γ−ブチロラクトン、γ−ペ
ンチロキシ−γ−ブチロラクトン、α−イソペンチロキ
シ−γ−ブチロラクトン、β−イソペンチロキシ−γ−
ブチロラクトン、γ−イソペンチロキシ−γ−ブチロラ
クトン、α−ヘキシロキシ−γ−ブチロラクトン、β−
ヘキシロキシ−γ−ブチロラクトン、γ−ヘキシロキシ
−γ−ブチロラクトン、α−ベンジロキシ−γ−ブチロ
ラクトン、β−ベンジロキシ−γ−ブチロラクトン、γ
−ベンジロキシ−γ−ブチロラクトン、α−フェノキシ
−γ−ブチロラクトン、β−フェノキシ−γ−ブチロラ
クトン、γ−フェノキシ−γ−ブチロラクトン、α−プ
ロピオニル−γ−ブチロラクトン、β−プロピオニル−
γ−ブチロラクトン、γ−プロピオニル−γ−ブチロラ
クトン、α−ブチリル−γ−ブチロラクトン、β−ブチ
リル−γ−ブチロラクトン、γ−ブチリル−γ−ブチロ
ラクトン、α−イソブチリル−γ−ブチロラクトン、β
−イソブチリル−γ−ブチロラクトン、γ−イソブチリ
ル−γ−ブチロラクトン、α−バレリル−γ−ブチロラ
クトン、β−バレリル−γ−ブチロラクトン、γ−バレ
リル−γ−ブチロラクトン、α−クロロ−γ−ブチロラ
クトン、β−クロロ−γ−ブチロラクトン、γ−クロロ
−γ−ブチロラクトン、α−ヨウ化−γ−ブチロラクト
ン、β−ヨウ化−γ−ブチロラクトン、γ−ヨウ化−γ
−ブチロラクトン、α−フッ化−γ−ブチロラクトン、
β−フッ化−γ−ブチロラクトン、γ−フッ化−γ−ブ
チロラクトン、α−臭化−γ−ブチロラクトン、β−臭
化−γ−ブチロラクトン、γ−臭化−γ−ブチロラクト
ン、α−シアノ−γ−ブチロラクトン、β−シアノ−γ
−ブチロラクトン、γ−シアノ−γ−ブチロラクトン、
α−ニトロ−γ−ブチロラクトン、β−ニトロ−γ−ブ
チロラクトン、γ−ニトロ−γ−ブチロラクトン、α−
アミノ−γ−ブチロラクトン、β−アミノ−γ−ブチロ
ラクトン、γ−アミノ−γ−ブチロラクトン、α−メチ
ルアミノ−γ−ブチロラクトン、β−メチルアミノ−γ
−ブチロラクトン、γ−メチルアミノ−γ−ブチロラク
トン、α−アニリノ−γ−ブチロラクトン、β−アニリ
ノ−γ−ブチロラクトン、γ−アニリノ−γ−ブチロラ
クトン、α−ジフェニルアミノ−γ−ブチロラクトン、
β−ジフェニルアミノ−γ−ブチロラクトン、γ−ジフ
ェニルアミノ−γ−ブチロラクトン、α−ジメチルアミ
ノ−γ−ブチロラクトン、β−ジメチルアミノ−γ−ブ
チロラクトン、γ−ジメチルアミノ−γ−ブチロラクト
ン、α−ジエチルアミノ−γ−ブチロラクトン、β−ジ
エチルアミノ−γ−ブチロラクトン、γ−ジエチルアミ
ノ−γ−ブチロラクトン、α−ジプロピルアミノ−γ−
ブチロラクトン、β−ジプロピルアミノ−γ−ブチロラ
クトン、γ−ジプロピルアミノ−γ−ブチロラクトン、
α−エチルメチルアミノ−γ−ブチロラクトン、β−エ
チルメチルアミノ−γ−ブチロラクトン、γ−エチルメ
チルアミノ−γ−ブチロラクトン、α−メチルプロピル
アミノ−γ−ブチロラクトン、β−メチルプロピルアミ
ノ−γ−ブチロラクトン、γ−メチルプロピルアミノ−
γ−ブチロラクトン、α−エチルプロピルアミノ−γ−
ブチロラクトン、β−エチルプロピルアミノ−γ−ブチ
ロラクトン、γ−エチルプロピルアミノ−γ−ブチロラ
クトン、α−クロロ−γ−ブチロラクトン、β−クロロ
−γ−ブチロラクトン等がある。Α-vinyl-γ-butyrolactone, β-vinyl-γ-butyrolactone, γ-vinyl-γ-butyrolactone, α-allyl-γ-butyrolactone, β-allyl-γ-butyrolactone, γ-allyl-γ-butyrolactone , Α-phenyl-γ-butyrolactone, β-phenyl-γ-butyrolactone, γ-phenyl-γ-butyrolactone, α-methoxy-γ-butyrolactone, β-methoxy-γ-butyrolactone, γ-methoxy-γ-butyrolactone, α -Ethoxy-γ-butyrolactone, β-ethoxy-γ-butyrolactone, γ-ethoxy-γ-butyrolactone, α-propoxy-γ-butyrolactone, β-
Propoxy-γ-butyrolactone, γ-propoxy-γ
-Butyrolactone, α-pentyloxy-γ-butyrolactone, β-pentyloxy-γ-butyrolactone, γ-pentyloxy-γ-butyrolactone, α-isopentyloxy-γ-butyrolactone, β-isopentyloxy-γ-
Butyrolactone, γ-isopentyloxy-γ-butyrolactone, α-hexyloxy-γ-butyrolactone, β-
Hexyloxy-γ-butyrolactone, γ-hexyloxy-γ-butyrolactone, α-benzyloxy-γ-butyrolactone, β-benzyloxy-γ-butyrolactone, γ
-Benzyloxy-γ-butyrolactone, α-phenoxy-γ-butyrolactone, β-phenoxy-γ-butyrolactone, γ-phenoxy-γ-butyrolactone, α-propionyl-γ-butyrolactone, β-propionyl-
γ-butyrolactone, γ-propionyl-γ-butyrolactone, α-butyryl-γ-butyrolactone, β-butyryl-γ-butyrolactone, γ-butyryl-γ-butyrolactone, α-isobutyryl-γ-butyrolactone, β
-Isobutyryl-γ-butyrolactone, γ-isobutyryl-γ-butyrolactone, α-valeryl-γ-butyrolactone, β-valeryl-γ-butyrolactone, γ-valeryl-γ-butyrolactone, α-chloro-γ-butyrolactone, β-chloro -Γ-butyrolactone, γ-chloro-γ-butyrolactone, α-iodinated-γ-butyrolactone, β-iodinated-γ-butyrolactone, γ-iodinated-γ
-Butyrolactone, α-fluorinated-γ-butyrolactone,
β-fluorinated-γ-butyrolactone, γ-fluorinated-γ-butyrolactone, α-brominated-γ-butyrolactone, β-brominated-γ-butyrolactone, γ-brominated-γ-butyrolactone, α-cyano-γ -Butyrolactone, β-cyano-γ
-Butyrolactone, γ-cyano-γ-butyrolactone,
α-nitro-γ-butyrolactone, β-nitro-γ-butyrolactone, γ-nitro-γ-butyrolactone, α-
Amino-γ-butyrolactone, β-amino-γ-butyrolactone, γ-amino-γ-butyrolactone, α-methylamino-γ-butyrolactone, β-methylamino-γ
-Butyrolactone, γ-methylamino-γ-butyrolactone, α-anilino-γ-butyrolactone, β-anilino-γ-butyrolactone, γ-anilino-γ-butyrolactone, α-diphenylamino-γ-butyrolactone,
β-diphenylamino-γ-butyrolactone, γ-diphenylamino-γ-butyrolactone, α-dimethylamino-γ-butyrolactone, β-dimethylamino-γ-butyrolactone, γ-dimethylamino-γ-butyrolactone, α-diethylamino-γ -Butyrolactone, β-diethylamino-γ-butyrolactone, γ-diethylamino-γ-butyrolactone, α-dipropylamino-γ-
Butyrolactone, β-dipropylamino-γ-butyrolactone, γ-dipropylamino-γ-butyrolactone,
α-ethylmethylamino-γ-butyrolactone, β-ethylmethylamino-γ-butyrolactone, γ-ethylmethylamino-γ-butyrolactone, α-methylpropylamino-γ-butyrolactone, β-methylpropylamino-γ-butyrolactone, γ-methylpropylamino-
γ-butyrolactone, α-ethylpropylamino-γ-
Butyrolactone, β-ethylpropylamino-γ-butyrolactone, γ-ethylpropylamino-γ-butyrolactone, α-chloro-γ-butyrolactone, β-chloro-γ-butyrolactone, and the like.
【００１２】本発明の電気化学素子駆動用電解液の溶質
としては、アンモニウム塩、アミン塩、ホスホニウム
塩、アルカリ金属塩が挙げられる。具体的には、エチル
アミン塩、トリエチルアミン塩、エタノールアミン塩、
ジエチルアミン塩、ジプロピルアミン塩、トリブチルア
ミン塩、１，２−ナフチレンジアミン塩、ベンジルアミ
ン塩、トリフェニルアミン塩、テトラメチルアンモニウ
ム塩、テトラエチルアンモニウム塩、メチルトリエチル
アンモニウム塩、ヒドラジン、テトラメチルホスホニウ
ム塩、テトラエチルホスホニウム塩、メチルトリエチル
ホスホニウム塩、リチウム塩、カリウム塩、ナトリウム
塩等が挙げられる。駆動用電解液の溶質を構成する酸基
は、有機モノカルボン酸、ジカルボン酸、ホウ酸、硝
酸、硫酸、塩酸、過塩素酸、リン酸、テトラフルオロホ
ウ酸、フルオロメタンスルホン酸、リンタングステン酸
であり、そしてカルボン酸としては、具体的には、安息
香酸、マレイン酸、フタル酸、アジピン酸、コハク酸、
マロン酸、シュウ酸、グルタル酸、ピメリン酸、スベリ
ン酸、ギ酸、ピクリン酸、γ−レゾルシル酸、アゼライ
ン酸、サリチル酸、セバチン酸、クエン酸、アクリル
酸、プロピオン酸、乳酸、酪酸、吉草酸、Ｄ−グルコン
酸、オクタン酸、パルミチン酸、オレイン酸、ステアリ
ン酸、Ｐ−ニトロ安息香酸、アントラニル酸、Ｎ−メチ
ルアントラニル酸、没食子酸、ジフェニル酢酸、タルト
ロン酸、シトラコン酸、Ｌ−リンゴ酸、Ｌ−酒石酸、ニ
トロフタル酸、トリカルバリル酸等と、以上の化合物の
一部アルキル置換体およびニトロ置換体等が挙げられ
る。溶質として好ましいものとしては、過塩素酸リチウ
ム、過塩素酸ナトリウム、フタル酸テトラエチルアンモ
ニウム、マレイン酸テトラエチルアンモニウム、テトラ
エチルフルオロほう酸テトラエチルアンモニウム、フタ
ル酸テトラメチルアンモニウム、マレイン酸テトラメチ
ルアンモニウム、テトラフルオロほう酸テトラメチルア
ンモニウム、フタル酸メチルトリエチルアンモニウム、
マレイン酸メチルトリエチルアンモニウム、テトラフル
オロほう酸メチルトリエチルアンモニウムが挙げられ
る。本発明の駆動用電解液を構成する溶質の濃度は、溶
質の高濃度化による溶質の移動度の低下のために電導度
が低下するのを防ぐため、５０ｗｔ％以下が望ましい。Examples of solutes in the electrolytic solution for driving the electrochemical device of the present invention include ammonium salts, amine salts, phosphonium salts and alkali metal salts. Specifically, ethylamine salt, triethylamine salt, ethanolamine salt,
Diethylamine salt, dipropylamine salt, tributylamine salt, 1,2-naphthylenediamine salt, benzylamine salt, triphenylamine salt, tetramethylammonium salt, tetraethylammonium salt, methyltriethylammonium salt, hydrazine, tetramethylphosphonium salt , Tetraethylphosphonium salt, methyltriethylphosphonium salt, lithium salt, potassium salt, sodium salt and the like. The acid groups constituting the solute of the driving electrolyte are organic monocarboxylic acid, dicarboxylic acid, boric acid, nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, tetrafluoroboric acid, fluoromethanesulfonic acid, phosphotungstic acid. And as the carboxylic acid, specifically, benzoic acid, maleic acid, phthalic acid, adipic acid, succinic acid,
Malonic acid, oxalic acid, glutaric acid, pimelic acid, suberic acid, formic acid, picric acid, γ-resorcylic acid, azelaic acid, salicylic acid, sebacic acid, citric acid, acrylic acid, propionic acid, lactic acid, butyric acid, valeric acid, D -Gluconic acid, octanoic acid, palmitic acid, oleic acid, stearic acid, P-nitrobenzoic acid, anthranilic acid, N-methylanthranilic acid, gallic acid, diphenylacetic acid, tartronic acid, citraconic acid, L-malic acid, L- Examples thereof include tartaric acid, nitrophthalic acid, tricarballylic acid, and the like, and partial alkyl-substituted compounds and nitro-substituted compounds of the above compounds. Preferred solutes include lithium perchlorate, sodium perchlorate, tetraethylammonium phthalate, tetraethylammonium maleate, tetraethylammonium tetraethylfluoroborate, tetramethylammonium phthalate, tetramethylammonium maleate, tetramethyltetrafluoroborate. Ammonium, methyltriethylammonium phthalate,
Examples thereof include methyltriethylammonium maleate and methyltriethylammonium tetrafluoroborate. The concentration of the solute constituting the driving electrolyte solution of the present invention is preferably 50 wt% or less in order to prevent the decrease in the conductivity due to the decrease in the mobility of the solute due to the high concentration of the solute.
【００１３】本発明の駆動用電解液に混合される溶媒お
よび添加剤としては、プロピルアルコール、イソプロピ
ルアルコール、１−ブタノール、２−ブタノール、イソ
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、２−ジエチルアミノエタノール、トリエチレ
ングリコール、フェニルグリコール、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、ジイソプ
ロピルエーテル、テトラヒドロフラン、テトラヒドロピ
ラン、アセトン、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジ
メチルアセトアミド、エチレングリコール、プロピレン
グリコール、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、グリセリン、γ−ブチロラクト
ン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルアセト
アミド、ホルムアミド、水、重水、アンモニア、硫酸、
二硫化炭素、四塩化炭素、ペンタン、ヘキサン、シクロ
ヘキサン、イソオクタン、オクタン、ベンゼン、トルエ
ン、クロロホルム、１，２−ジクロロエタン、１，２−
ジブロモエタン、トリクロロエチレン、テトラクロロエ
チレン、クロロベンゼン、ブロモベンゼン、０−ジクロ
ロベンゼン、メタノール、エタノール、２，２，２−ト
リフルオロエタノール、イソペンチルアルコール、シク
ロヘキサノール、２−エトキシエタノ−ル、フェノー
ル、１，４−ジオキサン、アニソール、１，２−ジメト
キシエタン、メチルカルビトール、エチルカルビトー
ル、フルフラール、エチルメチルケトン、シクロヘキサ
ノン、ギ酸、酢酸、無水酢酸、トリクロロ酢酸、トリフ
ルオロ酢酸、酢酸エチル、酢酸ブチル、エチレンカーボ
ネイト、プロピレンカーボネイト、ヘキサメチルリン酸
トリアミド、リン酸トリエチル、アセトニトリル、プロ
ピオニトリル、スクシノニトリル、ベンゾニトリル、ニ
トロメタン、ニトロベンゼン、エチレンジアミン、ピリ
ジン、モルホリン、ジメチルスルホキシド、スルホラ
ン、モノブチルリン酸エステル、ｐ−ニトロ安息香酸、
ｐ−ニトロフェノール、ポリオキシエチレンオクチルフ
ェニルエーテルリン酸エステル、０−クレゾール、正リ
ン酸、トリブチルリン酸エステル、五酸化リン、ピロリ
ン酸、ポリリン酸ブチルエステル、亜リン酸、Ｄ−ソル
ビット、マンニット、ポリビニルアルコール、グリセリ
ン、ポリエチレングリコール等が挙げられる。混合され
る溶媒および添加剤は、本発明の駆動用電解液に８０ｗ
ｔ％以下溶けていることが望ましい。Solvents and additives mixed in the driving electrolyte of the present invention include propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, diacetone alcohol, benzyl alcohol, 2-diethylaminoethanol, Triethylene glycol, phenyl glycol, diethyl ether, diethylene glycol dimethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, acetone, N-methylformamide, N, N-dimethylacetamide, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether,
Diethylene glycol, glycerin, γ-butyrolactone, N, N-dimethylformamide, N-methylacetamide, formamide, water, heavy water, ammonia, sulfuric acid,
Carbon disulfide, carbon tetrachloride, pentane, hexane, cyclohexane, isooctane, octane, benzene, toluene, chloroform, 1,2-dichloroethane, 1,2-
Dibromoethane, trichloroethylene, tetrachloroethylene, chlorobenzene, bromobenzene, 0-dichlorobenzene, methanol, ethanol, 2,2,2-trifluoroethanol, isopentyl alcohol, cyclohexanol, 2-ethoxyethanol, phenol, 1,4 -Dioxane, anisole, 1,2-dimethoxyethane, methyl carbitol, ethyl carbitol, furfural, ethyl methyl ketone, cyclohexanone, formic acid, acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, ethyl acetate, butyl acetate, ethylene carbonate , Propylene carbonate, hexamethylphosphoric triamide, triethyl phosphate, acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromethane, nitrobe Zen, ethylenediamine, pyridine, morpholine, dimethylsulfoxide, sulfolane, monobutyl ester, p- nitrobenzoic acid,
p-nitrophenol, polyoxyethylene octylphenyl ether phosphate, 0-cresol, orthophosphoric acid, tributyl phosphate, phosphorus pentoxide, pyrophosphoric acid, butyl polyphosphate, phosphorous acid, D-sorbit, mannite , Polyvinyl alcohol, glycerin, polyethylene glycol and the like. The solvent and the additive to be mixed are 80 w in the driving electrolyte solution of the present invention.
It is desirable that it is melted at t% or less.
【００１４】本発明の電気化学素子駆動用電解液に含ま
れる水分量は、ラクトン環の−ＣＯＯ−部分の開環反応
による駆動用電解液の特性劣化を防ぐために、５ｗｔ％
以下が望ましい。The amount of water contained in the electrolytic solution for driving the electrochemical device of the present invention is 5 wt% in order to prevent the characteristic deterioration of the driving electrolyte by the ring-opening reaction of the --COO-- portion of the lactone ring.
The following is desirable.
【００１５】以下、本発明の電気化学素子駆動用電解液
およびそれを用いた電気化学素子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。本発明は、従来の駆動用電解液の溶媒であるγ−ブ
チロラクトンに電子吸引性置換基を導入することによっ
て、ラクトン環の−ＣＯＯ−部分の加水分解反応を抑制
して駆動用電解液の特性劣化が促進されるのを防止する
ことができるとともに、駆動用電解液の酸化側分解電位
を高めることもでき、しかもこの電解液を使用した製品
においては、高耐電圧化および長寿命化が図れる電気化
学素子駆動用電解液およびそれを用いた電気化学素子を
提供することができるものである。Hereinafter, specific examples of the electrolytic solution for driving an electrochemical device of the present invention and the electrochemical device using the same will be described, but the present invention is not limited thereto. The present invention suppresses the hydrolysis reaction of the -COO- moiety of the lactone ring by introducing an electron-withdrawing substituent into γ-butyrolactone, which is a solvent for a conventional driving electrolyte solution, and thus the characteristics of the driving electrolyte solution are suppressed. It is possible to prevent the deterioration from being promoted and also to increase the decomposition potential on the oxidation side of the driving electrolyte, and in addition, the product using this electrolyte can have a high withstand voltage and a long life. It is possible to provide an electrolytic solution for driving an electrochemical device and an electrochemical device using the electrolytic solution.
【００１６】（表１）は、従来例１の駆動用電解液と本
発明の実施例１，２，３，４，５の駆動用電解液を使用
した定格電圧２５Ｖ、定格容量１０００μＦのアルミ電
解コンデンサのそれぞれについて、１０５℃で定格電圧
負荷を２０００時間かけた後の容量変化率を示したもの
である。これらの駆動用電解液の溶質としては、マレイ
ン酸テトラメチルアンモニウムを２０ｗｔ％またはフタ
ル酸テトラメチルアンモニウムを２０ｗｔ％使用した。Table 1 shows an aluminum electrolysis having a rated voltage of 25 V and a rated capacity of 1000 μF using the driving electrolytic solution of Conventional Example 1 and the driving electrolytic solutions of Examples 1, 2, 3, 4, and 5 of the present invention. It shows the rate of change in capacitance of each of the capacitors after applying a rated voltage load at 105 ° C. for 2000 hours. As the solute of these driving electrolytic solutions, 20 wt% of tetramethylammonium maleate or 20 wt% of tetramethylammonium phthalate was used.
【００１７】[0017]
【表１】 [Table 1]
【００１８】（表１）から明らかなように、本発明の実
施例１，２，３，４，５の駆動用電解液を使用したアル
ミ電解コンデンサは、従来例１の駆動用電解液を使用し
たアルミ電解コンデンサに比べて容量変化率を小さく抑
えることができるため、アルミ電解コンデンサの長寿命
化が図れるものである。As is clear from Table 1, the aluminum electrolytic capacitors using the driving electrolyte solutions of Examples 1, 2, 3, 4, and 5 of the present invention use the driving electrolyte solution of Conventional Example 1. Since the rate of change in capacitance can be suppressed to be smaller than that of the aluminum electrolytic capacitor described above, the life of the aluminum electrolytic capacitor can be extended.
【００１９】（表２）は、溶媒としてプロピレンカーボ
ネイトあるいはγ−ブチロラクトンを用いた従来例１，
２の駆動用電解液と、β−ビニル−γ−ブチロラクトン
を溶媒として用いた本発明の実施例１の駆動用電解液の
分解電位と、従来例１，２の駆動用電解液と本発明の実
施例１の駆動用電解液を使用した定格容量０．３３Ｆの
電気二重層コンデンサの耐電圧を示したものである。Table 2 shows the conventional example 1 using propylene carbonate or γ-butyrolactone as a solvent.
No. 2 driving electrolytic solution and the decomposition potential of the driving electrolytic solution of Example 1 of the present invention using β-vinyl-γ-butyrolactone as a solvent, and the driving electrolytic solutions of Conventional Examples 1 and 2 and the present invention. 2 shows the withstand voltage of an electric double layer capacitor having a rated capacity of 0.33 F using the driving electrolyte solution of Example 1.
【００２０】分解電位は、関数発生器により作用電極側
の電位を２ｍＶ／ｓで掃引し、対極の参照電極に対して
１μＡの電流が流れたところの電位を分解電位とした。
また電気二重層コンデンサの耐電圧は、定電圧を２００
時間印加した後に電気二重層コンデンサに流れる電流値
を測定し、１μＡの電流が流れたところの電位を電気二
重層コンデンサの耐電圧とした。そしてまたこれらの駆
動用電解液の溶質としては、０．６Ｍ−テトラフルオロ
ほう酸テトラエチルアンモニウムを用いた。Regarding the decomposition potential, the potential on the side of the working electrode was swept at 2 mV / s by the function generator, and the potential at which a current of 1 μA flowed to the reference electrode of the counter electrode was defined as the decomposition potential.
The withstand voltage of an electric double layer capacitor is a constant voltage of 200
The value of the current flowing through the electric double layer capacitor after applying for a time was measured, and the potential at which a current of 1 μA flowed was taken as the withstand voltage of the electric double layer capacitor. Further, as a solute of these driving electrolyte solutions, 0.6M-tetraethylammonium tetrafluoroborate was used.
【００２１】[0021]
【表２】 [Table 2]
【００２２】（表２）から明らかなように、本発明の実
施例１の駆動用電解液を使用した電気二重層コンデンサ
は、従来例１，２の駆動用電解液を使用した電気二重層
コンデンサに比べて耐電圧を大幅に改善することができ
るものである。As is clear from (Table 2), the electric double layer capacitor using the driving electrolytic solution of Example 1 of the present invention is the electric double layer capacitor using the driving electrolytic solutions of Conventional Examples 1 and 2. Withstand voltage can be greatly improved compared to.
【００２３】[0023]
【発明の効果】以上のように本発明の電気化学素子駆動
用電解液によれば、溶媒として、（化１）におけるＲ1
〜Ｒ6の少なくとも一つ以上が電子吸引性置換基を有す
る化合物を少なくとも含んでなるものを用いているた
め、ラクトン環の−ＣＯＯ−部分の加水分解反応を抑制
して駆動用電解液の特性劣化が促進されるのを防止する
ことができるとともに、駆動用電解液の酸化側分解電位
も高めることができ、しかもこの駆動用電解液を使用し
た電気化学素子においては、高耐電圧化および長寿命化
が図れるものである。As described above, according to the electrolytic solution for driving an electrochemical device of the present invention, R 1 in the chemical formula 1 is used as a solvent.
Since at least one of R 6 to R 6 contains at least a compound having an electron-withdrawing substituent, it is possible to suppress the hydrolysis reaction of the —COO— portion of the lactone ring and thus the characteristics of the driving electrolyte solution. It is possible to prevent the deterioration from being promoted, and also to increase the decomposition potential on the oxidation side of the driving electrolyte solution. Moreover, in an electrochemical device using this driving electrolyte solution, a high withstand voltage and The life can be extended.
Claims (18)
（化１）におけるＲ1〜Ｒ6の少なくとも一つ以上が電子
吸引性置換基を有する化合物を少なくとも含んでなるも
のを用いた電気化学素子駆動用電解液。 【化１】 1. An electric charge comprising a solvent and a solute, wherein at least one of R 1 to R 6 in the chemical formula 1 contains at least a compound having an electron-withdrawing substituent. Electrolyte for driving chemical elements. [Chemical 1]
不飽和炭化水素基である請求項１記載の電気化学素子駆
動用電解液。2. The electrolytic solution for driving an electrochemical device according to claim 1, wherein the electron-withdrawing substituent is an unsaturated hydrocarbon group having two or more carbon atoms.
フェニル基、ビニル基、アリル基である請求項２記載の
電気化学素子駆動用電解液。3. The unsaturated hydrocarbon group having 2 or more carbon atoms is
The electrolytic solution for driving an electrochemical device according to claim 2, which is a phenyl group, a vinyl group or an allyl group.
がビニル基である請求項１記載の電気化学素子駆動用電
解液。4. R 1 , R 2 , R 4 , R 5 and R 6 are hydrogen and R 3
The electrolytic solution for driving an electrochemical element according to claim 1, wherein is a vinyl group.
素数一つ以上の炭化水素基）で示される置換基である請
求項１記載の電気化学素子駆動用電解液。5. The electrolytic solution for driving an electrochemical device according to claim 1, wherein the electron-withdrawing substituent is a substituent represented by —OR 7 (R 7 is a hydrocarbon group having one or more carbon atoms).
炭素数二つ以上の炭化水素基）で示される置換基である
請求項１記載の電気化学素子駆動用電解液。6. The electrolytic solution for driving an electrochemical device according to claim 1, wherein the electron-withdrawing substituent is a substituent represented by —COR 8 (R 8 is a hydrocarbon group having two or more carbon atoms).
求項１記載の電気化学素子駆動用電解液。7. The electrolytic solution for driving an electrochemical device according to claim 1, wherein the electron-withdrawing substituent is halogen.
求項１記載の電気化学素子駆動用電解液。8. The electrolytic solution for driving an electrochemical element according to claim 1, wherein the electron-withdrawing group is a cyano group.
求項１記載の電気化学素子駆動用電解液。9. The electrolytic solution for driving an electrochemical device according to claim 1, wherein the electron-withdrawing group is a nitro group.
れる置換基である請求項１記載の電気化学素子駆動用電
解液。 【化２】 10. The electrolytic solution for driving an electrochemical device according to claim 1, wherein the electron-withdrawing substituent is a substituent represented by the formula (2). [Chemical 2]
ム塩、アルカリ金属塩の少なくとも一種以上からなる請
求項１〜１０のいずれかに記載の電気化学素子駆動用電
解液。11. The electrolytic solution for driving an electrochemical element according to claim 1, wherein the solute comprises at least one of ammonium salt, phosphonium salt and alkali metal salt.
硝酸、硫酸、塩酸、過塩素酸、テトラフルオロほう酸、
フルオロメタンスルホン酸である請求項１１記載の電気
化学素子駆動用電解液。12. The solute-constituting acid group is a carboxylic acid,
Nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, tetrafluoroboric acid,
The electrolytic solution for driving an electrochemical device according to claim 11, which is fluoromethanesulfonic acid.
は、安息香酸、マレイン酸、フタル酸、アジピン酸であ
る請求項１２記載の電気化学素子駆動用電解液。13. The electrolytic solution for driving an electrochemical device according to claim 12, wherein the carboxylic acid in the acid group constituting the solute is benzoic acid, maleic acid, phthalic acid or adipic acid.
ム塩は、テトラアンモニウム塩、テトラエチルアンモニ
ウム塩、メチルトリエチルアンモニウム塩である請求項
１１記載の電気化学素子駆動用電解液。14. The electrolytic solution for driving an electrochemical device according to claim 11, wherein the ammonium salt in the base constituting the solute is a tetraammonium salt, a tetraethylammonium salt, or a methyltriethylammonium salt.
請求項１〜１４のいずれかに記載の電気化学素子駆動用
電解液。15. The electrolytic solution for driving an electrochemical device according to claim 1, wherein the solute has a concentration of 50 wt% or less.
ある請求項１〜１５のいずれかに記載の電気化学素子駆
動用電解液。16. The electrolytic solution for driving an electrochemical element according to claim 1, wherein the amount of water in the electrolytic solution is 5 wt% or less.
トロ化合物を添加した請求項１〜１６のいずれかに記載
の電気化学素子駆動用電解液。17. The electrolytic solution for driving an electrochemical device according to claim 1, wherein a phosphorus compound or an aromatic nitro compound is added as an additive.
気化学素子駆動用電解液を用いた電気化学素子。18. An electrochemical device using the electrolytic solution for driving an electrochemical device according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07583094A JP3355776B2 (en) | 1994-04-14 | 1994-04-14 | Electrolyte for driving electrochemical element and electrochemical element using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07583094A JP3355776B2 (en) | 1994-04-14 | 1994-04-14 | Electrolyte for driving electrochemical element and electrochemical element using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07283083A true JPH07283083A (en) | 1995-10-27 |
| JP3355776B2 JP3355776B2 (en) | 2002-12-09 |
Family
ID=13587507
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07583094A Expired - Fee Related JP3355776B2 (en) | 1994-04-14 | 1994-04-14 | Electrolyte for driving electrochemical element and electrochemical element using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3355776B2 (en) |
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| US7875201B2 (en) | 2005-05-19 | 2011-01-25 | Panasonic Corporation | Electrolyte solution, electrochemical device using same, and electronic device |
| JP2008016252A (en) * | 2006-07-04 | 2008-01-24 | Sony Corp | Nonaqueous electrolyte composition and nonaqueous electrolyte battery |
| JP2008021534A (en) * | 2006-07-13 | 2008-01-31 | Sony Corp | Nonaqueous electrolyte composition and nonaqueous electrolyte secondary battery |
| JP2009123498A (en) * | 2007-11-14 | 2009-06-04 | Sony Corp | Nonaqueous electrolyte composition and nonaqueous electrolyte battery |
| JP2010171305A (en) * | 2009-01-26 | 2010-08-05 | Panasonic Corp | Electrolytic solution for driving electrolytic capacitor, and electrolytic capacitor using the same |
| JP2013048015A (en) * | 2011-07-27 | 2013-03-07 | Daikin Ind Ltd | Nonaqueous electrolyte, lithium ion secondary battery, and module |
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|---|---|
| JP3355776B2 (en) | 2002-12-09 |
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