JP3440607B2 - Electrolyte for electric double layer capacitors - Google Patents
Electrolyte for electric double layer capacitorsInfo
- Publication number
- JP3440607B2 JP3440607B2 JP4210195A JP4210195A JP3440607B2 JP 3440607 B2 JP3440607 B2 JP 3440607B2 JP 4210195 A JP4210195 A JP 4210195A JP 4210195 A JP4210195 A JP 4210195A JP 3440607 B2 JP3440607 B2 JP 3440607B2
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- electrolytic solution
- double layer
- mixed solvent
- electric double
- 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 - Lifetime
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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は各種電子機器のメモリー
バックアップ用大電流を必要とする電気自動車などのパ
ワーとして用いられる電気二重層コンデンサの内部に使
用される電気伝導率の高い電解液に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic solution having a high electric conductivity, which is used in an electric double layer capacitor used as a power for an electric vehicle requiring a large current for memory backup of various electronic devices.
【０００２】[0002]
【従来の技術】電気二重層コンデンサは、分極性電極と
電解液との界面に生成する電気二重層に電荷を蓄積する
素子である。通常、電気二重層コンデンサは活性炭粒子
をプレス成形したり、適当なバインダーと練り合わせた
ものを集電体金属上に塗布したり、あるいは、活性炭素
繊維上にアルミニウムをプラズマ溶射したものを分極性
電極として用い、この２つの分極性電極を電解液とセパ
レータを介して対向させ、ケースの中に密封させた構造
を有する。この電気二重層コンデンサに使用される電解
液としては、硫酸あるは水酸化カリウム水溶液などの水
系電解液と、プロピレンカーボネート、ジメチルスルホ
キシドなどの有機溶媒に四級アンモニウム塩、有機酸の
金属塩などを溶解した非水系電解液が特公昭５５−４１
０１５号公報に示されている。2. Description of the Related Art An electric double layer capacitor is an element for accumulating charges in an electric double layer generated at the interface between a polarizable electrode and an electrolytic solution. Usually, an electric double layer capacitor is obtained by press-molding activated carbon particles, coating a mixture with an appropriate binder on a current collector metal, or plasma-spraying aluminum on activated carbon fibers with a polarizable electrode. The two polarizable electrodes are opposed to each other via the electrolytic solution via the separator and are hermetically sealed in the case. As the electrolytic solution used in this electric double layer capacitor, an aqueous electrolytic solution such as sulfuric acid or an aqueous potassium hydroxide solution, a quaternary ammonium salt in an organic solvent such as propylene carbonate or dimethyl sulfoxide, a metal salt of an organic acid, etc. Dissolved non-aqueous electrolyte is JP-B-55-41
No. 015 publication.
【０００３】水系電解液は電気伝導率は高いが、分解電
圧が低いので、耐電圧の高い素子を得るためには積層直
列化する必要があり、小型化に難点があった。一方、非
水系電解液は分解電圧が高いので小型化できる長所はあ
るが、電気伝導率が低いので素子の内部抵抗が高くな
り、大電流が取り出せないという欠点を有していた。ま
た、電気二重層コンデンサ用の非水系電解液として、プ
ロピレンカーボネート溶媒にホウフッ化四級アンモニウ
ム塩（棚橋ら、電気化学、５６巻、８９２頁、１９８８
年）あるいはホウフッ化四級ホスホニウム塩（平塚ら、
電気化学、５９巻、２０９頁、１９９１年）が実用化さ
れている。しかし、これら電解液の電気伝導率はまだ充
分でなく、これら電解液と同等の耐電圧を有しながら、
さらに、高い電気伝導率を有する電解液の開発が望まれ
ている。更に、エチレンカーボネートとガンマーブチロ
ラクトンとの混合溶媒が電気二重層コンデンサ用電解液
として提案されているが、混合による電気伝導率の向上
はほとんど認められなかったと報告されている（森田
ら、Ｊ．Ａｐｐｌ．Ｅｌｅｃｔｒｏｃｈｅｍ．，２２
巻、９０１頁、１９９２年）。The aqueous electrolyte has a high electric conductivity, but has a low decomposition voltage. Therefore, in order to obtain an element having a high withstand voltage, it is necessary to make a serial connection in layers, and there is a difficulty in miniaturization. On the other hand, the non-aqueous electrolyte has an advantage that it can be miniaturized because of its high decomposition voltage, but it has a drawback that the internal resistance of the element becomes high and a large current cannot be taken out because of its low electric conductivity. Further, as a non-aqueous electrolytic solution for electric double layer capacitors, a quaternary ammonium borofluoride salt in a propylene carbonate solvent (Tanahashi et al., Electrochemistry, Vol. 56, p. 892, 1988).
Or quaternary phosphonium borofluoride salt (Hiratsuka et al.,
Electrochemistry, Vol. 59, p. 209, 1991) has been put to practical use. However, the electric conductivity of these electrolytes is not yet sufficient, while having a withstand voltage equivalent to these electrolytes,
Further, development of an electrolytic solution having high electric conductivity is desired. Furthermore, a mixed solvent of ethylene carbonate and gamma-butyrolactone has been proposed as an electrolytic solution for electric double layer capacitors, but it has been reported that an improvement in electric conductivity due to mixing was hardly observed (Morita et al., J. Appl. Electrochem., 22.
Vol. 901, 1992).
【０００４】[0004]
【発明が解決しようとする課題】本発明は、高い電気伝
導率を示す電気二重層コンデンサ用電解液を提供するこ
とを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrolytic solution for electric double layer capacitors which exhibits high electric conductivity.
【０００５】[0005]
【課題を解決するための手段】本発明は、分極性電極と
電解液との界面で形成される電気二重層を利用するコン
デンサに用いられる電解液において、電解液が鎖状カー
ボネートとエチレンカーボネートとの混合溶媒に溶質の
トリエチルメチルアンモニウム塩が溶解されたものから
成る電気二重層コンデンサ用電解液を提供するものであ
る。The present invention relates to an electrolytic solution used in a capacitor that utilizes an electric double layer formed at the interface between a polarizable electrode and the electrolytic solution, wherein the electrolytic solution is a chain carbonate and ethylene carbonate. Of solute in mixed solvent
The present invention provides an electrolytic solution for an electric double layer capacitor, which comprises a solution of triethylmethylammonium salt.
【０００６】[0006]
【作用】常温で固体であるエチレンカーボネートと粘度
の低い鎖状カーボネートとを混合することにより常温で
液状を示す混合溶媒とすることができる。この混合溶媒
を用いることにより溶質のトリエチルメチルアンモニウ
ム塩のイオン解離度を余り低下させることなく、イオン
移動度が向上し、電気伝導率の高い電解液となる。By mixing ethylene carbonate, which is solid at room temperature, and chain carbonate, which has a low viscosity, a mixed solvent that is liquid at room temperature can be obtained. By using this mixed solvent, the ion mobility of the solute triethylmethylammonium salt is not lowered so much, and the ion mobility is improved, resulting in an electrolytic solution having high electric conductivity.
【０００７】（発明の概要）
鎖状カーボネート本発明で使用する鎖状カーボネート
は、ジメチルカーボネート、エチルメチルカーボネート
およびジエチルカーボネートである。これらは単独で、
又、二種以上併用して用いられる。エチレンカーボネー
トエチレンカーボネートは高い誘電率を有する常温で固
体を示すものである。(Outline of the Invention) Chain Carbonate The chain carbonate used in the present invention is dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate. These alone
Further, two or more kinds are used in combination. Ethylene carbonate Ethylene carbonate has a high dielectric constant and is solid at room temperature.
【０００８】混合溶媒
混合溶媒は、１０〜６０重量％の鎖状カーボネートと、
９０〜４０重量％のエチレンカーボネートよりなる。混
合溶媒中に占める鎖状カーボネートの量が１０重量％未
満では電解液の電気伝導率の向上が望めず、逆に６０重
量％を越えるとエチレンカーボネートの析出が見られ
る。Mixed solvent The mixed solvent is 10 to 60% by weight of chain carbonate,
It consists of 90-40% by weight of ethylene carbonate. When the amount of the chain carbonate in the mixed solvent is less than 10% by weight, the improvement of the electric conductivity of the electrolytic solution cannot be expected, and when it exceeds 60% by weight, the precipitation of ethylene carbonate is observed.
【０００９】溶質
溶質として用いられるトリエチルメチルアンモニウム塩
としては、ホウフッ化トリエチルメチルアンモニウムお
よびリンフッ化トリエチルメチルアンモニウム等があ
り、これらは単独で、または二種以上混合して用いられ
る。電解液中に占める溶質のトリエチルメチルアンモニ
ウム塩に溶解量は、０．５〜２．０モル濃度（ｍｏｌ／
ｌ）である。Solutes Triethylmethylammonium salts used as solutes include triethylmethylammonium borofluoride and triethylmethylammonium phosphorofluoride, which may be used alone or in admixture of two or more. The amount of the solute occupying the triethylmethylammonium salt in the electrolytic solution is 0.5 to 2.0 molar concentration (mol / mol).
l).
【００１０】[0010]
【実施例】以下に、実施例を挙げて、本発明を更に具体
的に説明する。
実施例１
４０重量％のジメチルカーボネートと６０重量％のエチ
レンカーボネートとの混合溶媒に、１モル濃度のホウフ
ッ化トリエチルメチルアンモニウムを溶解し、減圧加熱
によって脱水（１００ｐｐｍ以下）し電解液を得た。こ
の電解液の２５℃における電気伝導率は２０．８ｍＳ／
ｃｍであった。また、グラッシーカーボン電極を用い、
１ｍＶ／ｓｃｃの走査電位速度で、分極測定をした時に
１ｍＡ／ｃｍ2の電流が流れる時の分解電位は飽和カロ
メル参照電極（ＳＣＥ）に対し、還元側−３．０Ｖ、酸
化側＋３．３Ｖであった。表１に得られた電解液の物性
を示す。 EXAMPLES The present invention will be described more specifically below with reference to examples. Example 1 In a mixed solvent of 40% by weight of dimethyl carbonate and 60% by weight of ethylene carbonate, 1 molar concentration of broth was added.
Triethylmethylammonium chloride was dissolved and dehydrated (100 ppm or less) by heating under reduced pressure to obtain an electrolytic solution. The electric conductivity of this electrolytic solution at 25 ° C. was 20. 8 mS /
It was cm. Also, using a glassy carbon electrode,
At the scanning potential rate of 1 mV / scc, the decomposition potential when a current of 1 mA / cm 2 flows when polarization measurement was performed was −3.0 V on the reduction side and +3.3 V on the oxidation side with respect to the saturated calomel reference electrode (SCE). It was Physical properties of the electrolytic solution obtained in Table 1
Indicates.
【００１１】比較例１ 実施例１において、混合溶媒に代えてプロピレンカーボ
ネートを単独で用いる他は同様にして得られた電解液の
物性を表１に示す。 Comparative Example 1 In Example 1, propylene carbohydrate was used instead of the mixed solvent.
Of the electrolyte solution obtained in the same manner except that nate is used alone.
The physical properties are shown in Table 1.
【００１２】[0012]
【表１】 [Table 1]
【００１３】[0013]
【発明の効果】電気伝導率の高い電解液である。EFFECT OF THE INVENTION An electrolytic solution having high electric conductivity.
【００１４】[0014]
【図面の簡単な説明】[Brief description of drawings]
【図１】混合溶媒のエチレンカーボネートとジメチルカ
ーボネートの混合比率を変えたときの電解液の電気伝導
率の変化を示す図である。FIG. 1 is a diagram showing a change in electric conductivity of an electrolytic solution when a mixing ratio of ethylene carbonate and dimethyl carbonate as a mixed solvent is changed.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平８−37133（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01G 9/038 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-8-37133 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) H01G 9/038
Claims (4)
る電気二重層を利用するコンデンサに用いられる電解液
において、電解液が鎖状カーボネートとエチレンカーボ
ネートとの混合溶媒に溶質のトリエチルメチルアンモニ
ウム塩が溶解されたものから成る電気二重層コンデンサ
用電解液。1. An electrolytic solution used in a capacitor utilizing an electric double layer formed at an interface between a polarizable electrode and the electrolytic solution, wherein the electrolytic solution is triethylmethyl which is a solute in a mixed solvent of chain carbonate and ethylene carbonate. An electrolytic solution for an electric double layer capacitor, comprising an ammonium salt dissolved therein.
ート、エチルメチルカーボネートおよびジエチルカーボ
ネートから選ばれたものである請求項１記載の電解液。2. The electrolytic solution according to claim 1, wherein the chain carbonate is selected from dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate.
フッ化トリエチルメチルアンモニウムおよびリンフッ化
トリエチルメチルアンモニウムから選ばれた１種以上で
ある請求項１記載の電解液。3. triethylmethylammonium salt Gaho c <br/> electrolyte according to claim 1, wherein at least one member selected from fluoride triethylmethylammonium and Rinfu' of triethyl methyl ammonium.
が１０〜６０重量％で、エチレンカーボネートの量が９
０〜４０重量％であり、電解液中に占める溶質のトリエ
チルメチルアンモニウム塩の溶解量が０．５〜２．０モ
ル濃度である請求項１記載の電解液。4. The amount of chain carbonate in the mixed solvent is 10 to 60% by weight, and the amount of ethylene carbonate is 9%.
0 to 40% by weight, triethanolamine of the solute occupied in the electrolyte
Electrolyte of claim 1 wherein the amount of dissolved Chirumechiru ammonium salt is 0.5 to 2.0 molar concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4210195A JP3440607B2 (en) | 1995-03-01 | 1995-03-01 | Electrolyte for electric double layer capacitors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4210195A JP3440607B2 (en) | 1995-03-01 | 1995-03-01 | Electrolyte for electric double layer capacitors |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08236404A JPH08236404A (en) | 1996-09-13 |
| JP3440607B2 true JP3440607B2 (en) | 2003-08-25 |
Family
ID=12626603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4210195A Expired - Lifetime JP3440607B2 (en) | 1995-03-01 | 1995-03-01 | Electrolyte for electric double layer capacitors |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3440607B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE602005000013T2 (en) | 2004-01-28 | 2006-10-05 | Honda Motor Co., Ltd. | Double layer capacitor and electrolyte solution for it |
| JP2008071777A (en) * | 2006-09-12 | 2008-03-27 | Meidensha Corp | Method of injecting electrolyte in manufacturing electric double-layer capacitor |
-
1995
- 1995-03-01 JP JP4210195A patent/JP3440607B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08236404A (en) | 1996-09-13 |
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