JPS6011452B2 - electric double layer capacitor - Google Patents
electric double layer capacitorInfo
- Publication number
- JPS6011452B2 JPS6011452B2 JP54019216A JP1921679A JPS6011452B2 JP S6011452 B2 JPS6011452 B2 JP S6011452B2 JP 54019216 A JP54019216 A JP 54019216A JP 1921679 A JP1921679 A JP 1921679A JP S6011452 B2 JPS6011452 B2 JP S6011452B2
- Authority
- JP
- Japan
- Prior art keywords
- double layer
- electric double
- layer capacitor
- weight
- 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.)
- Expired
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
Description
【発明の詳細な説明】
本発明は低電圧、大静電容量の特性を有する電気二重層
キャパシタの電解液に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrolytic solution for an electric double layer capacitor having characteristics of low voltage and large capacitance.
一般に、電気二重層キャパシタは、図に示すように黒鉛
、カーボンブラック「活性炭などの炭素電極体１と集電
体２とからなる電極間に電解液を含浸させたセパレータ
を介在させて巻回または積層した構成となっている。In general, an electric double layer capacitor is manufactured by winding or winding a separator impregnated with an electrolyte between electrodes consisting of a carbon electrode body 1 made of graphite, carbon black or activated carbon, and a current collector 2, as shown in the figure. It has a laminated structure.
ところで、これに使用する電解液は、このキャバシタの
耐電圧を決定する重要な材料であることから、本発明者
らは種々の検討を重ねてきた。By the way, since the electrolytic solution used in this is an important material that determines the withstand voltage of this capacitor, the present inventors have conducted various studies.
その結果、耐電圧の向上の手段として、非水電解液にと
りくみ、そして有機溶媒とそれに溶解性の良好な電解質
を溶かし、良電導性を得る有機溶媒として、ジメチルフ
オルムアミド、プロピレンカ−ボネＭト、ｙ−ブチロラ
クトン、テトラヒドロフランなどの非プロトン系の樋性
溶媒と、テトラエチルアンモニウムパークロレート、過
塩素酸アンモニウム、六弗化リン酸カリなどの高次化合
物からなる溶質を見し、出してきた。また、本発明者ら
は、これらから、最も良好な電解液を得るために種々検
討した結果、ｙーブチロラクトンとテトラエチルアンモ
ニウムパークロレートを混合した電解液が最も良好であ
ることを見し、出し、提供してきた。しかしながら、経
時変化（高温寿命テストにより確認）に対して、やや不
満足であることが判明夕した。As a result, as a means to improve withstand voltage, we have used dimethylformamide, propylene carbonate, M Solutes consisting of aprotic solvents such as t-, y-butyrolactone, and tetrahydrofuran, and higher-order compounds such as tetraethylammonium perchlorate, ammonium perchlorate, and potassium hexafluorophosphate were found and extracted. In addition, the present inventors conducted various studies to obtain the best electrolyte from these, and found that an electrolyte containing a mixture of y-butyrolactone and tetraethylammonium perchlorate was the best. have provided. However, it was found that the change over time (confirmed by high temperature life test) was somewhat unsatisfactory.
そこで、本発明者らは、この改良に新らたに第３の溶媒
を添加する２種の混合溶媒による方法で検討を行った。Therefore, the present inventors investigated a method using two mixed solvents in which a third solvent was newly added to improve this.
そして、プロピレンカーボネートの若干の添加は、‘１
耐電圧の低下をきたさない、０‘２）初期特性を悪化さ
せない、‘３’温度特性を悪化させない、という３つの
条件に、合致する良好な特性を与えることが判明した。
すなわち、本発明の電気二重層キャパシ夕においては、
電解液としてプロピレンカーボネート、タｙ−ブチロラ
クトン、テトラエチルアンモニウムパークロレートとか
らなる混合溶媒電解液を用いるものである。特に、本発
明においては、それらの材料の配合比をプロピレンカー
ボネートを５〜３の重量％、ｙ−ブチロラクトンを７０
〜９０重量％、テトラエチルアンモニウムパークロレー
トを５〜２広重量％とした場合に良好な結果を得ること
ができる。以下、本発明による電気二重層キャパシ外こ
ついて具体的実施例をもとに説明する。And some addition of propylene carbonate is '1
It has been found that it provides good characteristics that meet the following three conditions: 0'2) no reduction in withstand voltage, 0'2) no deterioration of initial characteristics, and 3) no deterioration of temperature characteristics.
That is, in the electric double layer capacitor of the present invention,
A mixed solvent electrolyte consisting of propylene carbonate, t-y-butyrolactone, and tetraethylammonium perchlorate is used as the electrolyte. In particular, in the present invention, the blending ratio of these materials is 5 to 3% by weight of propylene carbonate and 70% by weight of y-butyrolactone.
Good results can be obtained with a content of 5 to 2% by weight of tetraethylammonium perchlorate. Hereinafter, the outer structure of the electric double layer capacitor according to the present invention will be explained based on specific examples.
なお」以下の具体例では、供試品として定格電圧が１．
６Ｖ、静電容量が１価「 ケース寸法が１２．５肋？×
３５脚のものを使用している。また、電気二重層キャパ
シタの素子は、活性炭Ｌアセチレンブラック「若干のバ
インダーを混合した炭素電極体と集電体とで電極を構成
し、その間にセパレータと電解液とを介した構造となっ
ている。素子は、巻回式のものを使用したが、積層型の
ものや単に２枚の電極を対向させたのみのものもある。
これに使う電解液はも通常セパレータと電極とで素子を
構成した後、含浸している。表１に「ｙーブチロラクト
ンに第２の溶媒として種々のものを添加した場合の初期
特性を従来品と比較して示している。In addition, in the following specific example, the rated voltage is 1.
6V, monovalent capacitance "Case size is 12.5 ribs?
I am using one with 35 legs. In addition, the electric double layer capacitor element has a structure in which the electrode is composed of a carbon electrode body mixed with activated carbon L acetylene black and a small amount of binder and a current collector, with a separator and an electrolyte interposed between them. Although a wound type element was used, there are also laminated type elements and elements that simply have two electrodes facing each other.
The electrolytic solution used for this is usually impregnated after forming the element with the separator and electrode. Table 1 shows the initial characteristics when various second solvents are added to y-butyrolactone in comparison with conventional products.
なお、従来品としては、重量比でｙーブチロラクトン１
００、テトラエチルアンモニウム／ぐークロレート１５
のものを用いた。In addition, as a conventional product, the weight ratio is y-butyrolactone 1
00, Tetraethylammonium/Gucchlorate 15
I used the one from
また、表１中、「◎」は従来品に比べて優れている、ｒ
ｏ」は同等、「△ｊは劣っている、「×」は使用不可を
表わす。表 １上記表１の結果より、本発明の目的に適
するものとしてプロピレンカーボネートを選定した。In addition, in Table 1, "◎" indicates that the product is superior to the conventional product.
"o" indicates equivalent, "Δj" indicates inferior, and "x" indicates unusable. Table 1 Based on the results shown in Table 1 above, propylene carbonate was selected as suitable for the purpose of the present invention.
なお、これに用いた電解液の組成、配合は〜重量比で「
ｙ−ブチロラクトンが７０、第２の溶媒３０、テトラ
エチルアンモニウムパークロレートが１５であつた。ま
た、表２に、ｙ−ブチロラクトンとプロピレンカーボネ
ートの最適配合量の検討結果を示している。In addition, the composition and formulation of the electrolyte used for this is ~ in terms of weight ratio.
70 for y-butyrolactone, 30 for the second solvent, and 15 for tetraethylammonium perchlorate. Further, Table 2 shows the results of an examination of the optimum blending amounts of y-butyrolactone and propylene carbonate.
この表２ではテトラエチルアンモニウムパークロレート
を１５（重量比）と一定とし、ｙ−フチロラクトンとプ
ロピレンカーボネートの配合比を０〜１００の間におい
て、表２のように変えて行き、その時の初期の温度特性
と、高温寿命テスト後の結果を示した。表 ２
上記表２の結果より、プロピレンカーポネートの若干の
添加は、温度特性に殆んど影響を与えることなく高温負
荷後の静電容量の変化率を半減できることが判明した。In this Table 2, the tetraethylammonium perchlorate is kept constant at 15 (weight ratio), and the blending ratio of y-futhyrolactone and propylene carbonate is varied between 0 and 100 as shown in Table 2, and the initial temperature characteristics at that time are This shows the results after a high-temperature life test. Table 2 From the results shown in Table 2 above, it was found that the addition of a small amount of propylene carbonate could halve the rate of change in capacitance after high temperature loading, with almost no effect on the temperature characteristics.
表３に、電解質であるテトラエチルアンモニウムパーク
ロレ−トの最適配合量についての検討結＊＊果を示して
おり、この表３ではｙーブチロラクトンを７の重量％、
プロピレンカーボネートを３の重量％と一定とし、表３
のようにテトラエチルアンモニウムパークロレートの添
加量を変えて行った場合の温度特性と高温寿命テスト後
の静電容量の変化率を示している。表 ３
上記表３の結果より、テトラエチルアンモニウムパーク
ロレートの配合量は１５〜２の重量％の間が最適である
ことが判明した。Table 3 shows the results of an investigation regarding the optimum blending amount of tetraethylammonium perchlorate, which is an electrolyte.
Propylene carbonate is kept constant at 3% by weight, Table 3
It shows the temperature characteristics and the rate of change in capacitance after a high-temperature life test when the amount of tetraethylammonium perchlorate added was changed. Table 3 From the results shown in Table 3 above, it was found that the optimum amount of tetraethylammonium perchlorate is between 15 and 2% by weight.
また「表１〜表３の結果を総合すると、ｙーブチロラク
トンが７の重量％「 プロピレンカーボネートが３の重
量％し テトラエチルアンモニウムパークロレートが１
５重量％を最適配合量とする電解液が、最も良好なもの
であることが判明した。以上のように、本発明の電解液
を使用した電気二重層キャパシタによれば、従来の特性
を大きく改善して経時変化の少ない製品を得ることがで
き、その効果は大なるものである。Furthermore, ``If we combine the results in Tables 1 to 3, y-butyrolactone is 7% by weight, propylene carbonate is 3% by weight, and tetraethylammonium perchlorate is 1% by weight.''
An electrolytic solution with an optimum content of 5% by weight was found to be the most favorable. As described above, according to the electric double layer capacitor using the electrolytic solution of the present invention, it is possible to obtain a product that greatly improves the conventional characteristics and has little change over time, and its effects are significant.
図は一般的な電気二重層キャパシタの基本構造を示す構
成図である。
１・・・・・・炭素電極体、２……集電体、３・・・…
セパレータ。The figure is a configuration diagram showing the basic structure of a general electric double layer capacitor. 1... Carbon electrode body, 2... Current collector, 3...
Separator.
Claims (1)
対向させ、その間にセパレータの電解液を介在させてな
る電気二重層キヤパシタにおいて、電解液としてプロピ
レンカーボネート、γ−ブチロラクトン、テトラエチル
アンモニウムパークロレートからなる混合溶媒電解液を
用いたことを特徴とする電気二重層キヤパシタ。 ２ 電解液がプロピレンカーボネートを５〜３０重量％
、γ−ブチロラクトンを７０〜９０重量％、テトラエチ
ルアンモニウムパークロレートを５〜２０重量％の重量
比で混合したものであることを特徴とする特許請求の範
囲第１項に記載の電気二重層キヤパシタ。[Scope of Claims] 1. An electric double layer capacitor in which carbon electrodes such as graphite, carbon black, activated carbon, etc. are opposed and an electrolytic solution as a separator is interposed between them, and propylene carbonate, γ-butyrolactone, or tetraethylammonium is used as the electrolytic solution. An electric double layer capacitor characterized by using a mixed solvent electrolyte comprising perchlorate. 2 Electrolyte contains 5-30% by weight of propylene carbonate
, 70 to 90% by weight of γ-butyrolactone, and 5 to 20% by weight of tetraethylammonium perchlorate.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54019216A JPS6011452B2 (en) | 1979-02-20 | 1979-02-20 | electric double layer capacitor |
| US06/109,406 US4327400A (en) | 1979-01-10 | 1980-01-03 | Electric double layer capacitor |
| FR8000383A FR2446534A1 (en) | 1979-01-10 | 1980-01-09 | DOUBLE LAYER ELECTRIC CAPACITOR |
| GB8000701A GB2040570B (en) | 1979-01-10 | 1980-01-09 | Electric double layer capacitor |
| DE3000777A DE3000777C2 (en) | 1979-01-10 | 1980-01-10 | Method of manufacturing an electrical double layer capacitor - US Pat |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54019216A JPS6011452B2 (en) | 1979-02-20 | 1979-02-20 | electric double layer capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55111124A JPS55111124A (en) | 1980-08-27 |
| JPS6011452B2 true JPS6011452B2 (en) | 1985-03-26 |
Family
ID=11993171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP54019216A Expired JPS6011452B2 (en) | 1979-01-10 | 1979-02-20 | electric double layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6011452B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995020231A1 (en) * | 1994-01-20 | 1995-07-27 | Tovarischestvo S Ogranichennoi Otvetstvennostju 'amadeus' | Electrical accumulator |
-
1979
- 1979-02-20 JP JP54019216A patent/JPS6011452B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995020231A1 (en) * | 1994-01-20 | 1995-07-27 | Tovarischestvo S Ogranichennoi Otvetstvennostju 'amadeus' | Electrical accumulator |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55111124A (en) | 1980-08-27 |
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