JP2003109861A - Electrical double layer capacitor and electrolyte therefor - Google Patents
Electrical double layer capacitor and electrolyte thereforInfo
- Publication number
- JP2003109861A JP2003109861A JP2001303951A JP2001303951A JP2003109861A JP 2003109861 A JP2003109861 A JP 2003109861A JP 2001303951 A JP2001303951 A JP 2001303951A JP 2001303951 A JP2001303951 A JP 2001303951A JP 2003109861 A JP2003109861 A JP 2003109861A
- Authority
- JP
- Japan
- Prior art keywords
- double layer
- layer capacitor
- electric double
- butyrolactone
- electrolytic solution
- 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.)
- Pending
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]
【発明の属する技術分野】本発明は電気二重層コンデン
サおよび電気二重層コンデンサ用の電解液に関する。TECHNICAL FIELD The present invention relates to an electric double layer capacitor and an electrolytic solution for the electric double layer capacitor.
【０００２】[0002]
【従来の技術】電気二重層コンデンサ、例えば捲回型の
電気二重層コンデンサは、集電体である例えばアルミニ
ウム箔に引出しリードを固着し、同集電体の片面または
両面に例えば活性炭、カーボン、ポリテトラフルオロエ
チレン（ＰＴＦＥ）などからなる分極性電極層を設けて
なる２枚の電極を、分極性電極層を対向させるように配
置し、かつその間にセパレータを介在させて捲回してコ
ンデンサ素子となし、これに電解液を含浸させて、有底
の金属ケースに入れ、引出しリードを封口板のリード用
の貫通口を通して引き出すか、あるいは封口板を貫通す
るように配置された外部端子に固着した後、同封口体に
て金属ケースの開口部を密封してなる構造を有する。2. Description of the Related Art An electric double layer capacitor, for example, a wound type electric double layer capacitor, has a lead which is fixed to a current collector, for example, an aluminum foil, and one side or both sides of the current collector, for example, activated carbon, carbon, Two electrodes each having a polarizable electrode layer made of polytetrafluoroethylene (PTFE) or the like are arranged so that the polarizable electrode layers face each other, and a separator is interposed between the two electrodes to wind the electrode, thereby forming a capacitor element. None, impregnated with electrolytic solution, put in a metal case with a bottom, and pull out the extraction lead through the through hole for the lead of the sealing plate, or fix it to an external terminal arranged to penetrate the sealing plate. After that, it has a structure in which the opening of the metal case is sealed by the sealing body.
【０００３】電気二重層コンデンサ用の電解液として
は、例えば有機系の電解液では溶媒として例えばγーブ
チロラクトン（ＧＢＬ）、溶質としてテトラエチルアン
モニウム（ＴＥＡ）やトリエチルメチルアンモニウム
（ＴＥＭＡ）などの４級塩アンモニウムのテトラフロロ
ボレート塩が使用されている。As an electrolytic solution for an electric double layer capacitor, for example, in an organic electrolytic solution, a solvent is, for example, γ-butyrolactone (GBL), and a solute is a quaternary salt such as tetraethylammonium (TEA) or triethylmethylammonium (TEMA). The ammonium tetrafluoroborate salt has been used.
【０００４】[0004]
【発明が解決しようとする課題】しかしながらγーブチ
ロラクトン溶媒系の電解液を使用した電気二重層コンデ
ンサは、低温での内部抵抗は低いが、高温無負荷貯蔵す
ると内部抵抗が上昇するという欠点があった。However, an electric double layer capacitor using a γ-butyrolactone solvent-based electrolytic solution has a low internal resistance at low temperature, but has a drawback that the internal resistance rises when stored at high temperature without load. It was
【０００５】本発明は、γーブチロラクトン溶媒系の電
解液を使用した電気二重層コンデンサにおいて、すぐれ
た低温特性を有すると共に、高温無負荷貯蔵しても内部
抵抗の上昇が防止される電気二重層コンデンサおよび同
電気二重層コンデンサ用の電解液を提供することを目的
とする。The present invention relates to an electric double layer capacitor using a γ-butyrolactone solvent-based electrolytic solution, which has excellent low temperature characteristics and prevents an increase in internal resistance even when stored at high temperature without load. An object is to provide an electrolytic solution for a capacitor and the electric double layer capacitor.
【０００６】[0006]
【課題を解決するための手段】本発明では電気二重層コ
ンデンサ用の電解液において、４級塩アンモニウムのテ
トラフロロボレート塩を溶質とし、γーブチロラクトン
とプロピレンカーボネイトとを混合したものを溶媒とし
た。According to the present invention, in an electrolytic solution for an electric double layer capacitor, a tetrafluoroborate salt of quaternary ammonium salt is used as a solute, and a mixture of γ-butyrolactone and propylene carbonate is used as a solvent. .
【０００７】溶質である４級塩アンモニウムのテトラフ
ロロボレート塩としては、例えばテトラエチルアンモニ
ウムテトラフロロボレート（ＴＥＡ・ＢＦ４）やトリエ
チルメチルアンモニウムテトラフロロボレート（ＴＥＭ
Ａ・ＢＦ４）が好ましい。Examples of the tetrafluoroborate salt of quaternary ammonium salt which is a solute include tetraethylammonium tetrafluoroborate (TEA.BF 4 ) and triethylmethylammonium tetrafluoroborate (TEM).
A · BF 4 ) is preferred.
【０００８】４級塩アンモニウムのテトラフロロボレー
ト塩の濃度は０．６〜２．０ｍｏｌ／ｌ(モル／リット
ル)であるのが好ましく、濃度が０．６ｍｏｌ／ｌ未満
では初期の内部抵抗が大きくなり、また濃度が２．０ｍ
ｏｌ／ｌを超えると溶質の結晶析出が生じるため好まし
くない。The concentration of the tetrafluoroborate salt of quaternary ammonium salt is preferably 0.6 to 2.0 mol / l (mol / liter). When the concentration is less than 0.6 mol / l, the initial internal resistance is large. And the concentration is 2.0m
If it exceeds ol / l, solute crystal precipitation occurs, which is not preferable.
【０００９】溶媒であるγーブチロラクトンとプロピレ
ンカーボネイトとの混合率は、７５：２５〜２５：７５
の範囲内にあるのが好ましく、混合率がこの範囲外の８
０：２０や２０：８０のようになると低温での抵抗が大
きくなったりまたは高温貯蔵時の劣化が大きくなり好ま
しくない。The mixing ratio of the solvent γ-butyrolactone and propylene carbonate is 75:25 to 25:75.
Is preferably within the range of 8 and the mixing ratio is outside this range.
When it is 0:20 or 20:80, the resistance at low temperature becomes large, or the deterioration at high temperature storage becomes large, which is not preferable.
【００１０】[0010]
【実施例】表１のように溶質にトリエチルメチルアンモ
ニウムテトラフロロボレート（ＴＥＭＡ・ＢＦ４）を使
用して、溶媒であるγーブチロラクトン（ＧＢＬ）とプ
ロピレンカーボネイト（ＰＣ）との混合率を変えた実施
例１〜５および比較例１〜７の電解液を作製した。なお
比較例７ではγーブチロラクトンの代わりにγーバレロ
ラクトン（ＧＶＬ）を用いた。EXAMPLE As shown in Table 1, triethylmethylammonium tetrafluoroborate (TEMA.BF 4 ) was used as a solute to change the mixing ratio of γ-butyrolactone (GBL) and propylene carbonate (PC) as a solvent. The electrolytic solutions of Examples 1 to 5 and Comparative Examples 1 to 7 were prepared. In Comparative Example 7, γ-valerolactone (GVL) was used instead of γ-butyrolactone.
【００１１】[0011]
【表１】 [Table 1]
【００１２】次に、表２のように溶質にテトラエチルア
ンモニウムテトラフロロボレート（ＴＥＡ・ＢＦ４）を
使用して、溶媒であるγーブチロラクトン（ＧＢＬ）と
プロピレンカーボネイト（ＰＣ）との混合率を変えた実
施例６〜９および比較例８〜１３の電解液を作製した。Next, as shown in Table 2, tetraethylammonium tetrafluoroborate (TEA.BF 4 ) was used as a solute to change the mixing ratio of γ-butyrolactone (GBL) and propylene carbonate (PC) as a solvent. The electrolytic solutions of Examples 6 to 9 and Comparative Examples 8 to 13 were prepared.
【００１３】[0013]
【表２】 [Table 2]
【００１４】実施例１〜９および比較例１〜１３の電解
液を用いて、それぞれ捲回型の電気二重層コンデンサ
（静電容量１００Ｆ）をそれぞれ作製した。即ちアルミ
ニウム箔からなる集電体に引出しリードを固着し、同集
電体の片面にカーボンからなる分極性電極層を塗布して
設けてなる２枚の電極を、分極性電極層を対向させるよ
うに配置し、かつその間にセパレータを介在させて捲回
してコンデンサ素子（直径３５ｍｍ、高さ５０ｍｍ）と
なし、これに電解液を含浸させて、有底のアルミニウム
ケースに入れ、引出しリードを封口板のリード用の貫通
口を通して引き出して電気二重層コンデンサとした。Using the electrolytic solutions of Examples 1 to 9 and Comparative Examples 1 to 13, wound type electric double layer capacitors (capacitance 100F) were prepared. That is, the extraction lead is fixed to the current collector made of aluminum foil, and the polarizable electrode layer is made to face the two electrodes formed by coating the polarizable electrode layer made of carbon on one surface of the current collector. And a separator interposed between them to form a capacitor element (diameter 35 mm, height 50 mm), which is impregnated with an electrolytic solution and placed in an aluminum case with a bottom, and a lead lead for sealing plate. An electric double layer capacitor was obtained by pulling out through the lead through hole.
【００１５】これら電気二重層コンデンサの初期内部抵
抗（２５℃）、−４０℃中の内部抵抗、９０℃で１５０
時間電圧無印加状態で貯蔵後の内部抵抗をそれぞれ測定
した。その結果を表１および表２に示す。The initial internal resistance (25 ° C.) of these electric double layer capacitors, the internal resistance at -40 ° C., 150 at 90 ° C.
The internal resistance after storage was measured in the state where no voltage was applied for a time. The results are shown in Tables 1 and 2.
【００１６】表１および表２から、実施例の電気二重層
コンデンサは、溶媒がγーブチロラクトンのみである比
較例１および比較例８の電気二重層コンデンサと較べる
と、低温での内部抵抗はほぼ同様でありながら、高温無
負荷貯蔵後の内部抵抗が半分以下になっているのがわか
る。From Tables 1 and 2, the electric double layer capacitors of the Examples have almost no internal resistance at low temperature as compared with the electric double layer capacitors of Comparative Example 1 and Comparative Example 8 in which the solvent is γ-butyrolactone only. Although it is similar, it can be seen that the internal resistance after high temperature no-load storage is reduced to less than half.
【００１７】また、溶媒であるγーブチロラクトンとプ
ロピレンカーボネイトとの混合率が７５：２５〜２５：
７５の範囲外にあっては、比較例２〜４および比較例９
〜１１のように、高温無負荷貯蔵後の内部抵抗が大きい
か、高温無負荷貯蔵後の内部抵抗は小さいが低温での内
部抵抗が非常に大きくなってしまうことがわかる。The mixing ratio of γ-butyrolactone as a solvent and propylene carbonate is 75:25 to 25:
When it is out of the range of 75, Comparative Examples 2 to 4 and Comparative Example 9
It can be seen from Tables 1 to 11 that the internal resistance after high temperature no-load storage is large, or the internal resistance after high temperature no-load storage is small but the internal resistance at low temperature becomes very large.
【００１８】さらに溶質の濃度が０．６ｍｏｌ／ｌ未満
になると比較例５、１２のように初期の内部抵抗が大き
くなってしまい、また濃度が２．０ｍｏｌ／ｌを超える
と比較例６、１３のように溶質が完全に溶けきらずに製
品化できない。Further, when the concentration of the solute is less than 0.6 mol / l, the initial internal resistance increases as in Comparative Examples 5 and 12, and when the concentration exceeds 2.0 mol / l, Comparative Examples 6 and 13 As the solute does not completely melt, it cannot be commercialized.
【００１９】また、比較例７では、γーブチロラクトン
の代わりにγーバレロラクトン（ＧＶＬ）を用いたが、
低温での内部抵抗が非常に大きくなってしまうことがわ
かる。In Comparative Example 7, γ-valerolactone (GVL) was used instead of γ-butyrolactone.
It can be seen that the internal resistance becomes extremely large at low temperatures.
【００２０】なお、本発明は捲回型の電気二重層コンデ
ンサに限らずコイン型の電気二重層コンデンサなどその
他の電気二重層コンデンサにも適用できる。The present invention is not limited to the wound type electric double layer capacitor and can be applied to other electric double layer capacitors such as a coin type electric double layer capacitor.
【００２１】[0021]
【発明の効果】本発明によれば、γーブチロラクトン溶
媒系の電解液を使用した電気二重層コンデンサにおい
て、すぐれた低温特性を保持し、高温無負荷貯蔵しても
内部抵抗の上昇が防止される、電気二重層コンデンサお
よび同電気二重層コンデンサ用の電解液が得られる。According to the present invention, in an electric double layer capacitor using a γ-butyrolactone solvent-based electrolytic solution, excellent low temperature characteristics are maintained and an increase in internal resistance is prevented even when stored at high temperature without load. An electric double layer capacitor and an electrolytic solution for the electric double layer capacitor are obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岩野 直人 福島県西白河郡西郷村大字米字椙山９番地 32エルナー福島株式会社内 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Naoto Iwano Fukushima Prefecture Nishi-Shirakawa-gun Saigo-mura Large-scale US character Sugiyama 9 32 Elner Fukushima Co., Ltd.
Claims (6)
ト塩を溶質とし、γーブチロラクトンとプロピレンカー
ボネイトとを混合したものを溶媒とした、電気二重層コ
ンデンサ用の電解液。1. An electrolytic solution for an electric double layer capacitor, comprising a tetrafluoroborate salt of a quaternary ammonium salt as a solute and a mixture of γ-butyrolactone and propylene carbonate as a solvent.
Ａ）またはトリエチルメチルアンモニウム（ＴＥＭＡ）
のテトラフロロボレート塩である請求項１に記載の電気
二重層コンデンサ用の電解液。2. The solute is tetraethylammonium (TE
A) or triethylmethylammonium (TEMA)
The electrolyte solution for an electric double layer capacitor according to claim 1, which is a tetrafluoroborate salt of.
イトの混合率が７５：２５〜２５：７５である請求項１
または２に記載の電気二重層コンデンサ用の電解液。3. The mixing ratio of γ-butyrolactone and propylene carbonate is 75:25 to 25:75.
Alternatively, the electrolytic solution for the electric double layer capacitor as described in 2.
ト塩を溶質とし、γーブチロラクトンとプロピレンカー
ボネイトとを混合したものを溶媒とした電解液を使用し
た電気二重層コンデンサ。4. An electric double layer capacitor using an electrolytic solution containing, as a solvent, a tetrafluoroborate salt of quaternary ammonium salt as a solute and a mixture of γ-butyrolactone and propylene carbonate as a solvent.
（ＴＥＡ）またはトリエチルメチルアンモニウム（ＴＥ
ＭＡ）のテトラフロロボレート塩である請求項４に記載
の電気二重層コンデンサ。5. The solute of the electrolytic solution is tetraethylammonium (TEA) or triethylmethylammonium (TE).
The electric double layer capacitor according to claim 4, which is a tetrafluoroborate salt of (MA).
カーボネイトの混合率が７５：２５〜２５：７５である
請求項４または５に記載の電気二重層コンデンサ。6. The electric double layer capacitor according to claim 4, wherein the mixing ratio of γ-butyrolactone and propylene carbonate in the electrolytic solution is 75:25 to 25:75.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001303951A JP2003109861A (en) | 2001-09-28 | 2001-09-28 | Electrical double layer capacitor and electrolyte therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001303951A JP2003109861A (en) | 2001-09-28 | 2001-09-28 | Electrical double layer capacitor and electrolyte therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003109861A true JP2003109861A (en) | 2003-04-11 |
Family
ID=19123952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001303951A Pending JP2003109861A (en) | 2001-09-28 | 2001-09-28 | Electrical double layer capacitor and electrolyte therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003109861A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009041074A1 (en) | 2007-09-28 | 2009-04-02 | Nippon Chemi-Con Corporation | Polarizable electrode for electric double layer capacitor and electric double layer capacitor using the same |
| JP2010283309A (en) * | 2009-06-08 | 2010-12-16 | Mitsubishi Chemicals Corp | Electrolyte for electrochemical capacitor, and electrochemical capacitor using the same |
| WO2015045376A1 (en) * | 2013-09-24 | 2015-04-02 | Toyo Gosei Co., Ltd. | Electrolyte solution and capacitor |
-
2001
- 2001-09-28 JP JP2001303951A patent/JP2003109861A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009041074A1 (en) | 2007-09-28 | 2009-04-02 | Nippon Chemi-Con Corporation | Polarizable electrode for electric double layer capacitor and electric double layer capacitor using the same |
| JP2010283309A (en) * | 2009-06-08 | 2010-12-16 | Mitsubishi Chemicals Corp | Electrolyte for electrochemical capacitor, and electrochemical capacitor using the same |
| WO2015045376A1 (en) * | 2013-09-24 | 2015-04-02 | Toyo Gosei Co., Ltd. | Electrolyte solution and capacitor |
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