JP2006351915A - Electric-double-layer capacitor and electrolyte therefor - Google Patents

Electric-double-layer capacitor and electrolyte therefor Download PDF

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JP2006351915A
JP2006351915A JP2005177569A JP2005177569A JP2006351915A JP 2006351915 A JP2006351915 A JP 2006351915A JP 2005177569 A JP2005177569 A JP 2005177569A JP 2005177569 A JP2005177569 A JP 2005177569A JP 2006351915 A JP2006351915 A JP 2006351915A
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electrolyte
layer capacitor
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Kazumi Chiba
一美 千葉
Teruaki Kamei
照明 亀井
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Japan Carlit Co Ltd
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    • 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
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrolyte wherein the coefficient of its viscosity is low, and it exhibits an excellent low-temperature characteristic, and further, it exhibits a high conductivity over a wide temperature range, and moreover, it is excellent in a long-term reliability, and provide an electric-double-layer capacitor using the electrolyte. <P>SOLUTION: In the electrolyte for electric-double-layer capacitors and an electric-double-layer capacitor created by using the electrolyte, there is dissolved as the electrolyte in the mixed solvent of DMC, EC, and PC, a tetrafluoroboric acid fourth spiroammonium represented by a general formula (1). In the formula, each of n and m is the positive integer of 3-7, and each of X and Y represents hydrogen atom or either one substituent selected from the group comprising a halogen group and alkyl groups of the carbon numbers of 1-4. The n pieces of X and the m pieces of Y which are existent in a ring may be respectively identical with each other or different from each other. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、電気二重層キャパシタ用電解液及び電気二重層キャパシタに関する。   The present invention relates to an electrolytic solution for an electric double layer capacitor and an electric double layer capacitor.

電気二重層キャパシタは、分極性電極と電解液との界面に形成される電気二重層を利用した電荷蓄積デバイスである。   An electric double layer capacitor is a charge storage device using an electric double layer formed at the interface between a polarizable electrode and an electrolyte.

電気二重層キャパシタに用いられる電解液は、電解液の粘性率が高い及び／または電導度が低いとキャパシタの内部抵抗が大きくなり、充放電時に電圧が降下する等の不都合が生ずるため、低粘性率、高電導度で、かつ長期間の耐久性が要求される。   The electrolyte used for the electric double layer capacitor has a low viscosity because the electrolyte has a high viscosity and / or a low conductivity, which causes a problem that the internal resistance of the capacitor increases and the voltage drops during charging and discharging. High durability, high electrical conductivity, and long-term durability are required.

従来、電気二重層キャパシタ用電解液としては、特に長期間の耐久性を考慮し、プロピレンカーボネート（以下、「ＰＣ」と略記する。）中に、テトラフルオロホウ酸トリエチルメチルアンモニウム（以下、「ＴＥＭＡ−ＢＦ４」と略記する。）に代表される第４級アンモニウム塩からなる電解質を溶解させたものが一般的に用いられている（例えば、特許文献１参照）。 Conventionally, as an electrolytic solution for an electric double layer capacitor, triethylmethylammonium tetrafluoroborate (hereinafter referred to as “TEMA”) in propylene carbonate (hereinafter abbreviated as “PC”), particularly considering long-term durability. A solution in which an electrolyte made of a quaternary ammonium salt typified by -BF 4 ") is dissolved is generally used (see, for example, Patent Document 1).

しかしながら、ＰＣ溶媒は、温度３０℃での粘性率が約２．５ｍＰａ・ｓと高いため、該溶媒に電解質を溶解させた電解液は、粘性率が高く、かつ電導度が低いことから、該電解液を用いて作製した電気二重層キャパシタは、内部抵抗が大きくなってしまうという欠点があった。   However, since the PC solvent has a high viscosity of about 2.5 mPa · s at a temperature of 30 ° C., an electrolytic solution obtained by dissolving an electrolyte in the solvent has a high viscosity and a low electrical conductivity. The electric double layer capacitor produced using the electrolytic solution has a drawback that the internal resistance increases.

一方、ジメチルカーボネート（以下、「ＤＭＣ」と略記する。）等の鎖状カーボネートは、粘性率が低く、該溶媒に電解質を溶解させた電解液は、粘性率が低く、かつ電導度が高いことから、該電解液を用いて作製した電気二重層キャパシタは、内部抵抗が小さく、長期間の耐久性を有することが期待されているが、ＤＭＣは融点が約３℃であることから、低温領域で電解液が凝固し、電導度が著しく低下してしまい、電気二重層キャパシタが使用不能となるという欠点があった。   On the other hand, a chain carbonate such as dimethyl carbonate (hereinafter abbreviated as “DMC”) has a low viscosity, and an electrolytic solution obtained by dissolving an electrolyte in the solvent has a low viscosity and a high conductivity. Therefore, the electric double layer capacitor produced using the electrolytic solution is expected to have low internal resistance and long-term durability, but DMC has a melting point of about 3 ° C. As a result, the electrolytic solution is solidified, the conductivity is remarkably lowered, and the electric double layer capacitor becomes unusable.

さらに、一般的に電気二重層キャパシタ用電解液の電解質として使用されるテトラフルオロホウ酸テトラエチルアンモニウム（以下、「ＴＥＡ−ＢＦ４」と略記する。）及びＴＥＭＡ−ＢＦ４は、鎖状カーボネートへの溶解度が低く、高電導度と良好な低温特性を両立できる電解液が得られないという解決すべき課題が残されており、ＰＣとエチレンカーボネート（以下、「ＥＣ」と略記する。）及びＤＭＣとの混合溶媒に、これら従来型の電解質を溶解させて、電解液の特性向上を図った電解液については、低温特性が考慮されていないという欠点があった（特許文献２参照）。 Furthermore, tetraethylammonium tetrafluoroborate (hereinafter abbreviated as “TEA-BF 4 ”) and TEMA-BF 4 which are generally used as an electrolyte of an electrolytic solution for an electric double layer capacitor, There remains a problem to be solved that an electrolytic solution having low solubility and high electrical conductivity and good low-temperature characteristics cannot be obtained. PC, ethylene carbonate (hereinafter abbreviated as “EC”), and DMC However, there is a drawback that the low-temperature characteristics are not taken into consideration in the electrolytic solution in which these conventional electrolytes are dissolved in the mixed solvent to improve the characteristics of the electrolytic solution (see Patent Document 2).

ところで、テトラフルオロホウ酸第４級スピロアンモニウムはＤＭＣに溶解可能であることから、ＤＭＣとＰＣとの混合溶媒系電解液を構築することが可能であり、このようにして構築された電解液は、低温領域でも優れたキャパシタ特性を与えることが分かっている（特許文献３参照）。しかし、ＤＭＣは比誘電率が非常に低いため、ＤＭＣとＰＣとの混合溶媒における比誘電率も低下し、電解質の電離が有効に行われていない可能性があり、更なる電導度向上の余地が残されていた。   By the way, since quaternary spiro ammonium tetrafluoroborate can be dissolved in DMC, it is possible to construct a mixed solvent electrolyte of DMC and PC, and the electrolyte thus constructed is It has been found that excellent capacitor characteristics are provided even in a low temperature region (see Patent Document 3). However, since the relative permittivity of DMC is very low, the relative permittivity of the mixed solvent of DMC and PC also decreases, and the electrolyte may not be effectively ionized. Was left.

特開２０００−１１４１０５号公報JP 2000-114105 A 特開２０００−１７３８７４号公報JP 2000-173874 A 特願２００４−３７６９１０号Japanese Patent Application No. 2004-376910

本発明の目的は、粘性率が低く、優れた低温特性、すなわち低温領域においても電解液が凝固することなく、混合溶媒の比誘電率が高く、広い温度範囲で高い電導度を示し、かつ長期信頼性に優れた電気二重層キャパシタ用電解液と、該電解液を用いて作製されてなる電気二重層キャパシタを提供することにある。   The object of the present invention is to have a low viscosity, excellent low temperature characteristics, that is, the electrolyte does not solidify even in a low temperature region, the mixed solvent has a high relative dielectric constant, a high conductivity in a wide temperature range, and a long-term An object of the present invention is to provide an electrolytic solution for an electric double layer capacitor excellent in reliability and an electric double layer capacitor produced using the electrolytic solution.

本発明者らは、鋭意検討を行った結果、ＤＭＣ、ＥＣ及びＰＣからなる混合溶媒に、テトラフルオロホウ酸スピロ−（１，１’）−ビピロリジニウム（以下、「ＳＢＰ−ＢＦ４」と略記する。）に代表されるテトラフルオロホウ酸第４級スピロアンモニウムを溶解させた電解液が、粘性率が低く、低温領域でも凝固することなく、混合溶媒の比誘電率が高く、広い温度範囲で高い電導度を示し、かつ長期信頼性に優れていることを見いだし、本発明を完成するに至った。 As a result of intensive studies, the inventors of the present invention are abbreviated as “spiro- (1,1 ′)-bipyrrolidinium tetrafluoroborate (hereinafter“ SBP-BF 4 ”) in a mixed solvent composed of DMC, EC and PC. Electrolyte in which quaternary spiroammonium tetrafluoroborate represented by.) Is dissolved has a low viscosity, does not solidify even in a low temperature region, and has a high relative dielectric constant of the mixed solvent and is high in a wide temperature range. The inventors have found that it has electrical conductivity and is excellent in long-term reliability, and has completed the present invention.

すなわち、本発明は、ＤＭＣ、ＥＣ及びＰＣの混合溶媒中に、下記一般式（１）で表されるテトラフルオロホウ酸第４級スピロアンモニウムが電解質として含有されてなることを特徴とする電気二重層キャパシタ用電解液である。   That is, according to the present invention, a quaternary spiro ammonium tetrafluoroborate represented by the following general formula (1) is contained as an electrolyte in a mixed solvent of DMC, EC and PC. It is an electrolyte solution for multilayer capacitors.

Figure 2006351915
（式中、ｎ及びｍは、３〜７の正整数を表す。Ｘ及びＹは、水素原子、又は、ハロゲン基、炭素数１〜４のアルキル基からなる群から選ばれる置換基のいずれか一つを表す。環中に存在するｎ個のＸ及びｍ個のＹは、それぞれ同一又は異なっていても良い。）
Figure 2006351915
 (In the formula, n and m represent a positive integer of 3 to 7. X and Y are either a hydrogen atom or a substituent selected from the group consisting of a halogen group and an alkyl group having 1 to 4 carbon atoms. 1 represents one, and n X and m Y present in the ring may be the same or different.

また、本発明は、ジメチルカーボネート、エチレンカーボネート及びプロピレンカーボネートの混合溶媒において、ジメチルカーボネート容量混合比率が１０ないし４０、エチレンカーボネート容量混合比率が２０ないし３４、プロピレンカーボネート容量混合比率が２６ないし７０であることを特徴とする前記記載の電気二重層キャパシタ用電解液である。   In the mixed solvent of dimethyl carbonate, ethylene carbonate and propylene carbonate, the present invention has a dimethyl carbonate volume mixing ratio of 10 to 40, an ethylene carbonate volume mixing ratio of 20 to 34, and a propylene carbonate volume mixing ratio of 26 to 70. The electrolytic solution for an electric double layer capacitor as described above.

さらに、本発明は、前記記載の電気二重層キャパシタ用電解液を用いて作製されてなることを特徴とする電気二重層キャパシタである。   Furthermore, the present invention is an electric double layer capacitor produced using the above-described electrolytic solution for electric double layer capacitor.

本発明の電気二重層キャパシタ用電解液は、ＤＭＣ、ＥＣ及びＰＣの混合溶媒中に、テトラフルオロホウ酸第４級スピロアンモニウムを電解質として溶解させてなり、該電解液は、低粘性率かつ優れた低温特性を示し、また広い温度範囲で高い電導度を示す。特に、ＤＭＣ、ＥＣ及びＰＣの容量混合比率が、ＤＭＣ容量混合比率が１０ないし４０、ＥＣ容量混合比率が２０ないし３４、ＰＣ容量混合比率が２６ないし７０である電解液は、より低温特性に優れている。   The electrolytic solution for an electric double layer capacitor of the present invention is obtained by dissolving quaternary spiro ammonium tetrafluoroborate as an electrolyte in a mixed solvent of DMC, EC and PC, and the electrolytic solution has a low viscosity and an excellent It exhibits low temperature characteristics and high conductivity over a wide temperature range. In particular, an electrolyte having a DMC, EC, and PC volume mixing ratio of 10 to 40, a DMC volume mixing ratio of 20 to 34, and a PC volume mixing ratio of 26 to 70 has excellent low-temperature characteristics. ing.

また、本発明の電解液を用いて作製した電気二重層キャパシタは、広い温度範囲において、内部抵抗が低く、高電圧で作動させても静電容量の低下率及び内部抵抗の上昇率が小さく、耐電圧が高く長期信頼性に優れている。   In addition, the electric double layer capacitor produced using the electrolytic solution of the present invention has a low internal resistance in a wide temperature range, and the capacitance decrease rate and the internal resistance increase rate are small even when operated at a high voltage. High withstand voltage and excellent long-term reliability.

以下、本発明の電気二重層キャパシタ用電解液について、詳細に説明する。   Hereinafter, the electrolytic solution for electric double layer capacitor of the present invention will be described in detail.

本発明の電解二重層キャパシタ用電解液は、ＤＭＣ、ＥＣ及びＰＣの混合溶媒中に、一般式（１）で表されるテトラフルオロホウ酸第４級スピロアンモニウムを電解質として溶解させたものである。   The electrolytic solution for an electrolytic double layer capacitor of the present invention is obtained by dissolving quaternary spiro ammonium tetrafluoroborate represented by the general formula (1) as an electrolyte in a mixed solvent of DMC, EC and PC. .

テトラフルオロホウ酸第４級スピロアンモニウムは、ＤＭＣ、ＥＣ及びＰＣの混合溶媒への溶解度が高く、高濃度の電解液を調製することが可能であり、得られた電解液は、低粘性率、高誘電率、高電導度及び優れた低温特性を示す。   Tetrafluoroborate quaternary spiro ammonium has high solubility in a mixed solvent of DMC, EC and PC, and it is possible to prepare a high concentration electrolytic solution. The obtained electrolytic solution has a low viscosity, High dielectric constant, high conductivity and excellent low temperature characteristics.

一般式（１）で表される第４級スピロアンモニウムカチオンとしては、例えば、アザシクロブタン−１−スピロ−１’−アザシクロブチルイオン、ピロリジン−１−スピロ−１’−アザシクロブチルイオン、スピロ−（１，１’）−ビピロリジニウムイオン、ピペリジン−１−スピロ−１’−ピロリジニウムイオン、スピロ−（１，１’）−ビピペリジニウムイオン、３−エチルピロリジニウム−１−スピロ−１’−ピロリジニウムイオン、３−エチルピロリジニウム−１−スピロ−１’−（３’−エチル）ピロリジニウムイオン、２，４−ジフルオロピロリジニウム−１−スピロ−１’−ピロリジニウムイオン、２，４−ジフルオロピロリジニウム−１−スピロ−１’−（２’，４’−ジフルオロ）ピロリジニウムイオンがあげられる。
その中でも、特にスピロ−（１，１’）−ビピロリジニウムイオンが好適である。 Examples of the quaternary spiro ammonium cation represented by the general formula (1) include azacyclobutane-1-spiro-1′-azacyclobutyl ion, pyrrolidine-1-spiro-1′-azacyclobutyl ion, and spiro. -(1,1 ')-bipyrrolidinium ion, piperidine-1-spiro-1'-pyrrolidinium ion, spiro- (1,1')-bipiperidinium ion, 3-ethylpyrrolidinium-1-spiro -1′-pyrrolidinium ion, 3-ethylpyrrolidinium-1-spiro-1 ′-(3′-ethyl) pyrrolidinium ion, 2,4-difluoropyrrolidinium-1-spiro-1′-pyrrolidini And the 2,4-difluoropyrrolidinium-1-spiro-1 ′-(2 ′, 4′-difluoro) pyrrolidinium ion.
Among these, spiro- (1,1 ′)-bipyrrolidinium ion is particularly preferable.

ＤＭＣ、ＥＣ及びＰＣの混合比率は、ＤＭＣの容量混合比率が１０ないし４０、ＥＣの容量混合比率が２０ないし３４、ＰＣの容量混合比率が２６ないし７０であることが望ましく、更に望ましくはＤＭＣが３３、ＥＣが２７、ＰＣが４０の場合であり、ＤＭＣが４０以上、ＥＣが３４以上、ＰＣが２６以下では、低温において電解液が凝固するため、また、ＤＭＣが１０以下、ＥＣが２０以下、ＰＣが７０以上では、ＤＭＣおよびＥＣの添加効果が小さく、不都合である。   As for the mixing ratio of DMC, EC and PC, it is preferable that the volume mixing ratio of DMC is 10 to 40, the volume mixing ratio of EC is 20 to 34, and the volume mixing ratio of PC is 26 to 70, more preferably DMC is mixed. 33, EC is 27, PC is 40, DMC is 40 or more, EC is 34 or more, PC is 26 or less, because the electrolyte is solidified at low temperature, DMC is 10 or less, EC is 20 or less When the PC is 70 or more, the effect of adding DMC and EC is small, which is inconvenient.

上記電解液のテトラフルオロホウ酸第４級スピロアンモニウムの濃度は、０．５ｍｏｌ／Ｌ超、３．０ｍｏｌ／Ｌ以下、好ましくは、０．６ｍｏｌ／Ｌ超、２．５ｍｏｌ／Ｌ以下である。０．５ｍｏｌ／Ｌ以下では、電導度が不足し不都合であり、また、３．０ｍｏｌ／Ｌ超では、低温特性が著しく低下するとともに、経済性に劣り不都合である。   The concentration of quaternary spiro ammonium tetrafluoroborate in the electrolytic solution is more than 0.5 mol / L and not more than 3.0 mol / L, preferably more than 0.6 mol / L and not more than 2.5 mol / L. If it is 0.5 mol / L or less, the electric conductivity is insufficient, which is inconvenient, and if it exceeds 3.0 mol / L, the low-temperature characteristics are remarkably lowered and the economy is inferior.

本発明の電気二重層キャパシタは、セパレータを挟み込んだ分極性電極に、駆動用電解液となる本発明の電解液を含浸させた後、ステンレス等の外装ケースに収容させて作製される。   The electric double layer capacitor of the present invention is manufactured by impregnating a polarizable electrode sandwiching a separator with the electrolytic solution of the present invention as a driving electrolytic solution, and then housing it in an outer case made of stainless steel or the like.

上記分極性電極としては、活性炭粉末、活性炭繊維等の炭素材料や貴金属酸化物材料、あるいは導電性高分子材料等が用いられるが、炭素材料が安価で好ましい。また、セパレータとしては、ポリエチレン、ポリプロピレン系不織布など、公知の素材からなるセパレータを用いることができる。   As the polarizable electrode, a carbon material such as activated carbon powder or activated carbon fiber, a noble metal oxide material, a conductive polymer material, or the like is used. A carbon material is preferable because it is inexpensive. Moreover, as a separator, the separator which consists of well-known raw materials, such as polyethylene and a polypropylene-type nonwoven fabric, can be used.

本発明の電気二重層キャパシタは、フィルム型、コイン型、円筒型、箱形などの形状に作製することができ、特に限定されない。   The electric double layer capacitor of the present invention can be produced in a shape such as a film type, a coin type, a cylindrical type, and a box shape, and is not particularly limited.

以下、実施例を挙げ、本発明を更に詳しく説明する。なお、本発明は実施例によりなんら限定されない。   Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited at all by the Example.

実施例１
ＤＭＣ、ＥＣ及びＰＣの容量混合比率がそれぞれ３３、２７、４０である混合溶媒に、電解質であるＳＢＰ−ＢＦ４を溶解させて、濃度１．０ｍｏｌ／Ｌの電気二重層キャパシタ用電解液（以下、「発明品」と略記する。）を調製した。該電解液の温度−４０℃から３０℃における電導度及び温度−４０℃から２５℃における粘性率の測定値を図１及び図２に示す。 Example 1
SBP-BF 4 as an electrolyte is dissolved in a mixed solvent in which the volume mixing ratio of DMC, EC, and PC is 33, 27, and 40, respectively, and an electrolytic solution for an electric double layer capacitor having a concentration of 1.0 mol / L (hereinafter referred to as “electrolytic solution”) Abbreviated as “invention product”). FIG. 1 and FIG. 2 show measured values of the conductivity of the electrolytic solution at temperatures from −40 ° C. to 30 ° C. and the viscosity at temperatures from −40 ° C. to 25 ° C.

別に、分極性電極として、活性炭粉末（粒径２０μｍ、比表面積２，０００ｍ２／ｇ）９０質量％とポリテトラフルオロエチレン粉末１０質量％とをロールで混練、圧延して厚さ０．４ｍｍのシートを作製した。このシートを、直径１３ｍｍφに打ち抜いて、円板状電極を作製した。 Separately, as a polarizable electrode, 90% by mass of activated carbon powder (particle diameter 20 μm, specific surface area 2,000 m 2 / g) and 10% by mass of polytetrafluoroethylene powder were kneaded and rolled to a thickness of 0.4 mm. A sheet was produced. This sheet was punched into a diameter of 13 mmφ to produce a disk-shaped electrode.

円板状電極２枚に、ポリプロピレン製セパレータを挟み込み、先に調製した電解液を真空含浸させた後、ステンレス製外装ケースに収容して、定格電圧２．７Ｖ、静電容量１．５Ｆのコイン型電気二重層キャパシタを完成した。   A polypropylene separator is sandwiched between two disc-shaped electrodes, and the electrolyte prepared above is vacuum impregnated, and then accommodated in a stainless steel outer case. A coin having a rated voltage of 2.7 V and a capacitance of 1.5 F Type electric double layer capacitor was completed.

完成したキャパシタの温度特性の評価方法としては、まず２５℃に設定された恒温槽内にて、２．７Ｖの定電圧充電を１０分間行った後、２時間静置することによりキャパシタ内部までの温度安定化を図った。その後、再度２．７Ｖの定電圧充電を１０分間行い、１ｍＡにて所定電圧まで放電を行った際の電圧勾配より静電容量および内部抵抗を求めた。   As a method for evaluating the temperature characteristics of the completed capacitor, first, a constant voltage of 2.7 V was charged for 10 minutes in a thermostat set at 25 ° C., and then left for 2 hours to reach the inside of the capacitor. The temperature was stabilized. Then, the constant voltage charge of 2.7V was performed again for 10 minutes, and the electrostatic capacity and the internal resistance were determined from the voltage gradient when discharging to a predetermined voltage at 1 mA.

前述の方法にて、恒温槽の設定温度を１５℃、０℃、−１０℃、−２０℃、−３０℃、−４０℃と段階的に下げることにより、各温度で得られる静電容量、内部抵抗をもって温度特性とした。この温度特性を図３及び図４に示す。   Capacitance obtained at each temperature by stepwise lowering the set temperature of the thermostatic chamber to 15 ° C., 0 ° C., −10 ° C., −20 ° C., −30 ° C., −40 ° C. Temperature characteristics were determined by internal resistance. This temperature characteristic is shown in FIGS.

比較例
実施例１の電解液において、電解質に濃度１．０ｍｏｌ／ＬのＴＥＡ−ＢＦ４を用いた以外は同様にして、電気二重層キャパシタ用電解液を得（以下、「比較品１」と略記する。）電導度及び粘性率を測定した結果、並びに、同様に電解質に濃度１．０ｍｏｌ／ＬのＴＥＭＡ−ＢＦ４を用いた以外は実施例１と同様にして、電気二重層キャパシタ用電解液を得（以下、「比較品２」と略記する。）、電導度及び粘性率を測定した結果を図１及び図２に示す。また、電解液として、濃度１．０ｍｏｌ／ＬのＳＢＰ−ＢＦ４を電解質とするＤＭＣ＋ＰＣ溶液：混合割合ＤＭＣ３０、ＰＣ７０（以下、「比較品３」と略記する。）を用いた結果、並びに、電解液として、濃度１．０ｍｏｌ／ＬのＳＢＰ−ＢＦ４を電解質とするＰＣ溶液（以下、「比較品４」と略記する。）を用いた結果についても、それぞれを図１及び図２に示す。また、各比較例で得られた電解液を用いた以外は、実施例１と同様にして電気二重層キャパシタをそれぞれ作製し、温度特性試験を行った結果を図３及び図４に示す。 Comparative Example An electrolytic solution for an electric double layer capacitor was obtained in the same manner as in the electrolytic solution of Example 1 except that TEA-BF 4 having a concentration of 1.0 mol / L was used as the electrolyte (hereinafter referred to as “Comparative Product 1”). The electric double layer capacitor electrolysis was conducted in the same manner as in Example 1 except that TEMA-BF 4 having a concentration of 1.0 mol / L was similarly used as the electrolyte. A liquid was obtained (hereinafter abbreviated as “Comparative Product 2”), and the results of measuring the conductivity and viscosity are shown in FIG. 1 and FIG. Further, as an electrolytic solution, a result of using a DMC + PC solution containing SBP-BF 4 having a concentration of 1.0 mol / L as an electrolyte: a mixing ratio DMC30, PC70 (hereinafter abbreviated as “Comparative Product 3”), and electrolysis 1 and 2 also show the results of using a PC solution containing SBP-BF 4 having a concentration of 1.0 mol / L as an electrolyte (hereinafter abbreviated as “Comparative Product 4”). Moreover, the electric double layer capacitor was produced in the same manner as in Example 1 except that the electrolytic solution obtained in each comparative example was used, and the results of the temperature characteristic test are shown in FIGS.

本発明の実施例１の電解液は、高電導度と低粘性率を併せ持つ組成であり、図１及び図２に示すように、本発明品は、従来の一般的なテトラフルオロホウ酸第４級アンモニウムであるＴＥＡ−ＢＦ４及びＴＥＭＡ−ＢＦ４を電解質として含有させた電解液（比較品１及び２）が０から−２０℃付近で凝固してしまうのに対し、広い温度範囲にわたって優れた電導度と低温特性を併せ持ち、ＤＭＣ＋ＰＣ混合溶媒及びＰＣ単独の溶媒にテトラフルオロホウ酸第４級スピロアンモニウムを電解質として含有させた電解液（比較品３及び４）と比較しても、優れた電解液特性を示した。 The electrolytic solution of Example 1 of the present invention has a composition having both high electrical conductivity and low viscosity. As shown in FIGS. 1 and 2, the product of the present invention is a conventional tetrafluoroboric acid fourth compound. while the electrolytic solution which contains a TEA-BF 4 and TEMA-BF 4 is a grade ammonium as an electrolyte (comparative product 1 and 2) it will be solidified at around -20 ° C. from 0, excellent over a wide temperature range It has both conductivity and low-temperature characteristics, and is superior in electrolysis compared to electrolytes (comparative products 3 and 4) containing quaternary spiroammonium tetrafluoroborate as an electrolyte in a DMC + PC mixed solvent and PC alone. Liquid properties were shown.

また、図３及び図４に示すように、実施例１の電解液を用いて作製したキャパシタは、比較例の各電解液を用いて作製したキャパシタよりも、常温における内部抵抗、低温時の容量減少率および内部抵抗増加が小さく、良好な温度特性を示した。   Further, as shown in FIGS. 3 and 4, the capacitor produced using the electrolytic solution of Example 1 has an internal resistance at room temperature and a capacitance at low temperature, compared with the capacitor produced using each electrolytic solution of Comparative Example. The decrease rate and internal resistance increase were small, and good temperature characteristics were exhibited.

本発明である、ＤＭＣ、ＥＣ及びＰＣの混合溶媒とし、テトラフルオロホウ酸第４級スピロアンモニウムが電解質として含有されてなる電気二重層キャパシタ用電解液、及び該電解液を用いて作製されてなる電気二重層キャパシタは、広い温度範囲にわたって、優れたキャパシタ特性を有し、小型電子機器から大型自動車用途まで、広範な産業分野においての使用が可能である。   An electrolytic solution for an electric double layer capacitor, which is a mixed solvent of DMC, EC and PC according to the present invention and contains quaternary spiroammonium tetrafluoroborate as an electrolyte, and produced using the electrolytic solution. The electric double layer capacitor has excellent capacitor characteristics over a wide temperature range, and can be used in a wide range of industrial fields from small electronic devices to large automobile applications.

実施例１および比較例の電解液について、温度変化と電導度の変化の関係を示す図面Drawing which shows relation between temperature change and change in conductivity for electrolytes of Example 1 and Comparative Example 実施例１および比較例の電解液について、温度変化と粘性率の変化の関係を示す図面Drawing which shows relation between change of temperature and change of viscosity for electrolyte solutions of Example 1 and Comparative Example 実施例１および比較例の電気二重層キャパシタについて、温度変化と静電容量の関係を示す図面Drawing which shows relation between temperature change and electrostatic capacity about electric double layer capacitor of Example 1 and Comparative Example 実施例１および比較例の電気二重層キャパシタについて、温度変化と内部抵抗の関係を示す図面Drawing which shows relation between temperature change and internal resistance about electric double layer capacitor of Example 1 and Comparative Example

Claims (3)

ジメチルカーボネート、エチレンカーボネート及びプロピレンカーボネートの混合溶媒中に、下記一般式（１）で表されるテトラフルオロホウ酸第４級スピロアンモニウムが電解質として含有されてなることを特徴とする電気二重層キャパシタ用電解液。
Figure 2006351915
 （式中、ｎ及びｍは、３〜７の正整数を表す。Ｘ及びＹは、水素原子、又は、ハロゲン基、炭素数１〜４のアルキル基からなる群から選ばれる置換基のいずれか一つを表す。環中に存在するｎ個のＸ及びｍ個のＹは、それぞれ同一又は異なっていても良い。） An electric double layer capacitor characterized in that tetrafluoroborate quaternary spiro ammonium represented by the following general formula (1) is contained as an electrolyte in a mixed solvent of dimethyl carbonate, ethylene carbonate and propylene carbonate. Electrolytic solution.
Figure 2006351915
 (In the formula, n and m represent a positive integer of 3 to 7. X and Y are either a hydrogen atom or a substituent selected from the group consisting of a halogen group and an alkyl group having 1 to 4 carbon atoms. 1 represents one, and n X and m Y present in the ring may be the same or different. ジメチルカーボネート、エチレンカーボネート及びプロピレンカーボネートの混合溶媒において、ジメチルカーボネート容量混合比率が１０ないし４０、エチレンカーボネート容量混合比率が２０ないし３４、プロピレンカーボネート容量混合比率が２６ないし７０であることを特徴とする請求項１に記載の電気二重層キャパシタ用電解液。   The mixed solvent of dimethyl carbonate, ethylene carbonate and propylene carbonate has a dimethyl carbonate volume mixing ratio of 10 to 40, an ethylene carbonate volume mixing ratio of 20 to 34, and a propylene carbonate volume mixing ratio of 26 to 70. Item 2. The electrolytic solution for an electric double layer capacitor according to Item 1. 請求項１または請求項２に記載の電気二重層キャパシタ用電解液を用いて作製されてなることを特徴とする電気二重層キャパシタ。
An electric double layer capacitor produced by using the electrolytic solution for an electric double layer capacitor according to claim 1 or 2.
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