JP2002151360A - Electric double-layer capacitor - Google Patents
Electric double-layer capacitorInfo
- Publication number
- JP2002151360A JP2002151360A JP2000339924A JP2000339924A JP2002151360A JP 2002151360 A JP2002151360 A JP 2002151360A JP 2000339924 A JP2000339924 A JP 2000339924A JP 2000339924 A JP2000339924 A JP 2000339924A JP 2002151360 A JP2002151360 A JP 2002151360A
- Authority
- JP
- Japan
- Prior art keywords
- group
- electric double
- layer capacitor
- double layer
- ammonium salt
- 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
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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
- 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、特定のアンモニウ
ム塩を非水系溶媒に溶解して得られる電解液および該電
解液を有する電気二重層キャパシタに関するBACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic solution obtained by dissolving a specific ammonium salt in a non-aqueous solvent, and an electric double layer capacitor having the electrolytic solution.
【０００２】[0002]
【従来の技術】近年、バックアップ電源、補助電源など
として、重金属を使用していない、サイクル特性の高い
電気二重層キャパシタが注目を集めている。電気二重層
キャパシタは、一般的に一次電池および二次電池と比較
して瞬間充放電特性および繰り返し充放電特性に優れ、
充放電時に過電圧が無いために簡単な電気回路が適用で
き、また電気容量の残存量が分かり易く、さらに使用温
度範囲が広いなどの利点を有する。このような電気二重
層キャパシタは、マイコンやＩＣチップのメモリ、タイ
マー部分およびその他の制御機器バックアップ電源、停
電時電源などとして実用化されている。2. Description of the Related Art In recent years, an electric double layer capacitor that does not use heavy metals and has high cycle characteristics has attracted attention as a backup power supply and an auxiliary power supply. Electric double layer capacitors generally have better instantaneous charge / discharge characteristics and repetitive charge / discharge characteristics than primary batteries and secondary batteries,
Since there is no overvoltage during charging and discharging, a simple electric circuit can be applied, the remaining amount of electric capacity is easy to understand, and further, there are advantages such as a wide operating temperature range. Such an electric double layer capacitor has been put into practical use as a backup power supply for a memory of a microcomputer or an IC chip, a timer section and other control equipment, a power supply at the time of a power failure, and the like.
【０００３】電気二重層キャパシタは、用いる電解液の
種類により、水溶液系と非水溶液系に大別される。非水
溶液電解液としては、アルカリ金属または４級アンモニ
ウムの過塩素酸塩、四フッ化硼素塩、六フッ化燐酸塩な
どの電解質をプロピレンカーボネート、γ−ブチロラク
トン、ジメチルホルムアミド、アセトニトリルなどの非
水系溶媒に溶解したものが用いられる（特開昭５９−３
９１４号公報参照）。[0003] Electric double layer capacitors are broadly classified into aqueous solutions and non-aqueous solutions depending on the type of electrolyte used. As the non-aqueous electrolyte, an electrolyte such as a perchlorate of an alkali metal or quaternary ammonium, a boron tetrafluoride, a hexafluorophosphate or the like may be used as a non-aqueous solvent such as propylene carbonate, γ-butyrolactone, dimethylformamide, and acetonitrile. Is used (see JP-A-59-3).
914).
【０００４】電気二重層キャパシタの耐電圧は、電荷移
動反応である酸化還元反応が、正極および負極で起こり
始める電位によって規定される。例えば、ボタン型電気
二重層キャパシタでは、一般的に耐食性に優れたステン
レス系材料が集電を兼ねた金属ケースに使用されてい
る。すなわち、この場合に、電気二重層キャパシタの耐
電圧を決定する反応は、正極でのステンレスケースとの
酸化反応と、負極での電解液の還元分解反応である。負
極側では、電解液および電解質の還元分解反応が起こる
可能性があるが、非水系溶媒では還元反応が起こり難い
ため、多くの場合、電解質中に含まれるカチオンの還元
電位が問題である。The withstand voltage of an electric double layer capacitor is defined by a potential at which an oxidation-reduction reaction, which is a charge transfer reaction, starts to occur at a positive electrode and a negative electrode. For example, in a button-type electric double layer capacitor, a stainless steel material having excellent corrosion resistance is generally used for a metal case that also serves as a current collector. That is, in this case, the reactions that determine the withstand voltage of the electric double layer capacitor are an oxidation reaction with the stainless steel case at the positive electrode and a reductive decomposition reaction of the electrolytic solution at the negative electrode. On the negative electrode side, a reductive decomposition reaction of the electrolytic solution and the electrolyte may occur, but the reduction reaction does not easily occur in a non-aqueous solvent. Therefore, in many cases, the reduction potential of cations contained in the electrolyte is a problem.
【０００５】電気二重層キャパシタ用電解質としてアル
カリ金属塩が使用されることは知られている（特開昭４
８−５０２５５号公報参照）が、このようなアルカリ金
属塩を電気二重層キャパシタ用電解質として使用した場
合、過電圧の印加によって還元析出反応が促進し、デン
ドライト結晶が析出してしまうことがある。デンドライ
ト結晶はセパレータを貫通し、正極−負極を短絡させ、
使用不可な状態になるため、アルカリ金属塩は現実には
電解質として使用できない。It is known that an alkali metal salt is used as an electrolyte for an electric double layer capacitor (Japanese Patent Application Laid-open No. Sho 4).
However, when such an alkali metal salt is used as an electrolyte for an electric double layer capacitor, a reduction precipitation reaction is accelerated by application of an overvoltage, and a dendrite crystal may be precipitated. Dendrite crystals penetrate the separator, short-circuiting the positive electrode-negative electrode,
The alkali metal salt cannot be used as an electrolyte in reality because it cannot be used.
【０００６】また、四級アンモニウムカチオンはリチウ
ムイオンより還元され難く、たとえ過電圧が印可されて
も析出することはない。したがって、四級アンモニウム
カチオンは電気二重層キャパシタ用電解質として多用さ
れている（特開昭４９−６８２５４号公報および特開昭
５０−４４４６３号公報参照）。４級アンモニウムカチ
オンの耐電圧を向上させる方法として、４級アンモニウ
ムカチオンのアルキル基を長くし、立体的に嵩高くする
ことによって電極面への接触を妨げる方法が用いられ、
例えばテトラブチルアンモニウム塩、Ｎ，Ｎ−ジエチル
ピロリジニウム塩などが使用され（特開昭６３−１２７
５２０号公報および特開昭６３−２１５０３１号公報参
照）、また環状アンモニウム塩が使用されている（特開
平４−２３３２１０号公報参照）。Further, the quaternary ammonium cation is harder to be reduced than the lithium ion, and does not precipitate even if an overvoltage is applied. Therefore, quaternary ammonium cations are frequently used as electrolytes for electric double layer capacitors (see JP-A-49-68254 and JP-A-50-44463). As a method for improving the withstand voltage of the quaternary ammonium cation, a method is used in which the alkyl group of the quaternary ammonium cation is lengthened and the contact with the electrode surface is hindered by increasing the steric bulk.
For example, tetrabutylammonium salt, N, N-diethylpyrrolidinium salt and the like are used (JP-A-63-127).
520 and JP-A-63-215031), and a cyclic ammonium salt is used (see JP-A-4-233210).
【０００７】[0007]
【発明が解決しようとする課題】上記の特開昭６３−１
２７５２０号公報および特開昭６３−２１５０３１号公
報に記載されているカチオンでは、分子構造が大きくな
り過ぎ、イオンの移動が阻害されるため、伝導度が小さ
くなり電気抵抗が大きくなる。また、特開平４−２３３
２１０号公報に記載されたカチオンでは、電気抵抗の増
加は抑えられるものの、使用するアミンが非常に高価で
あり、経済的に不利である。The above-mentioned JP-A-63-1
In the cations described in Japanese Patent No. 27520 and JP-A-63-215031, the molecular structure becomes too large and the movement of ions is inhibited, so that the conductivity becomes small and the electric resistance becomes large. Also, Japanese Patent Laid-Open No.
In the cation described in Japanese Patent Publication No. 210, although the increase in electric resistance can be suppressed, the amine used is very expensive, which is economically disadvantageous.
【０００８】本発明の目的は、電気抵抗を増加させるこ
となく耐電圧を向上させ、かつ経済的に優位な４級アン
モニウム塩を非水系溶媒に溶解して得られる電解液を提
供することにある。本発明の他の目的は、かかる電解液
を有する電気二重層キャパシタを提供することにある。An object of the present invention is to provide an electrolytic solution obtained by dissolving an economically superior quaternary ammonium salt in a non-aqueous solvent while improving the withstand voltage without increasing the electric resistance. . Another object of the present invention is to provide an electric double layer capacitor having such an electrolytic solution.
【０００９】[0009]
【課題を解決するための手段】本発明によれば、上記の
目的は、一般式According to the present invention, the above objects have been achieved by the general formula
【００１０】[0010]
【化２】 Embedded image
【００１１】［式中、ＸはＢＦ4、ＰＦ6、ＣｌＯ4、Ａ
ｓＦ6、ＳｂＦ6、ＡｌＣｌ4またはＲｆＳＯ3（ここで、
Ｒｆはフルオロアルキル基を表す）を表し、ｎは０〜５
の整数を表し、Ｒ1、Ｒ2およびＲ3は水素原子、アルキ
ル基、アラルキル基、アルケニル基、アリール基もしく
は複素環基を表すか、またはＲ1とＲ2は互いに結合する
２つの炭素原子と一緒になって環構造を形成していても
よい。］で示されるアンモニウム塩（以下、これをアン
モニウム塩Ａと略称することがある）を非水系溶媒に溶
解して得られる電解液および該電解液を有する電気二重
層キャパシタを提供することによって達成される。[Wherein X is BF 4 , PF 6 , ClO 4 , A
sF 6 , SbF 6 , AlCl 4 or RfSO 3 (where
Rf represents a fluoroalkyl group), and n is 0 to 5
Wherein R 1 , R 2 and R 3 represent a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group or a heterocyclic group, or R 1 and R 2 represent two carbon atoms bonded to each other Together with to form a ring structure. The present invention has been attained by providing an electrolytic solution obtained by dissolving an ammonium salt represented by the following formula (hereinafter sometimes abbreviated as ammonium salt A) in a non-aqueous solvent, and an electric double layer capacitor having the electrolytic solution. You.
【００１２】[0012]
【発明の実施の形態】上記の一般式において、Ｒ1、Ｒ2
およびＲ3が表すアルキル基としては、例えばメチル
基、エチル基、プロピル基、ブチル基、イソプロピル基
などが挙げられ、アラルキル基としては、例えばベンジ
ル基などが挙げられ、アルケニル基としては、例えばア
リル基、クロチル基、プレニル基などが挙げられ、アリ
ール基としては、例えばフェニル基、ナフチル基などが
挙げられ、複素環基としては、例えばピリジル基、キノ
リル基、フリル基などが挙げられる。また、Ｒ1とＲ2が
互いに結合する２つの炭素原子と一緒になって形成する
環構造としては、例えばピペリジル基、ピロリジル基な
どが挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula, R 1 , R 2
And the alkyl group represented by R 3 include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and an isopropyl group, and the aralkyl group includes, for example, a benzyl group. Groups, a crotyl group, a prenyl group, and the like. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the heterocyclic group include a pyridyl group, a quinolyl group, and a furyl group. Examples of the ring structure formed by combining two carbon atoms where R 1 and R 2 are bonded to each other include a piperidyl group and a pyrrolidyl group.
【００１３】アンモニウム塩Ａは、対応するアミンをハ
ロゲン化アルキルなどで４級化した後に、アニオン交換
によって得ることができる。例えば、テトラメチルエチ
レンジアミンにヨウ化メチルを加えて４級化し、得られ
たジヨウ化ヘキサメチルエチレンジアンモニウムをさら
にテトラフルオロ硼酸水溶液でアニオン交換することに
よりヘキサメチルエチレンジアンモニウムテトラフルオ
ロボレートを得ることができる。得られるアンモニウム
塩Ａは、無水メタノールなどを用いて再結晶することに
より、残存するヨウ素イオンおよび水分を除去して使用
する。The ammonium salt A can be obtained by anion exchange after quaternizing the corresponding amine with an alkyl halide or the like. For example, quaternization can be performed by adding methyl iodide to tetramethylethylenediamine, and hexamethylethylenediammoniumtetrafluoroborate can be obtained by further anion-exchanging the obtained hexamethylethylenediamonium diiodide with an aqueous tetrafluoroboric acid solution. it can. The obtained ammonium salt A is used by removing the remaining iodide ions and water by recrystallization using anhydrous methanol or the like.
【００１４】本発明の電解液は、アンモニウム塩Ａを非
水系溶媒に溶解することによって調製される。非水系溶
媒としては、例えばジプロピルエーテル、ジブチルエー
テル、テトラヒドロフラン、テトラヒドロピランなどの
エーテル類；エチレンカーボネート、１，２−プロピレ
ンカーボネート、１，３−プロピレンカーボネートなど
のカーボネート類；γ―ブチロラクトン、α―メチル−
γ―ブチロラクトン、β―メチル−γ―ブチロラクトン
などのラクトン類；アセトニトリル、ベンゾニトリルな
どの二トリル類；ジメチルスルホキシドなどのスルホキ
シド類；ジメチルスルホランなどのスルホラン類などが
使用される。アンモニウム塩Ａの非水系溶媒中の濃度
は、高ければ高いほど好ましいが、低温でのアンモニウ
ム塩の溶解度を考慮して、通常０．０１〜５モル／リッ
トルの範囲であるのが好ましく、０．１〜３モル／リッ
トルの範囲であるのがより好ましい。The electrolytic solution of the present invention is prepared by dissolving ammonium salt A in a non-aqueous solvent. Examples of the non-aqueous solvent include ethers such as dipropyl ether, dibutyl ether, tetrahydrofuran and tetrahydropyran; carbonates such as ethylene carbonate, 1,2-propylene carbonate and 1,3-propylene carbonate; γ-butyrolactone, α- Methyl-
Lactones such as γ-butyrolactone and β-methyl-γ-butyrolactone; nitriles such as acetonitrile and benzonitrile; sulfoxides such as dimethylsulfoxide; sulfolanes such as dimethylsulfolane are used. The higher the concentration of the ammonium salt A in the non-aqueous solvent, the better. However, in consideration of the solubility of the ammonium salt at a low temperature, the concentration is usually preferably in the range of 0.01 to 5 mol / l, preferably 0.1 to 5 mol / l. More preferably, it is in the range of 1 to 3 mol / l.
【００１５】本発明の電気二重層キャパシタは、コイン
型（ボタン型）、フラット型、円筒型、巻型などの公知
の形状を取り得る。図１に、本発明の一実施形態に係る
コイン型電気二重層キャパシタの断面図を示す。図１に
示されるコイン型電気二重層キャパシタは、分極性電極
３，４がセパレータ２により分離されており、分極性電
極３，４のセパレータ２とは反対の面にそれぞれ集電極
１，５が接するように設置されており、全体が蓋（リー
ド電極）６で覆われた構造を有している。分極性電極
３，４は、活性炭とアセチレンブラック、カーボンブラ
ックなどの導電性補助材料およびテフロン（登録商
標）、ポリテトラフルオロエチレンなどの結着材の混錬
物である。これらの割合は、活性炭の電気伝導度および
自己結着力によって異なるが、通常活性炭８０重量部に
対して、導電性補助材料０〜２０重量部、結着材０〜２
０重量部の範囲で使用される。セパレータ２は二つの分
極性電極が接触しないように絶縁する役目を果たしてい
る。セパレータとしては、ガラス製ろ紙、ポリプロピレ
ン、ナイロンなどの不織布、ポリテトラフルオロエチレ
ンなどの多孔性フィルムが使用される。集電極１，５と
しては、例えば、活性炭繊維にニッケル、アルミニウ
ム、亜鉛、銅、スズ、鉛またはこれらの合金をプラズマ
溶射、アーク溶射することによって形成されたものが使
用される。蓋６は金属製であり、集電極保護の役目を果
す。用いられる材質としては導電性であればよく、ステ
ンレス製、アルミニウム製、ニッケル製などが使用され
る。The electric double layer capacitor of the present invention can take a known shape such as a coin type (button type), a flat type, a cylindrical type, and a wound type. FIG. 1 shows a sectional view of a coin-type electric double layer capacitor according to an embodiment of the present invention. In the coin-type electric double layer capacitor shown in FIG. 1, the polarizable electrodes 3 and 4 are separated by a separator 2, and collector electrodes 1 and 5 are provided on the surfaces of the polarizable electrodes 3 and 4 opposite to the separator 2, respectively. They are installed so as to be in contact with each other, and have a structure in which the whole is covered with a lid (lead electrode) 6. The polarizable electrodes 3 and 4 are a kneaded product of activated carbon, a conductive auxiliary material such as acetylene black and carbon black, and a binder such as Teflon (registered trademark) and polytetrafluoroethylene. These proportions vary depending on the electric conductivity and the self-binding force of the activated carbon, but usually 0 to 20 parts by weight of the conductive auxiliary material and 0 to 2 parts by weight of the binder with respect to 80 parts by weight of the activated carbon.
Used in the range of 0 parts by weight. The separator 2 serves to insulate the two polarizable electrodes from contacting each other. As the separator, a glass filter paper, a nonwoven fabric such as polypropylene or nylon, or a porous film such as polytetrafluoroethylene is used. As the collector electrodes 1 and 5, for example, those formed by plasma spraying or arc spraying nickel, aluminum, zinc, copper, tin, lead or an alloy thereof on activated carbon fibers are used. The lid 6 is made of metal and serves to protect the collector. Any material may be used as long as it is conductive, and stainless steel, aluminum, nickel and the like are used.
【００１６】[0016]
【実施例】以下に、実施例を挙げて本発明をより具体的
に説明するが、本発明はこれらの実施例に限定されるも
のではない。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
【００１７】実施例１〜４および比較例１〜３ 表１に示される電解質を用い、各々濃度０．５Ｍ／リッ
トルのプロピレンカーボネート溶液とし、これらの電解
液を充填した電気二重層キャパシタを作製した。これら
の電気二重層キャパシタをＨＩＯＫＩ ＥＤＬＣ評価シ
ステムを用いて、２．８Ｖの充放電試験を３０℃で１０
００回行った。表１に初期ＥＳＲ、１０００回の負荷試
験後のＥＳＲおよび静電容量を示す。Examples 1 to 4 and Comparative Examples 1 to 3 Using the electrolytes shown in Table 1, propylene carbonate solutions each having a concentration of 0.5 M / liter were prepared, and electric double layer capacitors filled with these electrolytes were produced. . These electric double layer capacitors were subjected to a 2.8 V charge / discharge test at 30 ° C. for 10 times using a HIOKI EDLC evaluation system.
It was performed 00 times. Table 1 shows the initial ESR, the ESR after 1000 load tests, and the capacitance.
【００１８】[0018]
【表１】 [Table 1]
【００１９】表１より明らかなように、実施例１〜４の
電気二重層キャパシタは、比較例１〜３の電気二重層キ
ャパシタに比べて、ＥＳＲの変化量が小さいことが分か
る。これは実施例１〜４の電気二重層キャパシタで用い
た電解質の耐電圧が向上したことに起因すると推定され
る。As is clear from Table 1, the electric double layer capacitors of Examples 1 to 4 have a smaller ESR variation than the electric double layer capacitors of Comparative Examples 1 to 3. This is presumed to be due to the improved withstand voltage of the electrolyte used in the electric double layer capacitors of Examples 1 to 4.
【００２０】参考例１ 温度計、ジムロート還流管および滴下ロートを装着した
１リットル容三つ口フラスコに、テトラメチルエチレン
ジアミン１１６ｇ（１モル）、キシレン３００ｇを取
り、窒素にて反応器内を置換した後、７０℃に昇温し
た。そこにヨウ化メチル３１９．５ｇ（２．２５モル）
を４時間で滴下した。滴下終了後、さらに１０時間加熱
攪拌した。−１０℃まで冷却し、析出した塩をろ取し
た。ジヨウ化ヘキサメチルエチレンジアンモニウムの収
量は３３２ｇ（収率８３％）であった。ジヨウ化ヘキサ
メチルエチレンジアンモニウム４０ｇ（０．１モル）を
温度計、ジムロート還流管および滴下ロートを装着した
１リットル容三つ口フラスコに取り、メタノール４００
ｇを加え、系内を窒素置換した後、反応液を−２０℃に
冷却した。そこに、ＨＢＦ4８８ｇ（１モル）を３時間
で滴下し、さらに１２時間攪拌した。析出した塩をろ過
によって除いた後、メタノールを減圧下に留去した。得
られた残渣をメタノール：水＝１：１の溶液２００ｇか
ら再結晶した。得られた粗結晶をさらに乾燥メタノール
から再結晶して、目的とするヘキサメチルエチレンジア
ンモニウムテトラフルオロボレート２１．１ｇ（収率６
６％）を得た。Reference Example 1 In a 1-liter three-necked flask equipped with a thermometer, a Dimroth reflux tube and a dropping funnel, 116 g (1 mol) of tetramethylethylenediamine and 300 g of xylene were placed, and the inside of the reactor was replaced with nitrogen. Thereafter, the temperature was raised to 70 ° C. 319.5 g (2.25 mol) of methyl iodide there
Was added dropwise over 4 hours. After completion of the dropwise addition, the mixture was further heated and stirred for 10 hours. After cooling to -10 ° C, the precipitated salt was collected by filtration. The yield of hexamethylethylene diammonium diiodide was 332 g (83% yield). 40 g (0.1 mol) of hexamethylethylenediammonium diiodide was placed in a 1-liter three-necked flask equipped with a thermometer, a Dimroth reflux tube and a dropping funnel, and methanol 400 was added.
g was added and the inside of the system was replaced with nitrogen, and then the reaction solution was cooled to -20 ° C. There, 88 g (1 mol) of HBF 4 was added dropwise over 3 hours, and the mixture was further stirred for 12 hours. After removing the precipitated salt by filtration, methanol was distilled off under reduced pressure. The obtained residue was recrystallized from 200 g of a 1: 1 methanol: water solution. The obtained crude crystals were further recrystallized from dry methanol to obtain 21.1 g of the desired hexamethylethylenediammonium tetrafluoroborate (yield 6).
6%).
【００２１】参考例２ ハステロイＣ製１リットル容オートクレーブに圧力計お
よび温度計を装着し、これにジエチレントリアミン１０
３ｇ（１モル）を取り、系内を窒素置換した後、ヨウ化
メチル１１３６ｇ（８モル）を加えて、１２０℃に加熱
した。２０時間過熱攪拌し、室温に冷却した後、内容物
を取り出し、固体であるトリヨウ化オクタメチルジエチ
レントリアンモニウム１７８ｇ（収率３３％）を得た。
トリヨウ化オクタメチルジエチレントリアンモニウム４
９．６ｇ（０．１モル）を温度計、ジムロート還流管お
よび滴下ロートを装着した１リットル容三つ口フラスコ
に取り、メタノール４００ｇを加え、系内を窒素置換し
た後、反応液を−２０℃に冷却した。そこにＨＢＦ4８
８ｇ（１モル）を３時間で滴下し、さらに１２時間攪拌
した。析出した塩をろ過によって除いた後、メタノール
を減圧下に留去した。得られた残渣をメタノール：水＝
１：１の溶液２００ｇから再結晶した。得られた粗結晶
をさらに乾燥メタノールから再結晶して、目的とするオ
クタメチルジエチレントリアンモニウムテトラフルオロ
ボレート２３．４ｇ（収率５２％）を得た。Reference Example 2 A pressure gauge and a thermometer were attached to a 1 liter autoclave made of Hastelloy C, and diethylene triamine 10
After taking 3 g (1 mol) and replacing the inside of the system with nitrogen, 1136 g (8 mol) of methyl iodide was added and heated to 120 ° C. After stirring with heating for 20 hours and cooling to room temperature, the contents were taken out to obtain 178 g (yield 33%) of octamethyldiethylenetriammonium triiodide as a solid.
Octamethyldiethylenetriammonium triiodide 4
9.6 g (0.1 mol) was placed in a 1-liter three-necked flask equipped with a thermometer, a Dimroth reflux tube and a dropping funnel, 400 g of methanol was added, and the system was purged with nitrogen. Cooled to ° C. There HBF 4 8
8 g (1 mol) was added dropwise over 3 hours, and the mixture was further stirred for 12 hours. After removing the precipitated salt by filtration, methanol was distilled off under reduced pressure. The obtained residue is methanol: water =
It was recrystallized from 200 g of a 1: 1 solution. The obtained crude crystals were further recrystallized from dry methanol to obtain 23.4 g (yield: 52%) of the target octamethyldiethylenetriammonium tetrafluoroborate.
【００２２】参考例３ 参考例１においてヨウ化メチル３１９．５ｇの代わりに
ヨウ化エチル３５１ｇを用いた以外は同様にして反応お
よび操作を行い、目的とするヘキサエチルエチレンジア
ンモニウムテトラフルオロボレート１３．９ｇ（収率３
４％）を得た。Reference Example 3 The reaction and operation were carried out in the same manner as in Reference Example 1 except that 351 g of ethyl iodide was used instead of 319.5 g of methyl iodide. 9 g (yield 3
4%).
【００２３】参考例４ 参考例２においてヨウ化メチル１１３６ｇの代わりにヨ
ウ化エチル１２４８ｇを用いた以外は同様にして反応お
よび操作を行い、目的とするオクタエチルジエチレント
リアンモニウムテトラフルオロボレート１５．４ｇ（収
率２７％）を得た。Reference Example 4 The reaction and operation were carried out in the same manner as in Reference Example 2 except for using 1248 g of methyl iodide instead of 1248 g of ethyl iodide, to obtain 15.4 g of the intended octaethyldiethylenetriammonium tetrafluoroborate (yield: 27%).
【００２４】[0024]
【発明の効果】本発明により、電気抵抗を増加させるこ
となく耐電圧を向上させ、かつ経済的に優位な、４級ア
ンモニウム塩を非水系溶媒に溶解して得られる電解液が
提供され、該電解液を有する電気二重層キャパシタが提
供される。According to the present invention, there is provided an electrolytic solution obtained by dissolving a quaternary ammonium salt in a non-aqueous solvent, which is improved in withstand voltage without increasing electric resistance and economically advantageous. An electric double layer capacitor having an electrolyte is provided.
【図１】本発明の一実施形態に係るコイン型電気二重層
キャパシタの断面図である。FIG. 1 is a sectional view of a coin-type electric double layer capacitor according to an embodiment of the present invention.
１，５…集電極、２…セパレータ、３，４…分極性電
極、６…蓋1,5 ... collector electrode, 2 ... separator, 3,4 ... polarizable electrode, 6 ... lid
Claims (2)
6、ＡｌＣｌ4またはＲｆＳＯ3（ここで、Ｒｆはフルオ
ロアルキル基を表す）を表し、ｎは０〜５の整数を表
し、Ｒ1、Ｒ2およびＲ3は水素原子、アルキル基、アラ
ルキル基、アルケニル基、アリール基もしくは複素環基
を表すか、またはＲ1とＲ2は互いに結合する２つの炭素
原子と一緒になって環構造を形成していてもよい。］で
示されるアンモニウム塩を非水系溶媒に溶解して得られ
る電解液。1. A compound of the general formula [Where X is BF 4 , PF 6 , ClO 4 , AsF 6 , SbF
6 , AlCl 4 or RfSO 3 (where Rf represents a fluoroalkyl group), n represents an integer of 0 to 5, and R 1 , R 2 and R 3 represent a hydrogen atom, an alkyl group, an aralkyl group, It may represent an alkenyl group, an aryl group or a heterocyclic group, or R 1 and R 2 may form a ring structure together with two carbon atoms bonded to each other. ] An electrolytic solution obtained by dissolving the ammonium salt represented by the formula (1) in a non-aqueous solvent.
キャパシタ。2. An electric double layer capacitor having the electrolytic solution according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000339924A JP4583582B2 (en) | 2000-11-08 | 2000-11-08 | Electric double layer capacitor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000339924A JP4583582B2 (en) | 2000-11-08 | 2000-11-08 | Electric double layer capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002151360A true JP2002151360A (en) | 2002-05-24 |
| JP4583582B2 JP4583582B2 (en) | 2010-11-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000339924A Expired - Fee Related JP4583582B2 (en) | 2000-11-08 | 2000-11-08 | Electric double layer capacitor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011132307A1 (en) * | 2010-04-23 | 2011-10-27 | 富士通株式会社 | Electrolyte and storage device using electrolyte |
| CN102584602A (en) * | 2011-01-05 | 2012-07-18 | 中国科学院长春应用化学研究所 | Quaternary ammonium salt and preparation method thereof |
| CN103688326A (en) * | 2011-08-30 | 2014-03-26 | 海洋王照明科技股份有限公司 | Double-center quaternary ammonium salt ion liquid, preparation method therefor and use thereof |
| EP2752409A1 (en) * | 2011-08-30 | 2014-07-09 | Ocean's King Lighting Science & Technology Co., Ltd. | Double-center bipyridyl cationic ion liquid, preparation method therefor and use thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000311839A (en) * | 1999-04-26 | 2000-11-07 | Mitsubishi Chemicals Corp | Electrolytic solution for electrochemical capacitor, and electrochemical capacitor using the same |
-
2000
- 2000-11-08 JP JP2000339924A patent/JP4583582B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000311839A (en) * | 1999-04-26 | 2000-11-07 | Mitsubishi Chemicals Corp | Electrolytic solution for electrochemical capacitor, and electrochemical capacitor using the same |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011132307A1 (en) * | 2010-04-23 | 2011-10-27 | 富士通株式会社 | Electrolyte and storage device using electrolyte |
| JPWO2011132307A1 (en) * | 2010-04-23 | 2013-07-18 | 富士通株式会社 | Electrolytic solution and power storage device using the electrolytic solution |
| JP5376052B2 (en) * | 2010-04-23 | 2013-12-25 | 富士通株式会社 | Electrolytic solution and power storage device using the electrolytic solution |
| US8804311B2 (en) | 2010-04-23 | 2014-08-12 | Fujitsu Limited | Electrolyte solution and electric energy storing device using electrolyte solution |
| CN102584602A (en) * | 2011-01-05 | 2012-07-18 | 中国科学院长春应用化学研究所 | Quaternary ammonium salt and preparation method thereof |
| CN103688326A (en) * | 2011-08-30 | 2014-03-26 | 海洋王照明科技股份有限公司 | Double-center quaternary ammonium salt ion liquid, preparation method therefor and use thereof |
| EP2752861A1 (en) * | 2011-08-30 | 2014-07-09 | Ocean's King Lighting Science&Technology Co., Ltd. | Double-center quaternary ammonium salt ion liquid, preparation method therefor and use thereof |
| EP2752409A1 (en) * | 2011-08-30 | 2014-07-09 | Ocean's King Lighting Science & Technology Co., Ltd. | Double-center bipyridyl cationic ion liquid, preparation method therefor and use thereof |
| EP2752861A4 (en) * | 2011-08-30 | 2015-04-01 | Oceans King Lighting Science | Double-center quaternary ammonium salt ion liquid, preparation method therefor and use thereof |
| EP2752409A4 (en) * | 2011-08-30 | 2015-04-29 | Oceans King Lighting Science | Double-center bipyridyl cationic ion liquid, preparation method therefor and use thereof |
| US9196424B2 (en) | 2011-08-30 | 2015-11-24 | Ocean's King Lighting Science & Technology Co., Ltd. | Double-center bipyridyl cationic ion liquid, preparation method therefor and use thereof |
| US9202632B2 (en) | 2011-08-30 | 2015-12-01 | Ocean's King Lighting Science & Technology Co., Ltd. | Double-center quaternary ammonium salt ion liquid, preparation method therefor and use thereof |
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|---|---|
| JP4583582B2 (en) | 2010-11-17 |
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