JPS63127519A - Electric double-layer capacitor - Google Patents
Electric double-layer capacitorInfo
- Publication number
- JPS63127519A JPS63127519A JP61273029A JP27302986A JPS63127519A JP S63127519 A JPS63127519 A JP S63127519A JP 61273029 A JP61273029 A JP 61273029A JP 27302986 A JP27302986 A JP 27302986A JP S63127519 A JPS63127519 A JP S63127519A
- Authority
- JP
- Japan
- Prior art keywords
- electric double
- carbon atoms
- layer capacitor
- double layer
- group
- 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
- 239000003990 capacitor Substances 0.000 title claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000005626 carbonium group Chemical group 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- -1 alkali metal salts Chemical class 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は電気二重層コンデンサに関するものである。[Detailed description of the invention] (Industrial application field) The present invention relates to an electric double layer capacitor.
（従来の技術）
電気二重層コンデンサに用いる電解液としては従来、過
塩素酸、６フツ化リン酸、４フツ化ホウ酸、またはトリ
フルオロメタンスルホン酸のアルカリ金属塩、テトラア
ルキルアンモニウム塩など電気化学的に安定な溶質を、
極性有機溶媒に溶解させたものが知られている（特開昭
４９−６８２５４号、特開昭５０−４４４６３号、特開
昭５９−２３２４０９号などの公報）。(Prior art) Electrolytes used in electric double layer capacitors have conventionally been electrochemical solutions such as perchloric acid, hexafluorophosphoric acid, tetrafluoroboric acid, alkali metal salts of trifluoromethanesulfonic acid, and tetraalkylammonium salts. a physically stable solute,
Those dissolved in polar organic solvents are known (JP-A-49-68254, JP-A-50-44463, JP-A-59-232409, etc.).
（発明が解決しようとする問題点）
しかしながら、これら公知の溶質を使用した電気二重層
コンデンサにおいては、耐電圧、容量値、長期信顛性な
どの点で十分な性能が得られないという問題点があった
。(Problems to be Solved by the Invention) However, electric double layer capacitors using these known solutes have the problem that sufficient performance cannot be obtained in terms of withstand voltage, capacitance value, long-term reliability, etc. was there.
本発明は、前記の問題点を解決して、耐電圧、容量およ
び長期信頼性に優れた電気二重層コンデンサを提供する
ことを目的とするものである。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and provide an electric double layer capacitor with excellent withstand voltage, capacity, and long-term reliability.
（問題点を解決するための手段）
本発明は前記の問題点を解決するため、分極性電極と電
解液との界面で形成される電気二重層コンデンサにおい
て、電解液の溶質が、一般式Ｒ１Ｃ−Ｘ （１） 、ま
たはＲＣＯ・Ｘ （Ｉｆ）で表されるカルボニウム塩よ
りなることを特徴とする電気二重層コンデンサを提供す
るものである。(Means for Solving the Problems) In order to solve the above problems, the present invention provides an electric double layer capacitor formed at the interface between a polarizable electrode and an electrolyte, in which the solute of the electrolyte has the general formula R1C The present invention provides an electric double layer capacitor characterized by being made of a carbonium salt represented by -X (1) or RCO.X (If).
ただし、前記一般式において、Ｒは水素原子、炭素数１
〜１５のアルキル基、アリル基、炭素数６〜１５のアリ
ール基、またはＯＲ’（Ｒ’は炭素数１〜工５のアルキ
ル基、または炭素数６〜１５のアリール基である）を示
し、ＸはＢＦ４、ＰＦ６、ＣｌＯ２、ＡｇＦ２．５ｂＦ
ｂ 、ＡｆｆＣｆｆ４またはＲｆＳＯ３（Ｒｔは炭素数
１〜８のフルオロアルキル基である）を示す。However, in the above general formula, R is a hydrogen atom, carbon number 1
-15 alkyl group, allyl group, aryl group having 6 to 15 carbon atoms, or OR'(R' is an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 15 carbon atoms), X is BF4, PF6, ClO2, AgF2.5bF
b represents AffCff4 or RfSO3 (Rt is a fluoroalkyl group having 1 to 8 carbon atoms).
本発明で用いる電解液の溶質としては、一般式Ｒ：ｌＣ
・Ｘ （Ｉ）またはＲＣＯ−Ｘ （ＩＩ）で表されるカ
ルボニウム塩を使用することが重要であり、一般式（［
）、（１１）においてＲは水素原子くただし、（１）に
おいてすべてＨであることはない）、炭素数１〜１５好
ましくは１〜４のアルキル基、アリル基（ＣＨｚ ＝
ＣＨＣＨｚ ） 、炭素数６〜１５好ましくは６〜１
０のアリール基、またはＯＲ’（Ｒ’は炭素数１〜１５
好ましくは１〜４のアルキル基、または炭素数６〜１５
好ましくは６〜１０のアリール基である）である。The solute of the electrolytic solution used in the present invention has the general formula R:lC
・It is important to use a carbonium salt represented by X (I) or RCO-X (II), and the general formula ([
), in (11), R is a hydrogen atom; in (1), R is not all H), an alkyl group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, an allyl group (CHz =
CHCHHz), carbon number 6-15, preferably 6-1
0 aryl group, or OR'(R' has 1 to 15 carbon atoms
Preferably an alkyl group having 1 to 4 carbon atoms or 6 to 15 carbon atoms
preferably 6 to 10 aryl groups).
さらに、一般式におけるＸは、ＢＦ４、ＰＦいＣＲＯａ
、ＡＳＦｂ 、５ｂＦｂ 、Ａｌ（ニア！ａまたはＲ
ｒ ＳＯ３（Ｒｒは炭素数１〜８好ましくは１〜４のフ
ルオロアルキル基を示す）である。Furthermore, X in the general formula is BF4, PF, CROa
, ASFb , 5bFb , Al (Nia!a or R
r SO3 (Rr represents a fluoroalkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms).
このような？８質（電解質）の電解液中の濃度としては
、０．１〜３．０Ｍ／ｌ、特に０．５〜１．５ Ｍ／ｅ
とすることが好適である。この濃度が低過ぎると内部抵
抗が増大することによりｂＪ失（ｔａｎ δ）が増大し
、一方、高過ぎると低温になったとき溶質が析出して安
定性が低下するなどの不具合を生ずる恐れがある。like this? The concentration of the 8 substances (electrolytes) in the electrolytic solution is 0.1 to 3.0 M/l, especially 0.5 to 1.5 M/e.
It is preferable that If this concentration is too low, bJ loss (tan δ) will increase due to an increase in internal resistance, while if it is too high, problems such as solute precipitation and decreased stability may occur at low temperatures. be.
本発明で用いる電解液の溶媒としては、特に限定される
ものではなく、プロピレンカーボネート、ブチレンカー
ボネート、β−フ゛チロラクトン、γ−ブチロラクトン
、アセトニトリル、ジメチルホルムアミド、■、２−ジ
メトキシエタン、スルホラン、ニトロメタンなどが単独
でまたは適宜混合して好適に使用される。The solvent for the electrolytic solution used in the present invention is not particularly limited, and examples include propylene carbonate, butylene carbonate, β-butyrolactone, γ-butyrolactone, acetonitrile, dimethylformamide, 2-dimethoxyethane, sulfolane, and nitromethane. They are preferably used alone or in appropriate mixtures.
本発明で用いる分極性電極の材質については、特に限定
されないが、電解液に対して電気化学的に不活性で、か
つ比表面積の大きな活性炭粉末あるいは活性炭繊維を使
用するのが好ましい。The material of the polarizable electrode used in the present invention is not particularly limited, but it is preferable to use activated carbon powder or activated carbon fiber that is electrochemically inert to the electrolyte and has a large specific surface area.
特に、活性炭粉末にポリテトラフルオロエチレン（ＰＴ
ＦＥ）などの結着剤を添加し、ロール成型してシート化
し、さらに好ましくは一軸または二輪方向に延伸処理を
施した電極は、単位体積当りの容量、強度および長期信
頼性に優れているので好適に使用される。In particular, activated carbon powder contains polytetrafluoroethylene (PT).
Electrodes that are made by adding a binder such as FE), roll-formed into a sheet, and preferably stretched in a uniaxial or biaxial direction have excellent capacity per unit volume, strength, and long-term reliability. Preferably used.
本発明で一対の分極性電極の間に介装されるセパレータ
としては電気二重層コンデンサ用の通常のセパレータ、
たとえばポリプロピレン繊維不織布またはガラス繊維混
抄不織布よりなるセパレータを使用することができる。In the present invention, the separator interposed between the pair of polarizable electrodes is a normal separator for electric double layer capacitors,
For example, a separator made of a polypropylene fiber nonwoven fabric or a glass fiber mixed nonwoven fabric can be used.
（実施例）
次に、実施例および比較例を図面に基づいて具体的に説
明する。(Example) Next, Examples and Comparative Examples will be specifically described based on the drawings.
本発明の実施例および比較例に共通のものとして第１図
に示すようなコイン型電気二重層コンデンサのユニット
セル（直径２０＋ｎ、厚み２．０朋）を次のようにして
作製した。まず、活性炭粉末（比表面積約２，０００
ｒｒｒ／ｇ”）に１０重量％のポリテトラフルオロエチ
レンを添加して湿式混純によってシート化した。このよ
うにして得られたシートを円板状に打ち抜いて分極性電
極１ （直径１５貢−１厚さ０．７ｍｍ）とし、分極性
電極ｌとこれと同一の組成、形状を有する分極性電極２
とをポリプロピレン繊維不織布よりなるセパレータ３を
介してステンレス鋼製のキヤ・ノブ４およびステンレス
ｔｍ製の缶５からなる外装容器中に収納する。次に、ユ
ニットセル中に所定の電解液を注入して分極性電極ｌ、
２およびセパレータ３中にこの電解液を充分に含浸させ
た後、ポリプロピレン製バッキング６を介してキャンプ
４および缶５の端部をかしめて封口し一体化した。A unit cell (diameter 20+n, thickness 2.0 mm) of a coin-type electric double layer capacitor as shown in FIG. 1, which is common to the examples and comparative examples of the present invention, was prepared in the following manner. First, activated carbon powder (specific surface area approximately 2,000
10 wt. 1 thickness of 0.7 mm) and having the same composition and shape as the polarizable electrode 1.
and are housed in an outer container consisting of a can knob 4 made of stainless steel and a can 5 made of stainless steel TM via a separator 3 made of a nonwoven polypropylene fiber fabric. Next, a predetermined electrolyte is injected into the unit cell, and the polarizable electrode l,
After sufficiently impregnating this electrolytic solution into 2 and separator 3, the ends of camp 4 and can 5 were caulked and sealed via polypropylene backing 6 to integrate them.
前述のようにして作製した電気二重層コンデンサのユニ
ットセルを使用し、第１表に示すような種々の電解液を
用いた各セルについて、２．８■の電圧を印加したとき
の初期容量および内部抵抗を測定した後、引続いてこの
セルに２．８■の電圧を印加しながら７０℃で１０００
時間貯蔵した後の容量を測定し、初期容量からの容量劣
化率（％）を算出した。これらの測定結果を実施例１〜
１４および比較例１．２として第１表に示した。Using the unit cells of the electric double layer capacitors prepared as described above, the initial capacitance and After measuring the internal resistance, the cell was heated at 70℃ for 1000℃ while applying a voltage of 2.8μ.
The capacity after storage for a period of time was measured, and the rate of capacity deterioration (%) from the initial capacity was calculated. These measurement results are shown in Example 1~
14 and Comparative Example 1.2 in Table 1.
なお、内部抵抗は、交流二端子法（周波数ＩＫＨｚ）に
よって測定した。Note that the internal resistance was measured by an AC two-terminal method (frequency IKHz).
（木頁、以下余白）
（発明の効果）
以上説明したように本発明によれば、耐電圧が高いため
高温条件下での容量劣化率が低く長期信頼性の高い電気
二重層コンデンサが得られる。(Wood page, blank space below) (Effects of the invention) As explained above, according to the present invention, an electric double layer capacitor with high withstand voltage, low capacity deterioration rate under high temperature conditions, and high long-term reliability can be obtained. .
第１図は本発明による電気二重層コンデンサの一実施態
様を示す部分断面図である。
１．２・・・・・・分極性電極
３・・・・・・セパレータ、
４・・・・・・キャップ、
５・・・・・・缶、
６・・・・・・バンキング。FIG. 1 is a partial sectional view showing one embodiment of an electric double layer capacitor according to the present invention. 1.2...Polarizable electrode 3...Separator, 4...Cap, 5...Can, 6...Banking.
Claims (2)
重層コンデンサにおいて、電解液の溶質が、一般式Ｒ＿
３Ｃ・Ｘ、またはＲＣＯ・Ｘで表されるカルボニウム塩
よりなることを特徴とする電気二重層コンデンサ。 ただし、前記一般式中、Ｒは水素原子、炭素数１〜１５
のアルキル基、アリル基、炭素数６〜１５のアリール基
、またはＯＲ′（Ｒ′は炭素数１〜１５のアルキル基、
または炭素数６〜１５のアリール基である）を示し、Ｘ
はＢＦ＿４、ＰＦ＿６、ＣｌＯ＿４、ＡｓＦ＿６、Ｓｂ
Ｆ＿６、ＡｌＣｌ＿４またはＲ＿ｆＳＯ＿３（Ｒ＿ｆは
炭素数１〜８のフルオロアルキル基である）を示す。(1) In an electric double layer capacitor formed at the interface between a polarizable electrode and an electrolyte, the solute of the electrolyte has the general formula R_
An electric double layer capacitor comprising a carbonium salt represented by 3C.X or RCO.X. However, in the above general formula, R is a hydrogen atom, and has 1 to 15 carbon atoms.
an alkyl group, an allyl group, an aryl group having 6 to 15 carbon atoms, or OR'(R' is an alkyl group having 1 to 15 carbon atoms,
or an aryl group having 6 to 15 carbon atoms), and
are BF_4, PF_6, ClO_4, AsF_6, Sb
F_6, AlCl_4 or R_fSO_3 (R_f is a fluoroalkyl group having 1 to 8 carbon atoms).
特許請求の範囲第１項記載の電気二重層コンデンサ。(2) The electric double layer capacitor according to claim 1, wherein the concentration of the solute is 0.1 to 3.0 M/l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61273029A JPS63127519A (en) | 1986-11-18 | 1986-11-18 | Electric double-layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61273029A JPS63127519A (en) | 1986-11-18 | 1986-11-18 | Electric double-layer capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63127519A true JPS63127519A (en) | 1988-05-31 |
Family
ID=17522175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61273029A Pending JPS63127519A (en) | 1986-11-18 | 1986-11-18 | Electric double-layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63127519A (en) |
-
1986
- 1986-11-18 JP JP61273029A patent/JPS63127519A/en active Pending
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