JPH01222425A - Electric double layer capacitor - Google Patents
Electric double layer capacitorInfo
- Publication number
- JPH01222425A JPH01222425A JP63045918A JP4591888A JPH01222425A JP H01222425 A JPH01222425 A JP H01222425A JP 63045918 A JP63045918 A JP 63045918A JP 4591888 A JP4591888 A JP 4591888A JP H01222425 A JPH01222425 A JP H01222425A
- Authority
- JP
- Japan
- Prior art keywords
- double layer
- electric double
- ion
- separator
- layer capacitor
- 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 abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract 3
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 125000005496 phosphonium group Chemical group 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- -1 polypropylene Polymers 0.000 description 5
- 150000002500 ions Chemical class 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
- 239000000203 mixture Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000010220 ion permeability Effects 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
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910003202 NH4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910006127 SO3X Inorganic materials 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 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
- 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
- 125000005497 tetraalkylphosphonium group Chemical group 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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
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としては従来、たとえば特開昭５
６−８３９２０号公報に記載されたように、分極性電極
間に介装するセパレータはイオン透過性と電子絶縁性を
付与するために微孔性セパレータと電子絶縁性セパレー
タとを組合わせて使用するようになされている。[Prior art] Conventional electric double layer capacitors include
As described in Publication No. 6-83920, the separator interposed between polarizable electrodes is a combination of a microporous separator and an electronically insulating separator to provide ion permeability and electronic insulation. It is done like this.
［発明の解決しようとする課題］
しかしながら、このような場合には、微孔性セパレータ
と絶縁性セパレータとを２枚重ねて使用するためにコン
デンサの内部抵抗が増大する欠点があった。[Problems to be Solved by the Invention] However, in such a case, there is a drawback that the internal resistance of the capacitor increases because the microporous separator and the insulating separator are used in a stacked manner.
また、従来用いられてきたポリプロピレン繊維不織布、
ガラス繊維混抄不織布などよりなるセパレータの場合に
は厚さ５０〜８０川程度が限界であり、厚さをそれ以下
にすると炭素電極から脱落した粉体がセパレータを透過
することによって漏れ電流が大きくなる欠点があった。In addition, conventionally used polypropylene fiber nonwoven fabrics,
In the case of a separator made of glass fiber mixed non-woven fabric, etc., the maximum thickness is about 50 to 80 mm, and if the thickness is less than that, the powder that has fallen off from the carbon electrode will pass through the separator, resulting in a large leakage current. There were drawbacks.
さらに、特開昭６１−９７９１０号公報にはイオン透過
性を有する電子絶縁体層を活性炭繊維よりなる電極の片
面に溶射法によって付与するものが記載されているが、
溶射法による場合には装置が高価であり、また大面積の
電極処理には適していない等の欠点があった。Furthermore, JP-A No. 61-97910 describes a method in which an electronic insulating layer having ion permeability is applied to one side of an electrode made of activated carbon fibers by a thermal spraying method.
The thermal spraying method has drawbacks such as expensive equipment and unsuitability for treating large areas of electrodes.
［課題を解決するための手段］
本発明はこれら諸欠点を排除したものであり、分極性電
極と電解液との界面で形成される電気二重層を利用する
電気二重層コンデンサにおいて、セパレータにイオン交
換体より膜状物を用いることを特徴とする電気二重層コ
ンデンサを提供するにある。[Means for Solving the Problems] The present invention eliminates these drawbacks, and is an electric double layer capacitor that utilizes an electric double layer formed at the interface between a polarizable electrode and an electrolyte. An object of the present invention is to provide an electric double layer capacitor characterized in that a membrane material is used rather than an exchanger.
本発明で用いるイオン交換体としては、通常のイオン交
換体が使用可能であるが、構造式（Ｉ）で表される重合
体が好適に使用される。As the ion exchanger used in the present invention, a normal ion exchanger can be used, but a polymer represented by the structural formula (I) is preferably used.
構造式（Ｉ）において、履は０または１．ｎは１〜５の
整数、ＲＣｉＣＯｇＸ 、 ＳＯ３Ｘ 、 ＰＯ，Ｘ（
Ｘはｌ 、 Ｌｉ 、 Ｋ 、 Ｎａ 、 ＮＨ４＊第
４級アンモニウム基または第４級ホスホニウム基）のい
ずれかである。In structural formula (I), 0 or 1. n is an integer from 1 to 5, RCiCOgX, SO3X, PO,X(
X is l, Li, K, Na, NH4*quaternary ammonium group or quaternary phosphonium group).
イオン交換体のイオン交換容量は好ましくは０．５〜２
．０ミリ当量／ｇ乾燥樹脂が適当である。The ion exchange capacity of the ion exchanger is preferably 0.5 to 2.
．． 0 meq/g dry resin is suitable.
本発明で用いる分極性電極の材料としては、活性炭ペー
スト、活性炭繊維、活性炭シートなどの材料から適宜選
択することができるが、信頼性の点から活性炭シートが
特に好ましい。活性炭シートよりなる電極は、活性炭お
よびカーボンブラックから選ばれた少なくとも１つの成
分からなる微粉末状炭素と、含フツ素樹脂重合体とを混
合して、この混合物に液状潤滑剤を添加して混練しシー
ト状に成型した後、成型物を好ましくは一軸または二軸
方向に延伸処理し、さらに必要に応じて焼成処理して得
られたものが好適に使用される。The material for the polarizable electrode used in the present invention can be appropriately selected from activated carbon paste, activated carbon fiber, activated carbon sheet, etc., but activated carbon sheet is particularly preferred from the viewpoint of reliability. Electrodes made of activated carbon sheets are made by mixing finely powdered carbon made of at least one component selected from activated carbon and carbon black with a fluorine-containing resin polymer, adding a liquid lubricant to this mixture, and kneading the mixture. After molding into a sheet, the molded product is preferably stretched in uniaxial or biaxial directions and, if necessary, fired, and the resulting product is preferably used.
本発明の分極性電極と組合せて使用する電解液としては
、特に限定されるものではなく、電気二重層コンデンサ
用として通常用いられるもの、すなわち電気化学的に安
定な溶質（電解質）を極性有機溶媒に溶解したものが適
宜使用される。電解液の溶媒としては、プロピレンカー
ボネート、ブチレンカーボネート、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、１．２−ジ
メトキシエタン、スルホラン、ニトロメタンなどが好適
に使用される。The electrolytic solution used in combination with the polarizable electrode of the present invention is not particularly limited, and is one that is commonly used for electric double layer capacitors, that is, an electrochemically stable solute (electrolyte) in a polar organic solvent. A solution dissolved in is used as appropriate. As the solvent for the electrolytic solution, propylene carbonate, butylene carbonate, γ-butyrolactone, acetonitrile, dimethylformamide, 1,2-dimethoxyethane, sulfolane, nitromethane, etc. are preferably used.
電解液の溶質としては、たとえば過塩素酸、６フツ化リ
ン酸、４フツ化ホウ酸、パーフルオロアルキルスルホン
酸などのアルカリ金属塩、アンモニウム塩、アミン塩、
テトラアルキルアンモニウム塩、テトラアルキルホスホ
ニウム塩などがあげられ、これらの溶質を前記の溶媒に
０．１〜３．０Ｍ ／ ｌ、好ましくは０．５〜１．５
Ｍ／ｌの濃度で溶解させた電解液が好適に使用される。Examples of solutes in the electrolytic solution include alkali metal salts, ammonium salts, amine salts, such as perchloric acid, hexafluorophosphoric acid, tetrafluoroboric acid, and perfluoroalkylsulfonic acid.
Examples include tetraalkylammonium salts and tetraalkylphosphonium salts, and these solutes are added to the above solvent at a concentration of 0.1 to 3.0 M/l, preferably 0.5 to 1.5
An electrolytic solution dissolved at a concentration of M/l is preferably used.
［実施例］
次に実施例及び比較例を説明する。本発明の実施例及び
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
の電気二重層コンデンサのユニットセル（直径２Ｇ＋＊
ｍ、厚さ２．０ｍｍ）を次のようにして作製した。まず
、活性炭粉末（比表面積的２０００ｍ”／ ｇ ）に１
０重量％のポリテトラフルオロエチレンを添加して湿式
混線によってシート化した。かかるシートを円板状に打
ち抜いて分極性電極ｌ（直径１５鳳鵬、厚さ０．７騰ｌ
）とし、これと同一の組成、形状を有する分極性電極２
とを第１表に示した種々のイオン交換体を有する前記構
造式においてｍ＝ｏ、ｎ＝３より成る膜状物（実施例１
〜１１）、ｍ＝１．ｎ＝２より成る膜状物（実施例１２
．１３）のセパレータ（直径１７ｍｍ） ３を介してス
テンレス鋼製のキャップ４およびステンレス鋼製のキャ
ップ４およびステンレス製の缶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、０．５モルのテトラ
エチルホスホニウムテトラフルオロボレートを１文の炭
酸プロピレンに溶解した電解液を注入して分極性電極１
．２及びセパレータ３中にこの電解液を充分に含浸させ
た。そしてガスケット６を介してキャップ４及び缶５の
端部をかしめて封口し一体化した。かくして作製したユ
ニットセルに２．８ｖの電圧を印加した際の３０分後の
漏れ電流値及び交流２端子法（周波数（１ｋＨｚ ）に
よって内部抵抗を測定した。[Example] Next, an example and a comparative example will be described. Common to the Examples and Comparative Examples of the present invention is a coin-shaped electric double layer capacitor unit cell (diameter 2G+*
m, thickness 2.0 mm) was produced as follows. First, activated carbon powder (specific surface area 2000 m”/g) was
0% by weight of polytetrafluoroethylene was added and formed into a sheet by wet cross-wiring. This sheet was punched out into a disk shape to form a polarizable electrode (diameter: 15 mm, thickness: 0.7 mm).
), and a polarizable electrode 2 having the same composition and shape as this
A film-like material (Example 1
~11), m=1. Film-like material consisting of n=2 (Example 12
．． 13) is housed in an outer container consisting of a stainless steel cap 4 and a stainless steel can 5 via a separator (diameter 17 mm) 3. Next, an electrolytic solution in which 0.5 mol of tetraethylphosphonium tetrafluoroborate was dissolved in 1 ml of propylene carbonate was injected into the unit cell, and the polarizable electrode 1
．． 2 and separator 3 were sufficiently impregnated with this electrolyte. Then, the end portions of the cap 4 and the can 5 were caulked via the gasket 6 to seal and integrate them. A leakage current value after 30 minutes when a voltage of 2.8 V was applied to the thus produced unit cell and internal resistance were measured by an AC two terminal method (frequency (1 kHz)).
結果を第１表に示した。The results are shown in Table 1.
第 １ 表
衣イオン交換容量 １．９ミリ当量／ｇ−乾燥樹脂［発
明の効果］
本発明によればイオン交換体より成る膜状物をセパレー
タに用いることで低内部抵抗、低漏れ電流を有する電気
二重層コンデンサを作製し得る。1. Outer coating ion exchange capacity 1.9 milliequivalents/g - dry resin [Effects of the invention] According to the present invention, by using a membrane material made of an ion exchanger as a separator, it has low internal resistance and low leakage current. Electric double layer capacitors can be produced.
第１図は本発明による電気二重層コンデンサの一実施例
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・・・パッキングFIG. 1 is a partial sectional view showing an embodiment of an electric double layer capacitor according to the present invention. 1.2... Polarizable electrode 3... Separator 4... Cap 5... Can 6... Packing
Claims (1)
層を利用する電気二重層コンデンサにおいて、セパレー
タにイオン交換体より成る膜状物を用いることを特徴と
する電気二重層コンデンサ。 ２）イオン交換体が、下記構造式で表される重合体であ
る請求項１記載の電気二重層コンデンサ。 ▲数式、化学式、表等があります▼ ただし、ｍは０又は１、ｎは１〜５の整数、ＲはＣＯ＿
２Ｘ，ＳＯ＿３Ｘ，ＰＯ＿３Ｘ（ＸはＬｉ，Ｎａ，Ｋ，
Ｎａ，ＮＨ＿４，第４級アンモニウム基または第４級ホ
スホニウム基）のいずれかである。[Claims] 1) An electric double layer capacitor that utilizes an electric double layer formed at the interface between a polarizable electrode and an electrolytic solution, characterized in that a membrane material made of an ion exchanger is used as a separator. Electric double layer capacitor. 2) The electric double layer capacitor according to claim 1, wherein the ion exchanger is a polymer represented by the following structural formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, m is 0 or 1, n is an integer from 1 to 5, and R is CO_
2X, SO_3X, PO_3X (X is Li, Na, K,
Na, NH_4, quaternary ammonium group, or quaternary phosphonium group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63045918A JPH01222425A (en) | 1988-03-01 | 1988-03-01 | Electric double layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63045918A JPH01222425A (en) | 1988-03-01 | 1988-03-01 | Electric double layer capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01222425A true JPH01222425A (en) | 1989-09-05 |
Family
ID=12732626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63045918A Pending JPH01222425A (en) | 1988-03-01 | 1988-03-01 | Electric double layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01222425A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6631074B2 (en) | 2000-05-12 | 2003-10-07 | Maxwell Technologies, Inc. | Electrochemical double layer capacitor having carbon powder electrodes |
| US6804108B2 (en) | 2000-05-12 | 2004-10-12 | Maxwell Electronics, Inc. | Electrochemical double layer capacitor having carbon powder electrodes |
| US6813139B2 (en) | 2001-11-02 | 2004-11-02 | Maxwell Technologies, Inc. | Electrochemical double layer capacitor having carbon powder electrodes |
-
1988
- 1988-03-01 JP JP63045918A patent/JPH01222425A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6631074B2 (en) | 2000-05-12 | 2003-10-07 | Maxwell Technologies, Inc. | Electrochemical double layer capacitor having carbon powder electrodes |
| US6804108B2 (en) | 2000-05-12 | 2004-10-12 | Maxwell Electronics, Inc. | Electrochemical double layer capacitor having carbon powder electrodes |
| US6813139B2 (en) | 2001-11-02 | 2004-11-02 | Maxwell Technologies, Inc. | Electrochemical double layer capacitor having carbon powder electrodes |
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