JPH0855761A - Electric double layer capacitor and manufacture - Google Patents
Electric double layer capacitor and manufactureInfo
- Publication number
- JPH0855761A JPH0855761A JP6215371A JP21537194A JPH0855761A JP H0855761 A JPH0855761 A JP H0855761A JP 6215371 A JP6215371 A JP 6215371A JP 21537194 A JP21537194 A JP 21537194A JP H0855761 A JPH0855761 A JP H0855761A
- Authority
- JP
- Japan
- Prior art keywords
- double layer
- electric double
- layer capacitor
- activated carbon
- fluoropolymer
- 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.)
- Withdrawn
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/42—Powders or particles, e.g. composition thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は電気二重層キャパシタお
よびその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric double layer capacitor and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】従来の電気二重層キャパシタは、集電体
上に活性炭電極層を設けた２枚の電極の間にセパレータ
を介在させて、これらを電解液と共に金属ケース、封口
板および両者を絶縁するガスケットによって密封する
か、もしくは電極とセパレータとを巻回することにより
電気二重層キャパシタ素子を構成し、この素子に電解液
を含浸させてアルミニウムケース内に収納し、このアル
ミニウムケースの開口部に電解液が蒸発しないように封
口部材を配置することにより構成している。2. Description of the Related Art In a conventional electric double layer capacitor, a separator is interposed between two electrodes provided with an activated carbon electrode layer on a current collector, and these are put together with an electrolytic solution into a metal case, a sealing plate and both. An electric double layer capacitor element is formed by sealing with an insulating gasket or by winding an electrode and a separator, and the element is impregnated with an electrolytic solution and housed in an aluminum case. The sealing member is arranged so that the electrolytic solution does not evaporate.
【０００３】また、大電流大容量向けに積層平板型の電
気二重層キャパシタも提案されている（特開平４−１５
４１０６、特開平３−２０３３１１、特開平４−２８６
１０８）。この電気二重層キャパシタは、矩形に成型さ
れた正極と負極を、セパレータを正負両極の間に介在さ
せて、交互に重ねて電極積層体を形成し、正極と負極の
端部に正極リード部材および負極リード部材をかしめに
より接続して電気二重層キャパシタ素子を形成し、この
電気二重層キャパシタ素子をケースに収納して、電解液
を素子に含浸し、上蓋で密閉することにより構成されて
いる。Further, a laminated flat plate type electric double layer capacitor has been proposed for large current and large capacity (Japanese Patent Laid-Open No. 4-15).
4106, JP-A-3-203311, and JP-A-4-286.
108). In this electric double layer capacitor, a positive electrode and a negative electrode formed in a rectangular shape are alternately stacked with a separator interposed between the positive and negative electrodes to form an electrode laminate, and a positive electrode lead member and a positive electrode lead member are provided at the ends of the positive electrode and the negative electrode. The negative electrode lead member is connected by caulking to form an electric double layer capacitor element, the electric double layer capacitor element is housed in a case, the element is impregnated with an electrolytic solution, and the element is sealed with an upper lid.
【０００４】従来、電気二重層キャパシタの電極を製造
するには、金属箔を集電体とし、バインダーとしてのポ
リテトラフルオロエチレンによって結合された活性炭と
導電性付与剤とを用いた電極層を集電体と共に圧延ロー
ラーにかけることによって、薄型電極を作成したり（特
公昭５４−１２６２０号）、活性炭粉末、含フッ素ポリ
マー及びメチルアルコールからなるペーストをアルミニ
ウムネット上に塗布したり（特開平４−１６２５１０
号）、活性炭粉末とアセチレンブラックと水とメタノー
ル混合溶液にカルボキシメチルセルロース水溶液を添加
したスラリーを粗面化したアルミニウム箔に付着させた
り（特開平４−１６２５１０号）、活性炭粉末とアセチ
レンブラックにバインダーとしてポリテトラフルオロエ
チレン水性ディスパージョンおよびポリビニルピロリド
ンを加えた混合物をアルミニウムエキスパンドメタルに
付着せしめたり（米国特許４，３２７，４００号）する
方法が提案されている。Conventionally, in order to manufacture an electrode of an electric double layer capacitor, a metal foil is used as a current collector, and an electrode layer using activated carbon bonded by polytetrafluoroethylene as a binder and a conductivity-imparting agent is collected. A thin electrode can be prepared by applying it to a rolling roller together with an electric body (Japanese Patent Publication No. 54-12620), or a paste composed of activated carbon powder, a fluoropolymer and methyl alcohol can be applied onto an aluminum net (Japanese Patent Laid-Open No. 4-206). 162510
No. 4), activated carbon powder, acetylene black, a mixture of water and methanol mixed with a carboxymethyl cellulose aqueous solution is attached to a roughened aluminum foil (JP-A-4-162510), or activated carbon powder and acetylene black are used as a binder. A method of depositing a mixture of polytetrafluoroethylene aqueous dispersion and polyvinylpyrrolidone on aluminum expanded metal (US Pat. No. 4,327,400) has been proposed.
【０００５】[0005]
【発明が解決しようとする課題】自動車向け等のパワー
用途向けに対しては単位体積当たりの高い容量と低い内
部抵抗を同時に満足する高エネルギー密度かつ高出力密
度の電気二重層キャパシタが要求され、また、メモリー
バックアップ用の電気二重層キャパシタに対しても内部
抵抗の低減が望まれている。しかしながら、上記の方法
で製造される従来の電気二重層キャパシタの特性は実用
上まだ不満足なものであった。For power applications such as automobiles, an electric double layer capacitor having a high energy density and a high output density which simultaneously satisfies a high capacity per unit volume and a low internal resistance is required. Further, reduction in internal resistance is also desired for electric double layer capacitors for memory backup. However, the characteristics of the conventional electric double layer capacitor manufactured by the above method are still unsatisfactory in practical use.
【０００６】例えば、ポリビニルピロリドンは水溶性で
あると共に、電気二重層キャパシタに用いられる有機電
解液、例えばプロピレンカーボネートに溶解して電気二
重層キャパシタの特性を劣化させる欠点がある。バイン
ダーとして用いられているポリテトラフルオロエチレン
はいずれの溶媒にも溶けないため、活性炭および導電性
付与剤との均一な混合が困難であり、良好なバインダー
とはならない難点がある。For example, polyvinylpyrrolidone is water-soluble and has a drawback that it dissolves in an organic electrolytic solution used for electric double layer capacitors, such as propylene carbonate, and deteriorates the characteristics of the electric double layer capacitors. Since polytetrafluoroethylene used as a binder is insoluble in any solvent, it is difficult to uniformly mix the activated carbon and the conductivity-imparting agent, and there is a problem that a good binder cannot be obtained.
【０００７】従って、本発明の目的は、上記課題を解決
し、内部抵抗の小さい電気二重層キャパシタを提供する
ことにある。Therefore, an object of the present invention is to solve the above problems and provide an electric double layer capacitor having a small internal resistance.
【０００８】[0008]
【課題を解決するための手段】本発明によれば、セパレ
ータを挟んで対向している集電体付きの分極性電極と電
解液とを内蔵する電気二重層キャパシタであって、前記
分極性電極がバインダーで結合された高比表面積活性炭
と導電性付与剤とを主要構成要素とするものであり、前
記バインダーが有機溶剤に可溶の含フッ素ポリマーであ
ることを特徴と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 electric double layer capacitor containing a polarizable electrode with a current collector and an electrolytic solution, which are opposed to each other with a separator interposed therebetween. Is a high specific surface area activated carbon bonded with a binder and a conductivity-imparting agent as a main component, the electric double layer capacitor characterized in that the binder is a fluorine-containing polymer soluble in an organic solvent. Provided.
【０００９】また、本発明によれば、高比表面積活性炭
と、導電性付与剤と、有機溶剤に可溶の含フッ素ポリマ
ーと、含フッ素ポリマーを溶解し得る有機溶剤とを主と
して混合したスラリーを集電体上にコートし、その後乾
燥して前記有機溶剤を除去する工程を有することを特徴
とする上記電気二重層キャパシタの製造方法が提供され
る。Further, according to the present invention, a slurry obtained by mainly mixing high specific surface area activated carbon, a conductivity-imparting agent, a fluoropolymer soluble in an organic solvent, and an organic solvent capable of dissolving the fluoropolymer is prepared. There is provided a method for producing the electric double layer capacitor, which comprises a step of coating on a current collector and then drying to remove the organic solvent.
【００１０】電気二重層キャパシタの分極性電極のバイ
ンダーとして、有機溶剤に可溶の含フッ素ポリマーを用
いれば、含フッ素ポリマーを有機溶剤に溶かした溶液に
高比表面積活性炭と導電性付与剤とを均一に混合するこ
とが可能となり、その後、有機溶剤を除去すれば、高比
表面積活性炭と導電性付与剤とがバインダーと均一に混
合された分極性電極が得られ、その結果、電気二重層キ
ャパシタの内部抵抗を低くすることができる。また、含
フッ素ポリマーは電気二重層キャパシタに用いられるプ
ロピレンカーボネート等の有機電解液に難溶であるの
で、電解液を変質して電気二重層キャパシタの特性を劣
化させることもない。さらに、含フッ素ポリマーは耐熱
性と耐薬品性にも優れているので、信頼性の高い電気二
重層キャパシタが得られる。If a fluoropolymer soluble in an organic solvent is used as a binder for a polarizable electrode of an electric double layer capacitor, a solution prepared by dissolving the fluoropolymer in an organic solvent contains a high specific surface area activated carbon and a conductivity-imparting agent. It becomes possible to mix uniformly, and if the organic solvent is removed thereafter, a polarizable electrode in which the high specific surface area activated carbon and the conductivity-imparting agent are uniformly mixed with the binder is obtained, and as a result, the electric double layer capacitor is obtained. The internal resistance of can be lowered. Further, since the fluoropolymer is hardly soluble in the organic electrolytic solution such as propylene carbonate used for the electric double layer capacitor, it does not deteriorate the characteristics of the electric double layer capacitor by modifying the electrolytic solution. Further, since the fluoropolymer is excellent in heat resistance and chemical resistance, a highly reliable electric double layer capacitor can be obtained.
【００１１】この場合に使用される架橋剤を用いない含
フッ素ポリマーとしては、少量でも大きい結合強度が得
られるので、ポリフッ化ビニリデン｛−（ＣＦ2 −ＣＨ
2 ）n −｝が好ましく、ポリフッ化ビニリデンのなかで
も融点１５６〜１８２℃、粒径１〜１０ミクロンのもの
が特に好ましい。この含フッ素ポリマーを溶解し得る有
機溶剤としては、Ｎメチルピロリドン、トルエン、エチ
ルアセテート、ジメチルフタレート等が、含フッ素ポリ
マーに対する溶解度が大きく使用量を少なくできるの
で、好ましく用いられる。例えば、融点１５６〜１８２
℃、粒径１〜１０ミクロンのポリフッ化ビニリデンをこ
れらの有機溶媒に溶解した溶液に活性炭粉末等の高比表
面積導電体と導電性付与剤粉末とを添加混合してスラリ
ーとなし、集電体箔上にコートせしめ、乾燥せしめて溶
剤を除去することによって分極性電極を形成する。As the fluorine-containing polymer which does not use a cross-linking agent used in this case, since a large bond strength can be obtained even in a small amount, polyvinylidene fluoride {-(CF 2 -CH
2 ) n −} is preferable, and among polyvinylidene fluoride, those having a melting point of 156 to 182 ° C. and a particle diameter of 1 to 10 μm are particularly preferable. As the organic solvent capable of dissolving the fluoropolymer, N-methylpyrrolidone, toluene, ethyl acetate, dimethyl phthalate and the like are preferably used since they have a large solubility in the fluoropolymer and can be used in a small amount. For example, melting point 156-182
A high-specific surface area conductor such as activated carbon powder and a conductivity-imparting agent powder are added to and mixed with a solution prepared by dissolving polyvinylidene fluoride having a particle diameter of 1 to 10 μm in these organic solvents to form a slurry. The polarizable electrodes are formed by coating on foil and drying to remove the solvent.
【００１２】また、更にプレスしたり、含フッ素ポリマ
ーの融点以上に加熱すると、分極性電極が緻密かつ強固
になり、その結果、電気二重層キャパシタの内部抵抗が
小さくなるなど、その特性が向上するので好ましい。含
フッ素ポリマーの融点以上に加熱しつつプレスすると特
性の向上が著しいので、特に好ましい。Further, when the electrode is further pressed or heated above the melting point of the fluoropolymer, the polarizable electrode becomes dense and strong, and as a result, the internal resistance of the electric double layer capacitor is reduced and its characteristics are improved. Therefore, it is preferable. Pressing while heating above the melting point of the fluoropolymer is particularly preferable because the characteristics are remarkably improved.
【００１３】本発明の電気二重層キャパシタを製造する
他の好ましい方法としては、含フッ素ポリマーとポリマ
ー硬化剤を有機溶剤に溶かした溶液に、高比表面積活性
炭と導電性付与剤とを添加混合してスラリーとなし、こ
のスラリーを集電体上に付着コートせしめた後、乾燥と
加熱により、有機溶剤の除去とポリマーの架橋を行な
い、分極性電極を集電体上に形成する方法が挙げられ
る。As another preferable method for producing the electric double layer capacitor of the present invention, a high specific surface area activated carbon and a conductivity-imparting agent are added and mixed to a solution prepared by dissolving a fluoropolymer and a polymer curing agent in an organic solvent. A slurry, and after coating the slurry on the current collector by adhesion, the organic solvent is removed and the polymer is crosslinked by drying and heating to form a polarizable electrode on the current collector. .
【００１４】架橋剤を用いる含フッ素ポリマーとしては
多くのポリマーが使用できるが、フルオロオレフィンビ
ニルエーテル共重合体｛−（ＣＦ2 −ＣＦ2 ）n −（Ｃ
Ｈ2−ＣＨ（ＯＲ））m −｝の架橋ポリマーを使用する
のが好ましい。耐熱性、耐薬品性に優れており、少量で
も大きい結合強度が得られるからである。架橋剤として
は、好ましくは、ポリイソシアネート類、アミン類、ビ
スフェノール類、パーオキサイド類、ポリアミン類が用
いられる。この含フッ素ポリマーと架橋剤を組み合せた
ものは、ルミフロンの商品名（旭硝子社製）で市販され
ている。この場合に使用される有機溶剤としては、入手
が容易で安価であるので、トルエン、キシレン等が好ま
しい。例えば、上記ポリマーと架橋剤とをトルエン、キ
シレン等の有機溶剤に溶解せしめた溶液に、活性炭粉末
等の高比表面積導電体と導電性付与剤粉末とを添加混合
してスラリーとなし、このスラリーを集電体箔上に付着
コートせしめ、５０〜１００℃で乾燥して有機溶剤を除
去し、１００〜１８０℃に加熱することにより、架橋硬
化させて分極性電極を形成する。[0014] As the fluorine-containing polymer using a crosslinking agent are a number of polymers can be used, fluoroolefin vinyl ether copolymer {- (CF 2 -CF 2) n - (C
H 2 -CH (OR)) m - is preferred to use a crosslinked polymer}. This is because it has excellent heat resistance and chemical resistance, and a large bond strength can be obtained even with a small amount. As the cross-linking agent, polyisocyanates, amines, bisphenols, peroxides and polyamines are preferably used. A combination of this fluoropolymer and a crosslinking agent is commercially available under the trade name of Lumiflon (manufactured by Asahi Glass Co., Ltd.). As the organic solvent used in this case, toluene, xylene and the like are preferable because they are easily available and inexpensive. For example, a solution prepared by dissolving the polymer and the cross-linking agent in an organic solvent such as toluene or xylene is added to and mixed with a high specific surface area conductor such as activated carbon powder and a conductivity-imparting agent powder to form a slurry. Is coated on a collector foil, dried at 50 to 100 ° C. to remove the organic solvent, and heated at 100 to 180 ° C. to crosslink and cure to form a polarizable electrode.
【００１５】架橋剤を用いる含フッ素ポリマーの他の例
としては、フルオロオレフィン共重合体｛−（ＣＦ2 −
ＣＦ2 ）n −（ＣＨ2 −ＣＨ（ＣＨ3 ））m −｝の架橋
ポリマーを使用するのが好ましい。耐熱性、耐薬品性に
優れており、少量でも大きい結合強度が得られるからで
ある。この場合の架橋剤としてはアミン類、ビスフェノ
ール類、パーオキサイド類等が好ましく用いられる。こ
のポリマーと架橋剤の組み合せは、エイトシールの商品
名（旭硝子社製）で市販されている。この場合に使用さ
れる有機溶剤としては、メチルエチルケトン、エチルア
セテート等がこれ等に対する溶解性が良好なので好まし
い。例えば、上記含フッ素ポリマーと架橋剤とを、メチ
ルエチルケトン、エチルアセテート等の有機溶剤に溶解
せしめた溶液に、活性炭粉末等の高比表面積活性炭と導
電性付与剤粉末とを添加混合してスラリーとなし、この
スラリーを集電体箔上に塗布し、５０〜１００℃で乾燥
後、１８０〜２２０℃で加熱硬化させて分極性電極を形
成する。このような架橋タイプの含フッ素ポリマー場
合、主剤と硬化剤の配合比率は一般的に５対１程度が好
ましく採用される。As another example of the fluoropolymer using a crosslinking agent, a fluoroolefin copolymer {-(CF 2-
CF 2) n - (CH 2 -CH (CH 3)) m -} is preferable to use a crosslinked polymer. This is because it has excellent heat resistance and chemical resistance, and a large bond strength can be obtained even with a small amount. In this case, amines, bisphenols, peroxides and the like are preferably used as the crosslinking agent. The combination of this polymer and the cross-linking agent is commercially available under the trade name of Eightseal (manufactured by Asahi Glass Co., Ltd.). As the organic solvent used in this case, methyl ethyl ketone, ethyl acetate and the like are preferable because they have good solubility in them. For example, the fluoropolymer and the cross-linking agent are dissolved in an organic solvent such as methyl ethyl ketone or ethyl acetate, and a high specific surface area activated carbon such as activated carbon powder and a conductivity-imparting agent powder are added and mixed to form a slurry. The slurry is applied on a collector foil, dried at 50 to 100 ° C., and then heat-cured at 180 to 220 ° C. to form a polarizable electrode. In the case of such a cross-linking type fluoropolymer, the compounding ratio of the main agent and the curing agent is generally preferably about 5 to 1.
【００１６】また、このような架橋ポリマーを用いる場
合であっても、更にプレスしたり、架橋含フッ素ポリマ
ーの融点以上に加熱することによって、分極性電極が緻
密かつ強固になり、その結果、内部抵抗を小さくできる
など電気二重層キャパシタの特性を向上させることがで
きる。架橋含フッ素ポリマーの融点以上に加熱しつつプ
レスすることによってさらに特性が向上する。Even when such a crosslinked polymer is used, the polarizable electrode becomes dense and strong by further pressing or heating above the melting point of the crosslinked fluorine-containing polymer, and as a result, the inside of the polarizable electrode is increased. It is possible to improve the characteristics of the electric double layer capacitor such that the resistance can be reduced. The characteristics are further improved by pressing while heating above the melting point of the crosslinked fluoropolymer.
【００１７】本発明の高比表面積活性炭としては、好ま
しくは比表面積が大きい活性炭が用いられる。活性炭と
しては、平均粒径が０．１μｍ以上、２０μｍ以下、比
表面積が１５００〜３０００ｍ2 ／ｇの粉末を使用する
と容量が大きくなるので好ましい。活性炭粉末には活性
炭繊維を混合し、併用することもできる。As the high specific surface area activated carbon of the present invention, activated carbon having a large specific surface area is preferably used. As the activated carbon, it is preferable to use a powder having an average particle size of 0.1 μm or more and 20 μm or less and a specific surface area of 1500 to 3000 m 2 / g because the capacity becomes large. Activated carbon fibers may be mixed with the activated carbon powder and used in combination.
【００１８】導電性付与剤としては、アセチレンブラッ
ク、カーボンブラック、ケッチェンブラック、黒鉛、グ
ラファイトウイスカー、酸化ルテニウム等が好ましく用
いられる。As the conductivity-imparting agent, acetylene black, carbon black, Ketjen black, graphite, graphite whiskers, ruthenium oxide and the like are preferably used.
【００１９】活性炭、導電性付与剤およびバインダーか
らなる分極性電極においては、実用的に好ましい容量と
内部抵抗を得るために、活性炭が６０〜９０重量％、導
電性付与剤が５〜３０重量％、バインダーが５〜２５重
量％の範囲とすることが好ましい。In a polarizable electrode comprising activated carbon, a conductivity-imparting agent and a binder, 60 to 90% by weight of activated carbon and 5 to 30% by weight of conductivity-imparting agent are used in order to obtain a practically preferable capacity and internal resistance. The binder content is preferably in the range of 5 to 25% by weight.
【００２０】集電体としては、電解液中で化学的、電気
化学的に安定な導電体が好ましく用いられる。電解液が
有機系の場合は、アルミニウム、ステンレス、チタン、
タンタル等が好適に用いられる。電解液が水溶液の場合
は、導電性ゴム、グラシーカーボン、グラファイト、ニ
ッケル、鉛等が好ましく選択される。集電体の形状につ
いては、特に制約がないが、箔、板、エキスパンド状等
が好ましく用いられる。特に箔状は電気二重層キャパシ
タの小型軽量化に適しているので特に好ましい。電気的
接触を良好とするため、集電体の表面は粗面化されてい
ることが好ましい。As the current collector, a conductor that is chemically and electrochemically stable in the electrolytic solution is preferably used. If the electrolyte is organic, aluminum, stainless steel, titanium,
Tantalum or the like is preferably used. When the electrolytic solution is an aqueous solution, conductive rubber, glassy carbon, graphite, nickel, lead and the like are preferably selected. The shape of the current collector is not particularly limited, but a foil, plate, expanded shape or the like is preferably used. The foil shape is particularly preferable because it is suitable for reducing the size and weight of the electric double layer capacitor. The surface of the current collector is preferably roughened in order to make good electrical contact.
【００２１】電解液には、硫酸水溶液、硫酸ナトリウム
水溶液、水酸化カリウム水溶液、テトラアルキルホスホ
ニウムテトラフルオロボレートのプロピレンカーボネー
ト溶液、テトラアルキルアンモニウムテトラフルオロボ
レートのプロピレンカーボネート溶液、ガンマブチロラ
クトン溶液またはスルホラン溶液等が好ましく用いられ
る。非水系有機電解液を使用すれば耐電圧を２．５〜
３．０Ｖと高くでき、耐電圧が１．０Ｖ前後の水溶液系
よりもエネルギー密度｛Ｅ＝（ＣＶ2 ）／２ （ここ
で、Ｅはエネルギー密度、Ｃは容量、Ｖは電圧であ
る。｝が４倍程度高くとれる点で好ましい。As the electrolytic solution, an aqueous solution of sulfuric acid, an aqueous solution of sodium sulfate, an aqueous solution of potassium hydroxide, a propylene carbonate solution of tetraalkylphosphonium tetrafluoroborate, a propylene carbonate solution of tetraalkylammonium tetrafluoroborate, a gamma butyrolactone solution or a sulfolane solution is used. It is preferably used. Withstand voltage of 2.5-
Energy density {E = (CV 2 ) / 2 (where E is energy density, C is capacity, and V is voltage) compared with an aqueous solution system that can be increased to 3.0 V and has a withstand voltage of about 1.0 V.} Is preferably about 4 times higher.
【００２２】[0022]
【実施例】以下、本発明の具体的な実施例について説明
するが、本発明はこれらの実施例によって限定されるも
のではない。EXAMPLES Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to these examples.
【００２３】［実施例１］活性炭粉末（比表面積１８０
０ｍ2 ／ｇ、平均粒径８μｍ）およびアセチレンブラッ
クにＮ−メチルピロリドンを添加し、アルミナボールを
用いてボールミル中で混合し、更にポリフッ化ビニリデ
ン粉末（融点１５６〜１８２℃）をＮ−メチルピロリド
ンに溶解せしめた溶液を添加し、再度ボールミル中で混
合し、活性炭、アセチレンブラック及びポリフッ化ビニ
リデンからなる固形分を１５重量％含むスラリーを得
た。固形分の組成は、活性炭７５重量％、アセチレンブ
ラック１４重量％、ポリフッ化ビニリデン１１重量％で
あった。このスラリーを厚さ８０ミクロンのアルミニウ
ムエッチング箔の片面に、バーコーターによりコートし
１００℃および１８５℃で乾燥した後、裏面に同様にコ
ートし１００℃および１８５℃で乾燥し、次いで１８５
℃でロール加熱プレスしてシート状電極を得た。得られ
たシート状電極から、図１に示すように、２枚の５８ｍ
ｍ×１３ｍｍの電極４、５を切り出した。電極４、５
は、それぞれ、アルミニウムエッチング箔からなる集電
体箔３の両面に、活性炭、アセチレンブラックおよびポ
リフッ化ビニリデンからなる分極性電極１、２がコート
された構成となっている。次に、分極性電極１、２の一
部を剥し、この部分にアルミニウム製タブ端子８、９を
溶接してそれぞれの電極４、５に接続し、電極４、５を
セパレータ６を介して巻回する。然る後、１３０℃で３
時間真空乾燥した。その後、１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含有するプロピレン
カーボネート溶液を巻回した電極４、５とセパレータ６
に含浸し、アルミニウムケース７中に挿入し、ブチルゴ
ム製の封口ゴム１０を介してカールして密封し、電気二
重層キャパシタ１００を作成した。この電気二重層キャ
パシタ１００の直径は８ｍｍであり、長さは２０ｍｍで
あった。[Example 1] Activated carbon powder (specific surface area 180
0 m 2 / g, average particle size 8 μm) and N-methylpyrrolidone were added to acetylene black and mixed in a ball mill using alumina balls, and then polyvinylidene fluoride powder (melting point 156 to 182 ° C.) was added to N-methylpyrrolidone. Was added and mixed again in a ball mill to obtain a slurry containing 15% by weight of solid content consisting of activated carbon, acetylene black and polyvinylidene fluoride. The composition of the solid content was 75% by weight of activated carbon, 14% by weight of acetylene black, and 11% by weight of polyvinylidene fluoride. This slurry was coated on one side of an 80-micron-thick aluminum etching foil with a bar coater and dried at 100 ° C. and 185 ° C., and then on the back side in the same manner and dried at 100 ° C. and 185 ° C., then 185
A sheet-shaped electrode was obtained by roll heating and pressing at ℃. From the obtained sheet electrode, as shown in FIG.
The electrodes 4 and 5 of m × 13 mm were cut out. Electrodes 4, 5
Has a structure in which polarizable electrodes 1 and 2 made of activated carbon, acetylene black and polyvinylidene fluoride are coated on both sides of a collector foil 3 made of an aluminum etching foil, respectively. Next, a part of the polarizable electrodes 1 and 2 is peeled off, aluminum tab terminals 8 and 9 are welded to these parts and connected to the respective electrodes 4 and 5, and the electrodes 4 and 5 are wound via a separator 6. Turn. After that, at 130 ℃ 3
Vacuum dried for an hour. Thereafter, electrodes 4 and 5 and a separator 6 wound with a propylene carbonate solution containing 1 mol of tetraethylphosphonium tetrafluoroborate were wound.
Then, the electric double layer capacitor 100 was manufactured by curling and sealing it through a sealing rubber 10 made of butyl rubber. The electric double layer capacitor 100 had a diameter of 8 mm and a length of 20 mm.
【００２４】［実施例２］活性炭粉末（比表面積２５０
０ｍ2 ／ｇ，平均粒径６μｍ）とケッチェンブラック粉
末にトルエンを添加し、ボールミル中で混合した後、フ
ルオロオレフィンビニルエーテル共重合体を主剤としポ
リイソシアネート類を架橋剤とする商品名ルミフロンＬ
Ｆ２００Ｃ（旭硝子社製）を、主剤／硬化剤（架橋剤）
の重量比率を５／１として添加し、更にトルエンを添加
し、再度ボールミル中で混合し、活性炭、ケッチエンブ
ラック及びバインダーからなる固形分を１２重量％含む
スラリーを得た。幅１０ｃｍ、長さ３０ｃｍ、厚さ３０
μｍのアルミニウムエッチング箔の片面にこのスラリー
をドクターブレード法によりコートし、８０℃で３時間
乾燥した後１２０℃で３０分間硬化させ、次いで箔の裏
面にも同様にしてコートして乾燥、硬化させ、シート状
電極を得た。このシート状電極を５８ｍｍ×１３ｍｍの
大きさに切り出し、図１に示すような電極４、５を得
た。電極４、５は、それぞれ、アルミニウムエッチング
箔からなる集電体箔３の両面に、活性炭、アセチレンブ
ラックおよびポリイソシアネート類で架橋されたフルオ
ロオレフィンビニルエーテル共重合体からなる分極性電
極１、２がコートされた構成となっている。次に、分極
性電極１、２の一部を剥し、この部分にアルミニウム製
タブ端子８、９を溶接してそれぞれの電極４、５と接続
し、電極４、５をセパレータ６を介して巻回し、１３０
℃で５時間真空乾燥し、実施例１と同じ組成の電解液を
素子に含浸し、アルミニウムケース７中に挿入し、封口
ゴム１０を介してカールして密封し、電気二重層キャパ
シタ１００を作成した。この電気二重層キャパシタ１０
０の直径は８ｍｍであり、長さは２０ｍｍであった。[Example 2] Activated carbon powder (specific surface area 250
0 m 2 / g, average particle size 6 μm) and toluene were added to Ketjenblack powder and mixed in a ball mill, and then fluoroolefin vinyl ether copolymer was used as the main component and polyisocyanates as the crosslinking agent.
F200C (manufactured by Asahi Glass Co., Ltd.) as the main agent / hardening agent (crosslinking agent)
Was added at a weight ratio of 5/1, toluene was further added, and the mixture was mixed again in a ball mill to obtain a slurry containing 12% by weight of solid content consisting of activated carbon, Ketchen black and a binder. Width 10 cm, length 30 cm, thickness 30
This slurry was coated on one side of an aluminum etching foil having a thickness of μm by the doctor blade method, dried at 80 ° C. for 3 hours and then cured at 120 ° C. for 30 minutes, and then similarly coated on the back side of the foil, dried and cured. A sheet electrode was obtained. This sheet electrode was cut into a size of 58 mm × 13 mm to obtain electrodes 4 and 5 as shown in FIG. The electrodes 4 and 5 are coated with polarizable electrodes 1 and 2 made of a fluoroolefin vinyl ether copolymer cross-linked with activated carbon, acetylene black and polyisocyanates on both sides of a collector foil 3 made of an aluminum etching foil. It has been configured. Next, a part of the polarizable electrodes 1 and 2 is peeled off, aluminum tab terminals 8 and 9 are welded to these parts and connected to the respective electrodes 4 and 5, and the electrodes 4 and 5 are wound via a separator 6. Turn, 130
After vacuum drying at 5 ° C. for 5 hours, the element was impregnated with the electrolytic solution having the same composition as in Example 1, inserted into an aluminum case 7, and curled and sealed with a sealing rubber 10 to prepare an electric double layer capacitor 100. did. This electric double layer capacitor 10
The diameter of 0 was 8 mm and the length was 20 mm.
【００２５】［実施例３］活性炭粉末（比表面積２２０
０ｍ2 ／ｇ，平均粒径５μｍ）、ケッチェンブラックか
らなる混合物に酢酸ブチルを添加しボールミル中で混合
した。ついで、テトラフルオロエチレン−プロピレン共
重合体を主剤としアミン類を架橋剤とする商品名エイト
シールＦ−１２０５（旭硝子社製）を、主剤／硬化剤
（架橋剤）の重量比率を５／１として添加し、活性炭、
ケッチェンブラック及びバインダーからなる固形分を１
２重量％含むスラリーを得た。あらかじめ部分的にテー
プによりマスキングされた、幅１０ｃｍ厚み５０ミクロ
ンの粗面化されたステンレス箔の片面にダイコーターに
よりこのスラリーを塗布した。ついで１００℃で３０分
乾燥した後、２００℃で３０分間硬化せしめた。次に、
箔の裏面にも同様にスラリーを塗布し、乾燥、硬化せし
め、図２に示したように、マスキングテープをはがし
て、２ｃｍ×４ｃｍの活性炭の付着していない集電端子
２０、２１と１０ｃｍ×１０ｃｍの活性炭の付着した部
分２２、２３とをそれぞれ有する電極２６、２７を打ち
抜いた。この活性炭の付着した部分２２、２３には、活
性炭、ケッチェンブラックおよびアミン類で架橋された
テトラフルオロエチレン−プロピレン共重合体からなる
分極性電極がコートされている。次に、電極２６、２７
をセパレータ２８を介して対向せしめ、合計で３０枚の
正極２７と３０枚の負極２６とをセパレータ２８を介し
て順次積層し、それぞれの集電端子２０および２１を集
電体リード３０および３１にかしめ接続して素子を形成
した。この素子を、２００℃で３時間真空乾燥した後ア
ルミニウムケース３２中に収納し、正極端子３３および
負極端子３４を有する上蓋３５で密封し、注液口（図示
せず）より１モル／リット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含有するプロピレンカーボ
ネート溶液を素子に含浸して、角型電気二重層キャパシ
タ２００を作成した。この角型電気二重層キャパシタ２
００の寸法は、高さが１２７ｍｍ、幅が１１４ｍｍ、厚
さが３０ｍｍであった。[Example 3] Activated carbon powder (specific surface area 220
Butyl acetate was added to a mixture consisting of Ketjen black (0 m 2 / g, average particle size 5 μm) and mixed in a ball mill. Then, trade name Eightseal F-1205 (manufactured by Asahi Glass Co., Ltd.) containing tetrafluoroethylene-propylene copolymer as a main agent and amines as a cross-linking agent was used with the weight ratio of the main agent / curing agent (cross-linking agent) being 5/1. Add, activated carbon,
1 solid content consisting of Ketjen Black and binder
A slurry containing 2% by weight was obtained. This slurry was applied by a die coater to one surface of a roughened stainless steel foil having a width of 10 cm and a thickness of 50 μm, which was partially masked in advance with a tape. Then, after drying at 100 ° C. for 30 minutes, it was cured at 200 ° C. for 30 minutes. next,
Similarly, the slurry is applied to the back surface of the foil, dried and cured, and the masking tape is peeled off as shown in FIG. The electrodes 26 and 27 having the portions 22 and 23 having 10 cm of activated carbon attached thereto were punched out. The active carbon-attached portions 22 and 23 are coated with a polarizable electrode made of tetrafluoroethylene-propylene copolymer cross-linked with activated carbon, Ketjen black and amines. Next, the electrodes 26, 27
Are opposed to each other via a separator 28, and a total of 30 positive electrodes 27 and 30 negative electrodes 26 are sequentially laminated via the separator 28, and the respective current collecting terminals 20 and 21 are connected to current collector leads 30 and 31. A device was formed by caulking and connecting. This device was vacuum dried at 200 ° C. for 3 hours, then housed in an aluminum case 32, sealed with an upper lid 35 having a positive electrode terminal 33 and a negative electrode terminal 34, and 1 mol / liter from a liquid injection port (not shown). The element was impregnated with a propylene carbonate solution containing tetraethylphosphonium tetrafluoroborate to prepare a rectangular electric double layer capacitor 200. This square electric double layer capacitor 2
The size of 00 was 127 mm in height, 114 mm in width, and 30 mm in thickness.
【００２６】［実施例４］実施例１において、１８５℃
におけるロールプレスの替わりに、室温においてロール
プレスしたほかは実施例１と同様にして電気二重層キャ
パシタ１００を作製した。Example 4 In Example 1, 185 ° C.
An electric double layer capacitor 100 was manufactured in the same manner as in Example 1 except that the roll pressing was performed at room temperature instead of the roll pressing.
【００２７】［比較例１］実施例１と同じ活性炭粉末と
アセチレンブラックとを、水とメタノールの混合溶液中
に均一に分散させた分散液を作成し、一方では、カルボ
キシメチルセルロースを水に溶解させた溶液を作成し
た。両液をボールミル中で混合して、活性炭、アセチレ
ンブラックおよびカルボキシメチルセルロースからなる
固形分を１５重量％含むスラリーを得た。固形分の組成
は、活性炭７５重量％、アセチレンブラック１４重量
％、カルボキシメチルセルロース１１重量％である。実
施例１と同じアルミニウムエッチング箔の両面に、バー
コーターによるコートと、１５０℃での乾燥をそれぞれ
施してシート状電極を得た。得られたシート状電極から
２枚の５８ｍｍ×１３ｍｍの電極４、５を切り出し、実
施例１と同様にして、直径８ｍｍ長さ２０ｍｍの電気二
重層キャパシタ１００を作製した。COMPARATIVE EXAMPLE 1 The same activated carbon powder and acetylene black as in Example 1 were uniformly dispersed in a mixed solution of water and methanol to prepare a dispersion, while carboxymethyl cellulose was dissolved in water. Prepared a solution. Both liquids were mixed in a ball mill to obtain a slurry containing 15% by weight of solid content composed of activated carbon, acetylene black and carboxymethyl cellulose. The composition of the solid content is 75% by weight of activated carbon, 14% by weight of acetylene black, and 11% by weight of carboxymethyl cellulose. Both sides of the same aluminum etching foil as in Example 1 were coated with a bar coater and dried at 150 ° C. to obtain a sheet electrode. Two 58 mm × 13 mm electrodes 4 and 5 were cut out from the obtained sheet-like electrode, and an electric double layer capacitor 100 having a diameter of 8 mm and a length of 20 mm was produced in the same manner as in Example 1.
【００２８】［比較例２］実施例１と同じ活性炭粉末と
アセチレンブラックにテトラフルオロエチレン微粉末を
水およびメタノールを加えてロール混練りし、実施例１
と同じアルミニウムエッチング箔からなる集電体箔の両
面にコートしてロール圧延し、シート状電極を形成し
た。集電体箔上の分極性電極の組成は、活性炭７５重量
％、アセチレンブラック１４重量％、ポリテトラフルオ
ロエチレン１１重量％であった。得られたシート状電極
から２枚の５８ｍｍ×１３ｍｍの電極４、５を切り出
し、実施例１と同様にして直径８ｍｍ長さ２０ｍｍの電
気二重層キャパシタ１００を作製した。[Comparative Example 2] The same activated carbon powder and acetylene black as in Example 1 were mixed with tetrafluoroethylene fine powder by adding water and methanol and roll-kneaded.
A sheet-shaped electrode was formed by coating both sides of a current collector foil made of the same aluminum etching foil as above and rolling. The composition of the polarizable electrode on the collector foil was 75% by weight of activated carbon, 14% by weight of acetylene black, and 11% by weight of polytetrafluoroethylene. Two 58 mm × 13 mm electrodes 4 and 5 were cut out from the obtained sheet-like electrode, and an electric double layer capacitor 100 having a diameter of 8 mm and a length of 20 mm was produced in the same manner as in Example 1.
【００２９】［比較例３］実施例１と同じ活性炭粉末と
アセチレンブラックの混合物に、ポリテトラフルオロエ
チレンを６０重量％含む水性デスパージョンと、ポリビ
ニルピロリドンとを添加してボールミル中で混合し、活
性炭とアセチレンブラックとポリテトラフルオロエチレ
ンとポリビニルピロリドンからなる固形分を１５重量％
含むスラリーを得た。固形分の組成は活性炭６５重量
％、アセチレンブラック１０重量％、ポリテトラフルオ
ロエチレン１２重量％、ポリビニルピロリドン１３重量
％である。実施例１と同じアルミニウムエッチング箔
に、このスラリーのバーコーターによるコートと１００
℃での乾燥を両面に施してシート状電極を得た。得られ
たシート状電極から２枚の５８ｍｍ×１３ｍｍの電極
４、５を切り出し、実施例１と同様にして直径８ｍｍ長
さ２０ｍｍの電気二重層キャパシタ１００を作製した。Comparative Example 3 To the same mixture of activated carbon powder and acetylene black as in Example 1, an aqueous dispersion containing 60% by weight of polytetrafluoroethylene and polyvinylpyrrolidone were added and mixed in a ball mill to obtain activated carbon. 15% by weight of solid content consisting of acetylene black, polytetrafluoroethylene and polyvinylpyrrolidone
A containing slurry was obtained. The composition of solids is 65% by weight of activated carbon, 10% by weight of acetylene black, 12% by weight of polytetrafluoroethylene and 13% by weight of polyvinylpyrrolidone. The same aluminum etching foil as in Example 1 was coated with this slurry using a bar coater and 100
Both sides were dried at ℃ to obtain a sheet electrode. Two 58 mm × 13 mm electrodes 4 and 5 were cut out from the obtained sheet-like electrode, and an electric double layer capacitor 100 having a diameter of 8 mm and a length of 20 mm was produced in the same manner as in Example 1.
【００３０】実施例１、２及び４並びに比較例１〜３の
電気二重層キャパシタ１００の定格電圧はいずれも２．
８Ｖである。実施例３の電気二重層キャパシタ２００の
定格電圧は２．５Ｖである。初期の容量と直流電流放電
により求めた初期内部抵抗とを測定した後、７０℃で定
格電圧を印加した状態で１０００時間経過した後に容量
と内部抵抗とを再び測定した。容量については、初期容
量からの容量変化率（％）を算出して示した。実施例１
から４および比較例１から３における測定結果を表１に
示す。The rated voltages of the electric double layer capacitors 100 of Examples 1, 2 and 4 and Comparative Examples 1 to 3 are all 2.
It is 8V. The rated voltage of the electric double layer capacitor 200 of Example 3 is 2.5V. After measuring the initial capacity and the initial internal resistance obtained by direct current discharge, the capacity and internal resistance were measured again after 1000 hours had passed with the rated voltage applied at 70 ° C. Regarding the capacity, the capacity change rate (%) from the initial capacity was calculated and shown. Example 1
To 4 and Comparative Examples 1 to 3 are shown in Table 1.
【００３１】[0031]
【表１】 [Table 1]
【００３２】表１によれば、本発明の実施例において
は、内部抵抗が小さい電気二重層キャパシタが得られて
いる。また、７０℃で２．８Ｖ印加したまま１０００時
間経過した後においても、本発明の実施例に係る電気二
重層キャパシタは初期容量からの容量変化率が小さく、
小さい内部抵抗が保持され、非常に信頼性と耐久性の高
い電気二重層キャパシタが得られている。さらに、実施
例１と実施例４とを比較すれば、１８５℃でロールプレ
スした実施例１の方が、室温でロールプレスした実施例
４よりも優れた特性を示していることがわかる。According to Table 1, in the examples of the present invention, electric double layer capacitors having a small internal resistance were obtained. In addition, even after 1000 hours elapsed while applying 2.8 V at 70 ° C., the electric double layer capacitors according to the examples of the present invention had a small rate of change in capacitance from the initial capacitance,
An electric double layer capacitor having a very low internal resistance and extremely high reliability and durability is obtained. Further, comparing Example 1 and Example 4, it can be seen that Example 1 roll-pressed at 185 ° C. exhibits better characteristics than Example 4 roll-pressed at room temperature.
【００３３】[0033]
【発明の効果】本発明によれば、内部抵抗が低く、信頼
性と耐久性の高い電気二重層キャパシタを得ることが出
来る。According to the present invention, an electric double layer capacitor having low internal resistance and high reliability and durability can be obtained.
【図１】本発明の実施例１、２及び４並びに比較例１〜
３の電気二重層キャパシタの構造を説明するための部分
断面斜視図である。FIG. 1 is a schematic diagram of Examples 1, 2 and 4 of the present invention and Comparative Examples 1
3 is a partial cross-sectional perspective view for explaining the structure of the electric double layer capacitor of FIG.
【図２】本発明の実施例３の角型電気二重層キャパシタ
に用いられる正極および負極の構造および積層方法を説
明するための斜視図である。FIG. 2 is a perspective view for explaining a structure and a stacking method of a positive electrode and a negative electrode used in a rectangular electric double layer capacitor of Example 3 of the present invention.
【図３】本発明の実施例３の角型電気二重層キャパシタ
の構造を説明するための部分断面斜視図である。FIG. 3 is a partial cross-sectional perspective view for explaining the structure of a rectangular electric double layer capacitor according to a third embodiment of the present invention.
１、２…分極性電極 ３…集電体箔 ４、５…電極 ６、２８…セパレータ ７…アルミニウムケース ８、９…アルミニウム製タブ端子 １０…封口ゴム ２０、２１…集電端子 ２２、２３…活性炭の付着した部分 ２６…負極 ２７…正極 ３０、３１…集電体リード ３２…アルミニウムケース ３３…正極端子 ３４…負極端子 ３５…上蓋 1, 2 ... Polarizable electrode 3 ... Current collector foil 4, 5 ... Electrode 6, 28 ... Separator 7 ... Aluminum case 8, 9 ... Aluminum tab terminal 10 ... Sealing rubber 20, 21 ... Current collecting terminal 22, 23 ... Active carbon attached portion 26 ... Negative electrode 27 ... Positive electrode 30, 31 ... Current collector lead 32 ... Aluminum case 33 ... Positive electrode terminal 34 ... Negative electrode terminal 35 ... Top lid
フロントページの続き (72)発明者 森本 剛 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内 (72)発明者 池田 克治 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内 (72)発明者 小林 真直 神奈川県藤沢市辻堂新町２丁目２番１号 エルナー株式会社内Front page continuation (72) Inventor Go Morimoto 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory (72) Inventor Katsuji Ikeda 1150, Hazawa-machi, Kanagawa-ku Yokohama City, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Center (72) Inventor Masanao Kobayashi 2-2-1 Tsujido Shinmachi, Fujisawa City, Kanagawa Elner Co., Ltd.
Claims (6)
きの分極性電極と電解液とを内蔵する電気二重層キャパ
シタであって、前記分極性電極がバインダーで結合され
た高比表面積活性炭と導電性付与剤とを主要構成要素と
するものであり、前記バインダーが有機溶剤に可溶の含
フッ素ポリマーであることを特徴とする電気二重層キャ
パシタ。1. An electric double layer capacitor containing a polarizable electrode with a current collector and an electrolytic solution, which are opposed to each other with a separator interposed therebetween, wherein the polarizable electrode has a high specific surface area activated carbon bonded with a binder. An electric double layer capacitor comprising: a conductive polymer and a conductivity-imparting agent as main components, wherein the binder is a fluoropolymer soluble in an organic solvent.
高比表面積活性炭、５〜２５重量％の前記バインダーお
よび残部の前記導電性付与剤を含むものである請求項１
記載の電気二重層キャパシタ。2. The polarizable electrode contains 60 to 90% by weight of the high specific surface area activated carbon, 5 to 25% by weight of the binder, and the balance of the conductivity imparting agent.
The electric double layer capacitor described.
デン、フルオロオレフィンビニルエーテル共重合ポリマ
ーまたはテトラフルオロエチレン−プロピレン共重合ポ
リマーである請求項１または２記載の電気二重層キャパ
シタ。3. The electric double layer capacitor according to claim 1, wherein the fluoropolymer is polyvinylidene fluoride, a fluoroolefin vinyl ether copolymer or a tetrafluoroethylene-propylene copolymer.
０ｍ2 ／ｇの比表面積を有するものであり、前記導電性
付与剤がアセチレンブラック及び／又はケッチェンブラ
ックであり、前記集電体が粗面化されたアルミニウム箔
又は粗面化されたステンレス箔であり、前記電解液が有
機電解液である請求項１〜３のいずれか１つに記載の電
気二重層キャパシタ。4. The high specific surface area activated carbon is 1500 to 300.
It has a specific surface area of 0 m 2 / g, the conductivity-imparting agent is acetylene black and / or Ketjen black, and the current collector is a roughened aluminum foil or a roughened stainless steel foil. The electric double layer capacitor according to any one of claims 1 to 3, wherein the electrolytic solution is an organic electrolytic solution.
素ポリマーの融点以上の温度で加熱プレスされたもので
ある請求項１〜４のいずれか１つに記載の電気二重層キ
ャパシタ。5. The electric double layer capacitor according to claim 1, wherein the polarizable electrode with the current collector is heated and pressed at a temperature equal to or higher than the melting point of the fluoropolymer.
機溶剤に可溶の含フッ素ポリマーと、前記含フッ素ポリ
マーを溶解し得る有機溶剤とを主として混合したスラリ
ーを集電体上にコートし、その後乾燥して前記有機溶剤
を除去する工程を有することを特徴とする請求項１記載
の電気二重層キャパシタの製造方法。6. A slurry in which a high specific surface area activated carbon, a conductivity-imparting agent, a fluoropolymer soluble in an organic solvent, and an organic solvent capable of dissolving the fluoropolymer are mainly mixed on a current collector. The method of manufacturing an electric double layer capacitor according to claim 1, further comprising a step of coating and then drying to remove the organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6215371A JPH0855761A (en) | 1994-08-16 | 1994-08-16 | Electric double layer capacitor and manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6215371A JPH0855761A (en) | 1994-08-16 | 1994-08-16 | Electric double layer capacitor and manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0855761A true JPH0855761A (en) | 1996-02-27 |
Family
ID=16671194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6215371A Withdrawn JPH0855761A (en) | 1994-08-16 | 1994-08-16 | Electric double layer capacitor and manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0855761A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6288888B1 (en) | 1998-12-25 | 2001-09-11 | Nec Corporation | Electric double layer capacitor |
| WO2003065391A1 (en) * | 2002-01-29 | 2003-08-07 | Power Systems Co., Ltd. | Electrode formulation for polarized electrode and method for preparation thereof, and polarized electrode using the electrode formulation |
| JP2003297701A (en) * | 2002-03-29 | 2003-10-17 | Tdk Corp | Electrochemical device and method of manufacturing the same |
| JP2003297696A (en) * | 2002-03-29 | 2003-10-17 | Tdk Corp | Electric double-layer capacitor and method of manufacturing the same |
| KR100479188B1 (en) * | 2001-02-06 | 2005-03-25 | 엔이씨 도낀 가부시끼가이샤 | Electric double layer capacitor with improved activated carbon electrodes |
| WO2005041225A1 (en) * | 2003-10-24 | 2005-05-06 | Zeon Corporation | Binder for electrode of electric double layer capacitor |
| WO2006068291A1 (en) * | 2004-12-21 | 2006-06-29 | Teijin Limited | Electric double layer capacitor |
| WO2006103967A1 (en) * | 2005-03-25 | 2006-10-05 | Matsushita Electric Industrial Co., Ltd. | Polarizable electrode, capacitor using same, and method for manufacturing polarizable electrode |
| JP2008072069A (en) * | 2006-09-11 | 2008-03-27 | Dynic Corp | Electrode material for electric double layer capacitor and method of manufacturing the same |
| JP2009123931A (en) * | 2007-11-15 | 2009-06-04 | Nichicon Corp | Electric double layer capacitor |
| US20130114183A1 (en) * | 2011-11-04 | 2013-05-09 | Samsung Electro-Mechanics Co., Ltd. | Electrode active material composition, method for preparing the same, and electrochemical capacitor using the same |
| US20130163146A1 (en) * | 2011-12-23 | 2013-06-27 | Samsung Electro-Mechanics Co., Ltd. | Electrode active material-conductive agent composite, method for preparing the same, and electrochemical capacitor comprising the same |
| KR20160140888A (en) | 2014-04-01 | 2016-12-07 | 스미토모 세이카 가부시키가이샤 | Binder for electric double-layer capacitor electrode, electric double-layer capacitor electrode comprising same binder, electric double-layer capacitor using same electrode, and electric apparatus |
| WO2017025792A1 (en) * | 2015-08-11 | 2017-02-16 | Юнаско Лимитед | Method of manufacturing an electrode for an electrochemical double layer capacitor |
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-
1994
- 1994-08-16 JP JP6215371A patent/JPH0855761A/en not_active Withdrawn
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|---|---|---|---|---|
| US6288888B1 (en) | 1998-12-25 | 2001-09-11 | Nec Corporation | Electric double layer capacitor |
| KR100479188B1 (en) * | 2001-02-06 | 2005-03-25 | 엔이씨 도낀 가부시끼가이샤 | Electric double layer capacitor with improved activated carbon electrodes |
| WO2003065391A1 (en) * | 2002-01-29 | 2003-08-07 | Power Systems Co., Ltd. | Electrode formulation for polarized electrode and method for preparation thereof, and polarized electrode using the electrode formulation |
| US7491352B2 (en) | 2002-01-29 | 2009-02-17 | Junji Ito | Method for preparing an electrode material for a polarized electrode |
| US6912116B2 (en) | 2002-03-29 | 2005-06-28 | Tdk Corporation | Electrochemical device and process for producing same |
| JP2003297696A (en) * | 2002-03-29 | 2003-10-17 | Tdk Corp | Electric double-layer capacitor and method of manufacturing the same |
| JP2003297701A (en) * | 2002-03-29 | 2003-10-17 | Tdk Corp | Electrochemical device and method of manufacturing the same |
| WO2005041225A1 (en) * | 2003-10-24 | 2005-05-06 | Zeon Corporation | Binder for electrode of electric double layer capacitor |
| US7939600B2 (en) | 2003-10-24 | 2011-05-10 | Zeon Corporation | Binder for electric double layer capacitor electrode |
| JPWO2005041225A1 (en) * | 2003-10-24 | 2007-06-21 | 日本ゼオン株式会社 | Binder for electric double layer capacitor electrode |
| WO2006068291A1 (en) * | 2004-12-21 | 2006-06-29 | Teijin Limited | Electric double layer capacitor |
| WO2006103967A1 (en) * | 2005-03-25 | 2006-10-05 | Matsushita Electric Industrial Co., Ltd. | Polarizable electrode, capacitor using same, and method for manufacturing polarizable electrode |
| JPWO2006103967A1 (en) * | 2005-03-25 | 2008-09-04 | 松下電器産業株式会社 | Polarized electrode, capacitor using the same, and method for producing polarizable electrode |
| JP2008072069A (en) * | 2006-09-11 | 2008-03-27 | Dynic Corp | Electrode material for electric double layer capacitor and method of manufacturing the same |
| JP2009123931A (en) * | 2007-11-15 | 2009-06-04 | Nichicon Corp | Electric double layer capacitor |
| US20130114183A1 (en) * | 2011-11-04 | 2013-05-09 | Samsung Electro-Mechanics Co., Ltd. | Electrode active material composition, method for preparing the same, and electrochemical capacitor using the same |
| US20130163146A1 (en) * | 2011-12-23 | 2013-06-27 | Samsung Electro-Mechanics Co., Ltd. | Electrode active material-conductive agent composite, method for preparing the same, and electrochemical capacitor comprising the same |
| KR20160140888A (en) | 2014-04-01 | 2016-12-07 | 스미토모 세이카 가부시키가이샤 | Binder for electric double-layer capacitor electrode, electric double-layer capacitor electrode comprising same binder, electric double-layer capacitor using same electrode, and electric apparatus |
| US10068717B2 (en) | 2014-04-01 | 2018-09-04 | Sumitomo Seika Chemicals Co., Ltd. | Binder for electric double-layer capacitor electrode, electric double-layer capacitor electrode comprising same binder, electric double-layer capacitor using same electrode, and electric apparatus |
| WO2017025792A1 (en) * | 2015-08-11 | 2017-02-16 | Юнаско Лимитед | Method of manufacturing an electrode for an electrochemical double layer capacitor |
| CN107818874A (en) * | 2017-11-28 | 2018-03-20 | 广州驰裕网络科技有限公司 | A kind of ultracapacitor and preparation method thereof |
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