JP2003347172A - Active carbon for electric double-layer capacitor, and electrode for electric double-layer capacitor - Google Patents
Active carbon for electric double-layer capacitor, and electrode for electric double-layer capacitorInfo
- Publication number
- JP2003347172A JP2003347172A JP2002148150A JP2002148150A JP2003347172A JP 2003347172 A JP2003347172 A JP 2003347172A JP 2002148150 A JP2002148150 A JP 2002148150A JP 2002148150 A JP2002148150 A JP 2002148150A JP 2003347172 A JP2003347172 A JP 2003347172A
- Authority
- JP
- Japan
- Prior art keywords
- electric double
- layer capacitor
- activated carbon
- electrode
- double layer
- 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.)
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Links
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
Description
【０００１】[0001]
【発明の技術分野】本発明は、電気二重層キャパシタ用
活性炭及び電気二重層キャパシタ用電極に関し、さらに
詳しく強度等に優れた電気二重層キャパシタ用電極が得
られるような電気二重層キャパシタ用活性炭及び電気二
重層キャパシタ用電極に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an activated carbon for an electric double layer capacitor and an electrode for an electric double layer capacitor, and more particularly to an activated carbon for an electric double layer capacitor capable of obtaining an electrode for an electric double layer capacitor having excellent strength and the like. The present invention relates to an electrode for an electric double layer capacitor.
【０００２】[0002]
【発明の技術的背景】電気二重層キャパシタ（電気二重
層コンデンサ）は、電気二重層に基づく物理的な電荷の
蓄積によるコンデンサであって、化学的反応の二次電池
と比べて高出力な急速充電・放電が可能で、有害な物質
を使用していないなど、多くの利点を有しており、電子
機器用などの小型のものから車のバッテリーなどの大型
のものまで、多種の用途への利用が期待されている。BACKGROUND OF THE INVENTION An electric double-layer capacitor (electric double-layer capacitor) is a capacitor based on electric double-layers and accumulating physical charges, and has a higher output and a higher speed than a secondary battery of a chemical reaction. It can be charged and discharged and has many advantages, such as no use of harmful substances.It can be used for a variety of applications, from small ones for electronic devices to large ones such as car batteries. Use is expected.
【０００３】電気二重層コンデンサの電極としては、活
性炭などの炭素材を主成分とした電極が用いられてお
り、主に炭素材と含フッ素樹脂とを含有する電極が用い
られている。そして電気二重層コンデンサの小型軽量化
のために、電極をシート状に薄型化することが求められ
ていた。従来、シート状の分極性電極は、炭素微粉末
（活性炭および／またはカーボンブラック）、ポリテト
ラフルオロエチレン（ＰＴＦＥ）樹脂および液状潤滑剤
からなるペースト状の粘稠混和物を、圧延ロールによっ
て直接、シート状に成形することによって製造されてい
た。ところが、このような方法でシートの厚さを薄くし
ようとすると、強度がなく、液状潤滑剤の付着力のため
にシートが折重なってくっつき合い、その取扱いは、実
質上不可能であった。そして、このような方法で製造で
きるシート厚さの下限は、０．６ｍｍ程度であった。As an electrode of an electric double layer capacitor, an electrode mainly containing a carbon material such as activated carbon is used, and an electrode mainly containing a carbon material and a fluorine-containing resin is used. In order to reduce the size and weight of the electric double-layer capacitor, it has been required to reduce the thickness of the electrode into a sheet. Conventionally, a sheet-like polarizable electrode is obtained by directly applying a paste-like viscous admixture composed of carbon fine powder (activated carbon and / or carbon black), polytetrafluoroethylene (PTFE) resin and a liquid lubricant by a rolling roll. It was manufactured by molding into a sheet. However, when the thickness of the sheet is reduced by such a method, the sheet is not strong, and the sheets are folded and adhered due to the adhesive force of the liquid lubricant, so that the handling thereof is practically impossible. The lower limit of the sheet thickness that can be produced by such a method was about 0.6 mm.
【０００４】このような問題を解決する手段として、炭
素微粉末と含フッ素重合体樹脂と液状潤滑剤の混練物を
シート状に一旦、予備成形した後に、液状潤滑剤を除去
し、次いで得られた成形物を延伸処理する方法などが提
案されている（特開昭６３−１０７０１１号公報）。こ
の方法によれば、薄型のシート状電極も製造できるが、
ペースト状の混和物をシート状に圧延する圧延工程（予
備成形）の後、さらに延伸工程を行うなど、複雑な工程
が必要であった。また、工業的には、さらに長尺なシー
ト状電極を一挙に製造する方法の出現が望まれていた。As a means for solving such a problem, a kneaded product of fine carbon powder, a fluoropolymer resin, and a liquid lubricant is once preformed into a sheet form, and then the liquid lubricant is removed. A method of stretching a molded article has been proposed (Japanese Patent Application Laid-Open No. 63-107011). According to this method, a thin sheet-like electrode can be manufactured,
After the rolling process (preliminary forming) of rolling the paste-like mixture into a sheet, a complicated process was required, such as further performing a stretching process. In addition, industrially, it has been desired to develop a method for manufacturing a longer electrode sheet at a time.
【０００５】これに対して、薄型で、かつ長尺なシート
状電極を製造する方法としては、炭素微粉末と含フッ素
重合体樹脂と液状潤滑剤との混合物を、シート状に予備
成形し、予備成形体同士を端部で重ねて圧延接合して、
連続した長尺の予備成形体にした後に、液状潤滑剤を除
去し、次いで予備成形体を加熱した圧延ロールで成形す
る方法が提案されている（特開平２−２３５３２０号公
報）。On the other hand, as a method for producing a thin and long sheet-like electrode, a mixture of fine carbon powder, a fluoropolymer resin and a liquid lubricant is preliminarily formed into a sheet, The preforms are overlapped at the end and roll-joined,
A method has been proposed in which a continuous long preform is formed, the liquid lubricant is removed, and then the preform is formed by a heated rolling roll (JP-A-2-235320).
【０００６】しかしながらこの方法で長尺のシート状電
極を得るためには、ペースト状の粘稠混和物を調製し、
それを圧延して厚さ１ｍｍ程度のシート状の予備成形体
を複数調製し、複数の予備成形体同士を端部で重ねて圧
延ロールで接合するという複雑な工程を経て長尺の予備
成形体を製造する必要があった。また、通常シート状の
予備成形物は厚さおよび硬さのばらつきを有することが
多く、さらにその端部を重ねて接合すると、接合部がそ
の他の部位と均質にはならないため、接合された長尺の
シート状の予備成形体は、厚さおよび硬さのばらつきを
有する。したがって、このような予備成形体を圧延して
得られる薄型のシート状電極は、厚さおよび硬さが均一
にならないという問題があった。However, in order to obtain a long sheet-like electrode by this method, a paste-like viscous mixture is prepared,
It is rolled to prepare a plurality of sheet-like preforms having a thickness of about 1 mm, and a plurality of preforms are overlapped at their ends and joined by a rolling roll to form a long preform. Had to be manufactured. Also, usually, sheet-shaped preforms often have variations in thickness and hardness, and furthermore, when the end portions are overlapped and joined, the joined portion is not uniform with other portions, so the joined length is not long. The preform in the form of a sheet having a length has variations in thickness and hardness. Therefore, there is a problem that a thin sheet-like electrode obtained by rolling such a preform does not have a uniform thickness and hardness.
【０００７】このため、均質な性状を有する連続した長
尺のシート状電極を、工業的に一挙に製造する方法の確
立が求められていた。そこで、本願出願人は、先に、特
開２００１−８５２８０号公報にて、活性炭および／ま
たは導電性カーボンを好ましくは特定量比で含有する炭
素微粉末と、含フッ素重合体樹脂と液状潤滑剤とからな
り、かつ、圧縮方向の最大長さと、圧縮方向と直交する
横方向の最大長さとが、特定の関係を満たすロッド状予
備成形物を、圧延処理してシート状電極を成形すること
による、含フッ素重合体樹脂を含むシート状電極の製造
方法を提案した。この方法によれば、簡素な工程で均質
なシート状電極を製造し得る。[0007] For this reason, there has been a demand for the establishment of a method for industrially producing a continuous long sheet-like electrode having uniform properties at once. Therefore, the applicant of the present application disclosed in Japanese Unexamined Patent Application Publication No. 2001-85280 that carbon fine powder containing activated carbon and / or conductive carbon, preferably in a specific ratio, a fluoropolymer resin and a liquid lubricant And, the maximum length in the compression direction and the maximum length in the transverse direction perpendicular to the compression direction are obtained by forming a rod-shaped preform satisfying a specific relationship by rolling and forming a sheet-like electrode. A method for producing a sheet-like electrode containing a fluoropolymer resin was proposed. According to this method, a homogeneous sheet-like electrode can be manufactured by a simple process.
【０００８】しかしながら、該公報に記載の方法で用い
られるロッド状予備成形物は、活性炭の種類が変化する
と、シートへの成形性（シート強度）が大きく異なるな
ど、更なる改良の余地があり、また、得られる電極は、
強度等の点で更なる改良の余地があった。However, the rod-shaped preform used in the method described in the publication has room for further improvement, such as a change in the form of a sheet (sheet strength) when the type of activated carbon is changed. The resulting electrode is
There was room for further improvement in terms of strength and the like.
【０００９】[0009]
【発明の目的】本発明は、上記のような従来技術に伴う
問題点を解決しようとするものであって、強度等に優れ
た薄型で均質なシート状の電気二重層キャパシタ用電極
が得られるような電気二重層キャパシタ用活性炭を提供
することを目的としている。また本発明は、簡単な方法
で得られる、強度等に優れた薄型で均質なシート状の電
気二重層キャパシタ用電極を提供することを目的として
いる。SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and a thin and uniform sheet-like electrode for an electric double layer capacitor having excellent strength and the like can be obtained. It is an object of the present invention to provide such an activated carbon for an electric double layer capacitor. Another object of the present invention is to provide a thin and uniform sheet-like electrode for an electric double layer capacitor which is obtained by a simple method and has excellent strength and the like.
【００１０】[0010]
【発明の概要】本発明に係る電気二重層キャパシタ用活
性炭は、平均粒子径が２０〜６０μｍで、粒度分布を示
す標準偏差値が０．４００〜０．６００の範囲にあるこ
とを特徴としている。本発明の好ましい態様では、上記
活性炭は、粒子径が２０μｍ未満の活性炭（ａ１）２５
〜５０％と、粒子径が２０μｍ以上〜４０μｍ未満の活
性炭（ａ２）１５〜５５％と、粒子径が４０μｍ以上の
活性炭（ａ３）２０〜５０％（（ａ１）＋（ａ２）＋
（ａ３）＝１００％）とからなることが好ましい。SUMMARY OF THE INVENTION The activated carbon for an electric double layer capacitor according to the present invention is characterized in that the average particle diameter is 20 to 60 μm and the standard deviation indicating the particle size distribution is in the range of 0.400 to 0.600. . In a preferred embodiment of the present invention, the activated carbon is activated carbon (a1) 25 having a particle diameter of less than 20 μm.
５０50%, activated carbon (a2) having a particle size of 20 μm or more and less than 40 μm, 15-55%, and activated carbon (a3) having a particle size of 40 μm or more (a3) + (a2) +
(A3) = 100%).
【００１１】本発明に係る電気二重層キャパシタ用電極
は、上記の活性炭と、導電性カーボンと、バインダーと
を含有することを特徴としている。本発明に係る電気二
重層キャパシタ用電極には、上記活性炭が、該電気二重
層キャパシタ用電極中に、１０〜９５重量％の量で含ま
れていることが望ましい。本発明によれば、強度等に優
れた薄型で均質なシート状の電気二重層キャパシタ用電
極が得られるような電気二重層キャパシタ用活性炭が提
供される。[0011] An electrode for an electric double layer capacitor according to the present invention is characterized by containing the above-mentioned activated carbon, conductive carbon, and a binder. In the electrode for an electric double layer capacitor according to the present invention, it is preferable that the activated carbon is contained in the electrode for an electric double layer capacitor in an amount of 10 to 95% by weight. ADVANTAGE OF THE INVENTION According to this invention, the activated carbon for electric double layer capacitors which can obtain the thin and uniform sheet-like electrode for electric double layer capacitors excellent in strength etc. is provided.
【００１２】また本発明によれば、簡単な方法で得られ
る、強度等に優れた薄型で均質なシート状の電気二重層
キャパシタ用電極が提供される。Further, according to the present invention, there is provided a thin and uniform sheet-like electrode for an electric double layer capacitor which is obtained by a simple method and has excellent strength and the like.
【００１３】[0013]
【発明の具体的説明】以下、本発明に係る電気二重層キ
ャパシタ用活性炭及び電気二重層キャパシタ用電極並び
にその製法について具体的に説明する。＜電気二重層キャパシタ用活性炭＞
本発明に係る電気二
重層キャパシタ用活性炭には、粒子径［測定法：レーザ
ー回折・散乱法］が通常、０.１μｍ以上で、２０μｍ
未満の活性炭（ａ１）２５〜５０％、好ましくは３０〜
５０％と、粒子径が２０μｍ以上〜４０μｍ未満の活性
炭（ａ２）１５〜５５％、好ましくは２０〜４５％と、
粒子径が４０μｍ以上の活性炭（ａ３）２０〜５０％、
好ましくは２５〜４０％（（ａ１）＋（ａ２）＋（ａ
３）＝１００％）とが含まれている。このような量比で
粒径の異なる特定の粒径の活性炭が複数種含まれている
と、該活性炭を用いてなるロッド状予備成形物は成形性
に優れ、薄くても充分な強度を有しており良好にシート
状などに成形でき、また得られる電気二重層キャパシタ
は、引張強度に代表される強度などに優れる傾向があ
る。DETAILED DESCRIPTION OF THE INVENTION The activated carbon for an electric double layer capacitor, the electrode for an electric double layer capacitor, and the method for producing the same according to the present invention will be specifically described below. <Activated carbon for electric double layer capacitor> The activated carbon for electric double layer capacitor according to the present invention usually has a particle diameter [measurement method: laser diffraction / scattering method] of 0.1 μm or more and 20 μm or more.
Activated carbon (a1) less than 25-50%, preferably 30-
50%, activated carbon (a2) having a particle diameter of 20 μm or more and less than 40 μm, 15 to 55%, preferably 20 to 45%,
Activated carbon (a3) having a particle diameter of 40 μm or more, 20 to 50%,
Preferably, 25 to 40% ((a1) + (a2) + (a
3) = 100%). When a plurality of types of activated carbon having specific particle diameters different in particle diameter are contained in such a quantitative ratio, a rod-shaped preform made of the activated carbon has excellent moldability and has sufficient strength even when thin. Thus, the electric double layer capacitor obtained can be favorably formed into a sheet or the like, and the obtained electric double layer capacitor tends to have excellent strength such as tensile strength.
【００１４】更に詳説すると、電気二重層キャパシタ用
活性炭として、もし、含まれる活性炭粒子の粒子径が小
さく（例：平均粒子径２０μｍ未満（但し、５μｍ以
上））、粒度分布がシャープ（例：粒度分布を示す標準
偏差が０.１５〜０.３である場合には、電気二重層キャ
パシタ用電極（シート状電極）中に含まれる一定量のバ
インダーにてバインドすべき活性炭粒子の個数が多くな
り、得られる電気二重層キャパシタ用電極がシート状の
場合、該シート強度が低下する傾向がある。More specifically, as activated carbon for an electric double layer capacitor, if the activated carbon particles contained therein have a small particle size (eg, an average particle size of less than 20 μm (however, 5 μm or more)) and a sharp particle size distribution (eg, a particle size When the standard deviation indicating the distribution is 0.15 to 0.3, the number of activated carbon particles to be bound with a certain amount of binder contained in the electric double layer capacitor electrode (sheet electrode) increases. When the obtained electrode for an electric double layer capacitor has a sheet shape, the sheet strength tends to decrease.
【００１５】また、もし、活性炭粒子径が大きく（例：
平均粒子径２０μｍ以上）、粒度分布がシャープ（例：
粒度分布を示す標準偏差が０.１５〜０.３である場合に
は、電気二重層キャパシタ用電極中に含まれる一定量の
バインダーにてバインドすべき活性炭粒子個数が少なく
なり、活性炭粒子間の隙間が大きくなり嵩密度が低くな
る。このため、シート状電極中のバインダーなどの各成
分重量比が一定の場合、同一重量のバインダーにてバイ
ンドすべき活性炭粒子の体積が増加する。その結果、単
位体積当たりのバインダー重量は減少し、シート強度が
低下する傾向がある。If the activated carbon particle diameter is large (for example,
Average particle diameter of 20 μm or more), sharp particle size distribution (Example:
When the standard deviation indicating the particle size distribution is 0.15 to 0.3, the number of activated carbon particles to be bound with a fixed amount of binder contained in the electrode for an electric double layer capacitor decreases, and The gap increases and the bulk density decreases. Therefore, when the weight ratio of each component such as a binder in the sheet-like electrode is constant, the volume of activated carbon particles to be bound with the same weight of the binder increases. As a result, the binder weight per unit volume tends to decrease, and the sheet strength tends to decrease.
【００１６】これに対して本発明では、上記したよう
に、特定粒径の活性炭を特定量比で組み合わせて用いて
いるため、粒径の大きいものを含み、しかも粒度分布が
ブロード（例：粒度分布を示す標準偏差が０．４００〜
０．６００）であるため、活性炭粒子径が小さい（例：
粒子径２０μｍ未満）もののみである場合に比して、活
性炭粒子の個数が少なくなる。また、活性炭粒子の粒度
分布がブロードなため、シート中の活性炭の充填密度も
上がり、嵩密度も高くなる。すなわち、活性炭の粒度分
布がブロードなため、様々な大きさ（粒径）の活性炭粒
子が存在し、大粒径の活性炭粒子の間隙に、小粒径の活
性炭粒子が充填配置され、全体として、嵩密度が高くな
っている。その結果、活性炭粒子径が全て小さい場合に
比して、バインドすべき粒子数が減り、さらに、バイン
ドすべき活性炭粒子の体積も少なくなり、このため、シ
ート強度が高くなるのであろうと考えられる。On the other hand, in the present invention, as described above, since activated carbon having a specific particle size is used in combination at a specific ratio, it includes those having a large particle size and a broad particle size distribution (eg, particle size distribution). The standard deviation indicating the distribution is 0.400 to
0.600), the activated carbon particle size is small (eg:
(The particle diameter is less than 20 μm), the number of activated carbon particles is smaller than in the case where only the particles are used. Further, since the particle size distribution of the activated carbon particles is broad, the packing density of the activated carbon in the sheet is increased, and the bulk density is also increased. That is, since the particle size distribution of activated carbon is broad, activated carbon particles of various sizes (particle diameters) are present, and small-sized activated carbon particles are filled and arranged between the large-sized activated carbon particles. Bulk density is high. As a result, it is considered that the number of particles to be bound is reduced and the volume of the activated carbon particles to be bound is also reduced as compared with the case where all the activated carbon particle diameters are small, so that the sheet strength may be increased.
【００１７】なお、この粒子径が２０μｍ未満の活性炭
（ａ１）の含有量が上記範囲より少ないと嵩密度が低く
なる傾向があり、上記範囲より多いと電気二重層キャパ
シタ用電極中のバインダーによりバインドすべき活性炭
粒子数が多くなり、シート強度が低下する傾向があり、
粒子径が４０μｍ以上の活性炭（ａ３）の含有量が上記
範囲より少ないと同一の活性炭配合量の電極の場合、活
性炭粒子数が多くなる傾向があり、上記範囲より多いと
嵩密度が低くなる傾向がある。If the content of the activated carbon (a1) having a particle size of less than 20 μm is less than the above range, the bulk density tends to be low. If the content is more than the above range, the binder is bound by the binder in the electric double layer capacitor electrode. The number of activated carbon particles to be increased tends to decrease the sheet strength,
When the content of the activated carbon (a3) having a particle diameter of 40 μm or more is less than the above range, in the case of an electrode having the same amount of activated carbon, the number of activated carbon particles tends to increase, and when the content is more than the above range, the bulk density tends to decrease. There is.
【００１８】またこのような電気二重層キャパシタ用活
性炭の標準偏差は、通常、０．４００〜０．６００、好
ましくは０.５〜０.６である。このような標準偏差のブ
ロードな電気二重層キャパシタ用活性炭を用いてなるロ
ッド状予備成形物は成形性に優れ、薄くても充分な強度
を有しており良好に薄いシート状などに成形でき、また
得られる電気二重層キャパシタは、引張強度に代表され
る強度などに優れる傾向がある。The standard deviation of such activated carbon for electric double layer capacitors is usually 0.400 to 0.600, preferably 0.5 to 0.6. The rod-shaped preform using the activated carbon for an electric double layer capacitor having such a standard deviation is excellent in formability, has sufficient strength even if thin, and can be formed into a thin sheet or the like, Further, the obtained electric double layer capacitor tends to have excellent strength represented by tensile strength.
【００１９】また、このような電気二重層キャパシタ用
活性炭の全体としての平均粒径は、通常、２０〜６０μ
ｍ、好ましくは２０〜４０μｍであることが最適な粒径
の分布となる点で望ましい。このような電気二重層キャ
パシタ用活性炭（活性炭）は、電気二重層キャパシタ用
電極中に、通常、１０〜９５重量％、好ましくは７０〜
９０重量％となるような量で配合されることが静電容量
の点で好ましい。The average particle size of the activated carbon for an electric double layer capacitor as a whole is usually 20 to 60 μm.
m, preferably 20 to 40 μm, in order to obtain an optimal particle size distribution. Such activated carbon for an electric double layer capacitor (activated carbon) is usually contained in an electrode for an electric double layer capacitor in an amount of 10 to 95% by weight, preferably 70 to 95% by weight.
It is preferable from the point of view of the capacitance that the compounding is performed in such an amount as to become 90% by weight.
【００２０】このような粒度分布の電気二重層キャパシ
タ用活性炭を得るには、粒子径が通常、０.１μｍ以上
で、２０μｍ未満の活性炭（ａ１）と、粒子径が２０μ
ｍ以上〜４０μｍ未満の活性炭（ａ２）と、粒子径が４
０μｍ以上の活性炭（ａ３）とをそれぞれ上記量で配合
し、混合、攪拌等すればよい。＜電気二重層キャパシタ用電極＞
本発明に係る電気二重
層キャパシタ用電極は、上記の電気二重層キャパシタ用
活性炭（活性炭）と、導電性カーボンと、バインダーと
を含有している。In order to obtain an activated carbon for an electric double layer capacitor having such a particle size distribution, activated carbon (a1) having a particle diameter of usually 0.1 μm or more and less than 20 μm, and a particle diameter of 20 μm or less.
activated carbon (a2) having a particle size of not less than 4 m and less than 40 μm.
Activated carbon (a3) having a particle size of 0 μm or more may be blended in the above amounts, followed by mixing and stirring. <Electrode for Electric Double Layer Capacitor> The electrode for an electric double layer capacitor according to the present invention contains the above-mentioned activated carbon for an electric double layer capacitor (activated carbon), conductive carbon, and a binder.
【００２１】このような電気二重層キャパシタ用電極
は、強度、特に引張強度等に優れている。このような電
気二重層キャパシタ用電極には、上記活性炭が、通常、
１０〜９５重量％、好ましくは７０〜９０重量％の量で
含まれていることが強度、静電容量の点で望ましい。Such an electrode for an electric double layer capacitor is excellent in strength, particularly in tensile strength and the like. In such an electrode for an electric double layer capacitor, the activated carbon is usually
It is desirable in terms of strength and capacitance that it is contained in an amount of 10 to 95% by weight, preferably 70 to 90% by weight.
【００２２】また、導電性カーボンは、この電気二重層
キャパシタ用電極中に、通常、０〜５０重量％、好まし
くは、５〜２０重量％の量で含まれていることが抵抗値
の点で望ましい。また、バインダーは、この電気二重層
キャパシタ用電極中に、通常、１〜５０重量％、好まし
くは、５〜２０重量％の量で含まれていることが強度、
抵抗の点で望ましい。導電性カーボン
導電性カーボンとしては、例えば、アセチレンブラック
（平均粒径：０．００５〜０．０９５μｍ、商品名「デ
ンカブラック」、電気化学工業（株）製）、「ケッチェ
ンブラック」（ケッチェン・ブラック・インターナショ
ナル（株）製）等が挙げられる。In view of the resistance value, the conductive carbon is usually contained in the electric double layer capacitor electrode in an amount of 0 to 50% by weight, preferably 5 to 20% by weight. desirable. The strength of the binder for the electric double layer capacitor is generally such that the binder is contained in an amount of 1 to 50% by weight, preferably 5 to 20% by weight.
Desirable in terms of resistance. Examples of conductive carbon include acetylene black (average particle size: 0.005 to 0.095 μm, trade name “DENKA BLACK”, manufactured by Denki Kagaku Kogyo KK), and “Ketjen Black” (Ketjen Black). Black International Co., Ltd.).
【００２３】これら導電性カーボンの平均粒径は、電気
二重層キャパシタ用活性炭の平均粒径に比して極めて小
さく、通常、０．１μｍ以下である。さらに、本発明で
用いられる上記導電性カーボンと上記活性炭について付
言すると、何れも炭素質であるが、導電性カーボンと
は、通常、ファーネスカーボンやアセチレンブラックな
どのカーボンブラックのことを言い、導電性を付与する
のに使用されている。一般的な導電性カーボンは、数〜
数十nmという非常に小さな炭素のコロイド様微粒子から
出来ている。The average particle size of the conductive carbon is extremely smaller than the average particle size of the activated carbon for electric double layer capacitors, and is usually 0.1 μm or less. Furthermore, when the conductive carbon and the activated carbon used in the present invention are additionally mentioned, they are both carbonaceous, and the conductive carbon usually means carbon black such as furnace carbon or acetylene black, Is used to grant Typical conductive carbon is several to
It is made of very small carbon colloid-like particles of several tens of nm.
【００２４】これに対して、本発明で用いられる活性炭
は、気体や色素の分子などに対して特に高い吸着能力を
示す炭素質の粒状または粉状物質であり、ヤシ炭・褐炭
・泥炭などを原料とし、炭化・賦活処理により製造さ
れ、その多孔性構造により非常に大きな比表面積（数百
〜数千m2/g）を持っている。一般的な粉状活性炭で数〜
数十μmの大きさである。バインダー
バインダーとしては、上記の電気二重層キャパシタ用活
性炭（活性炭）と導電性カーボンとを結合・結着可能な
樹脂であれば特に限定されないが、繊維状のものが好ま
しい。このようなバインダーとしては、従来より公知の
ものを広く使用でき、天然樹脂系、合成樹脂系の何れで
もよく、例えば、ＰＴＦＥ系繊維、セルロース系繊維等
が挙げられる。On the other hand, the activated carbon used in the present invention is a carbonaceous granular or powdery substance having a particularly high ability to adsorb gas and pigment molecules. It is produced as a raw material by carbonization and activation treatment and has a very large specific surface area (several hundreds to several thousand m 2 / g) due to its porous structure. It is several to common powdered activated carbon
The size is several tens of μm. Binder The binder is not particularly limited as long as it is a resin capable of binding and binding the above-mentioned activated carbon for an electric double layer capacitor (activated carbon) and conductive carbon, but a fibrous one is preferred. As such a binder, conventionally known binders can be widely used, and any of a natural resin type and a synthetic resin type may be used, and examples thereof include PTFE fiber and cellulose fiber.
【００２５】＜電気二重層キャパシタ用電極の製造＞こ
のような電気二重層キャパシタ用活性炭（活性炭）と、
導電性カーボンと、バインダーとを含有し、通常、さら
に液状潤滑剤などを含有しているロッド状（棒状）予備
成形物から、本発明の電気二重層キャパシタ用電極を製
造するには、例えば、特開２００１−８５２８０号公報
に記載の方法に準ずればよい。 <Production of Electrode for Electric Double Layer Capacitor> Such activated carbon for an electric double layer capacitor (activated carbon)
In order to manufacture the electrode for an electric double layer capacitor of the present invention from a rod-shaped (rod-shaped) preform containing conductive carbon and a binder and usually further containing a liquid lubricant, for example, What is necessary is just to follow the method of Unexamined-Japanese-Patent No. 2001-85280.
【００２６】すなわち、図１に示すロッド状予備成形物
を、該成形物の径方向外方（図１では、「圧縮方向」と
表示。）から該成形物の仮想中心軸Ｘに向かって加圧す
る等の方法で圧延処理すればよく、このように圧延処理
するとシート状電極を形成することができる。この際の
ロッド状予備成形物は、図１において、圧縮方向の最大
長さ（長径）ｄと、圧縮方向と直交する横方向の最大長
さ（短径）ｄ0とが、０．１＜ｄ／ｄ0＜１０の関係を満
たすことが望ましい。That is, the rod-shaped preform shown in FIG. 1 is applied from the radial outside of the molded product (in FIG. 1, indicated as “compression direction”) toward the virtual center axis X of the molded product. Rolling may be performed by a method such as pressing, and a sheet-like electrode can be formed by such rolling. In this case, in FIG. 1, the rod-shaped preform has a maximum length (major axis) d in the compression direction and a maximum length (minor axis) d 0 in the transverse direction orthogonal to the compression direction of 0.1 <0.1. It is desirable to satisfy the relationship d / d 0 <10.
【００２７】なお、該ロッド状予備成形物の仮想軸（長
手方向）Ｘに直交する方向（径方向）の断面形状は、特
に限定されないが、仮想軸Ｘ上の切断部位に依らず一定
（同一形状）であることが得られるシート状電極の性能
が部位に依らず一定（均一）となるため望ましい。この
断面形状は、例えば、図１（ａ）に示すように長円（楕
円）であってもよく、また図１（ｂ）に示すように多角
形（例：六角形）、図示せぬ円形等の何れでもよい。The cross-sectional shape of the rod-shaped preform in the direction (radial direction) perpendicular to the virtual axis (longitudinal direction) X is not particularly limited, but is constant (same regardless of the cut portion on the virtual axis X). Shape) is desirable because the performance of the obtained sheet-like electrode becomes constant (uniform) regardless of the position. The cross-sectional shape may be, for example, an ellipse (ellipse) as shown in FIG. 1A, a polygon (eg, hexagon) as shown in FIG. And so on.
【００２８】また上記圧延処理条件としては、圧延温度
は液状潤滑剤の沸点以下の温度、好ましくは２０〜２０
０℃の範囲内の一定温度で、圧延ロール温度：２０〜９
０℃の条件で、０．０５〜２ｔ／ｃｍでの高圧縮を加え
て、原長（ロッド状予備成形物の長手方向の長さ：ロッ
ド長）の５〜１０００倍程度に圧延するのが望ましく、
このような圧延処理を行うと、樹脂の繊維化が促進さ
れ、優れた強度、特に引張強度を有する長尺のシート状
電極を得ることができる。As the rolling conditions, the rolling temperature is a temperature lower than the boiling point of the liquid lubricant, preferably 20 to 20.
Rolling roll temperature: 20 to 9 at a constant temperature in the range of 0 ° C.
Under the condition of 0 ° C., high compression of 0.05 to 2 t / cm is applied, and the material is rolled to about 5 to 1000 times the original length (length in the longitudinal direction of the rod-shaped preform: rod length). Desirably,
By performing such a rolling treatment, the fiberization of the resin is promoted, and a long sheet-like electrode having excellent strength, particularly, tensile strength can be obtained.
【００２９】このようなシート状の電気二重層キャパシ
タ用電極中においては、図２に示す模式図に示すよう
に、導電性カーボンと上記電気二重層キャパシタ用活性
炭（活性炭）などとをバインドするように、繊維状等の
バインダー、例えば、ＰＴＦＥ繊維がこれらの間隙を埋
め、シートの強度（特に引張強度）を高めているのであ
ろうと考えられる。In such a sheet-like electrode for an electric double-layer capacitor, as shown in the schematic diagram of FIG. 2, conductive carbon and activated carbon for the electric double-layer capacitor (activated carbon) are bound. In addition, it is considered that a fibrous binder or the like, for example, PTFE fiber fills these gaps and increases the strength (particularly, tensile strength) of the sheet.
【００３０】このように圧延処理して得られた圧延処理
物は、通常、乾燥処理される。乾燥処理は、例えば、バ
インダーが含フッ素重合体樹脂である場合、該バインダ
ーが溶融しない温度たとえばＰＴＦＥなどの場合には、
８０〜３２０℃で、空気中または不活性ガス雰囲気下で
行うのが望ましい。以上のようにして得られた長尺のシ
ート状電極は、適宜所望の大きさ・形状に切断し、電極
として使用することができる。[0030] The rolled product obtained by the rolling process is usually dried. The drying treatment is, for example, when the binder is a fluoropolymer resin, when the temperature at which the binder does not melt, such as PTFE,
It is desirable to carry out at 80 to 320 ° C. in air or in an inert gas atmosphere. The long sheet-like electrode obtained as described above can be appropriately cut into a desired size and shape and used as an electrode.
【００３１】本発明のシート状電極の形状は、シート状
であればよく、その電極を使用する電気二重層コンデン
サなどの電池の大きさ、電気容量などによるものであっ
て、その厚さ、面積、形状などは特に限定されるもので
はない。このような本発明のシート状電極は、炭素電極
を用いる電池類に広く用いることができるが、特に電気
二重層コンデンサ用の分極性電極として好ましく用いる
ことができる。The shape of the sheet-like electrode of the present invention may be a sheet-like shape, and depends on the size and electric capacity of a battery such as an electric double layer capacitor using the electrode, and its thickness and area. The shape, shape and the like are not particularly limited. Such a sheet-like electrode of the present invention can be widely used for batteries using a carbon electrode, but is particularly preferably used as a polarizable electrode for an electric double layer capacitor.
【００３２】なお、上記ロッド状予備成形物の調製方法
は、特に限定されず、特開２００１−８５２８０号公報
等に記載の方法に準ずればよく、例えば、電気二重層キ
ャパシタ用活性炭（活性炭）と、導電性カーボンと、分
散媒に分散（又は溶媒に溶解）したバインダーとを混合
し、必要により分散媒（又は溶媒）を揮散・除去した
後、さらに液状潤滑剤を加えて混練するなどの方法で、
上記活性炭、導電性カーボン、含フッ素重合体樹脂等の
バインダーおよび液状潤滑剤を含有する混練物を調製
し、さらに得られた混練物を、押出成形などの方法によ
って、ロッド状に成形する方法が挙げられる。The method for preparing the rod-shaped preform is not particularly limited, and may be in accordance with the method described in JP-A-2001-85280. For example, activated carbon for an electric double layer capacitor (activated carbon) , Conductive carbon, and a binder dispersed (or dissolved in a solvent) in a dispersion medium, and after volatilizing and removing the dispersion medium (or solvent) as necessary, a liquid lubricant is further added and kneaded. By the way,
A method of preparing a kneaded material containing a binder and a liquid lubricant such as the activated carbon, the conductive carbon, and the fluoropolymer resin, and further molding the obtained kneaded material into a rod by a method such as extrusion molding. No.
【００３３】バインダーの１種である含フッ素重合体樹
脂としては、ポリテトラフルオロエチレン（ＰＴＦ
Ｅ）、変性ＰＴＦＥ、ＰＶＤＦ、ＥＴＦＥ、ＰＣＴＦ
Ｅ、ＦＥＰおよびＰＦＡなどが挙げられる。分散媒とし
ては水、アルコール、グリコールなどの液体、特に水が
好ましい。液状潤滑剤としては、水、アルコール、エチ
レングリコール、プロピレングリコール、グリセリン、
ホワイトオイルなどが挙げられる。As the fluoropolymer resin which is one kind of the binder, polytetrafluoroethylene (PTF)
E), modified PTFE, PVDF, ETFE, PCTF
E, FEP and PFA. As the dispersion medium, a liquid such as water, alcohol, or glycol, particularly water is preferable. Liquid lubricants include water, alcohol, ethylene glycol, propylene glycol, glycerin,
White oil and the like.
【００３４】液状潤滑剤が、ロッド状予備成形物中に５
〜７０重量％程度の割合で含有されていると、後述する
圧延処理を行う際にバインダー（例：含フッ素重合体樹
脂）の繊維化を促進し、亀裂を生じたり小片化したりす
ることなく、均一なシート状電極を製造できるため好ま
しい。The liquid lubricant is added to the rod-shaped preform by 5%.
When it is contained at a ratio of about 70% by weight, it promotes fiberization of a binder (eg, a fluoropolymer resin) at the time of performing a rolling treatment described later, without causing cracking or fragmentation. This is preferable because a uniform sheet-like electrode can be manufactured.
【００３５】[0035]
【発明の効果】本発明によれば、強度等に優れた薄型で
均質なシート状の電気二重層キャパシタ用電極が得られ
るような電気二重層キャパシタ用活性炭が提供される。
また本発明によれば、簡単な方法で得られる、強度等に
優れた薄型で均質なシート状の電気二重層キャパシタ用
電極が提供される。According to the present invention, there is provided an activated carbon for an electric double layer capacitor capable of obtaining a thin and uniform sheet-like electrode for an electric double layer capacitor having excellent strength and the like.
Further, according to the present invention, there is provided a thin and uniform sheet-like electrode for an electric double layer capacitor which is obtained by a simple method and has excellent strength and the like.
【００３６】また本発明によれば、均質な性状を有する
薄型のシート状電極を、一度の圧延処理により長尺で製
造することができ、亀裂、小片化またはピンホールの発
生などの問題を生じることなく、幅および厚みの一定な
シート状電極を工業的規模で効率的に量産することがで
きる。Further, according to the present invention, a thin sheet-like electrode having a uniform property can be manufactured in a long length by a single rolling process, which causes problems such as cracks, fragmentation, and generation of pinholes. Without this, sheet electrodes having a constant width and thickness can be efficiently mass-produced on an industrial scale.
【００３７】[0037]
【実施例】以下、実施例に基づいて本発明をさらに具体
的に説明するが、本発明はこれらの実施例により何ら限
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.
【００３８】[0038]
【実施例１】活性炭として、粒子径が２０μｍ未満の活
性炭（ａ１）３９.５％と、粒子径が２０μｍ以上〜４
０μｍ未満の活性炭（ａ２）２０.５％と、粒子径が４
０μｍ以上の活性炭（ａ３）４０％（（ａ１）＋（ａ
２）＋（ａ３）＝１００％）とからなり、全平均粒子径
２８．６μｍ、比表面積1640ｍ2/ｇ、標準偏差０．５４
３の活性炭、導電性カーボンとしてアセチレンブラッ
ク、および平均粒径が０．２μｍのＰＴＦＥを用いて、
活性炭：導電性カーボン：ＰＴＦＥが、８：１：１の重
量比になるように混合した。Example 1 As activated carbon, activated carbon (a1) having a particle diameter of less than 20 μm was 39.5%, and a particle diameter of 20 μm or more to 4 μm.
20.5% of activated carbon (a2) having a particle diameter of less than 0 μm
0% or more activated carbon (a3) 40% ((a1) + (a
2) + (a3) = 100%), the total average particle diameter is 28.6 μm, the specific surface area is 1640 m 2 / g, and the standard deviation is 0.54.
Using activated carbon of No. 3, acetylene black as conductive carbon, and PTFE having an average particle size of 0.2 μm,
Activated carbon: conductive carbon: PTFE was mixed in a weight ratio of 8: 1: 1.
【００３９】次いでこの混合物とエタノールとの合計量
に対して６０重量％となるように、液状潤滑剤としてエ
タノールを添加し、混練して混練物を得た。この混練物
を６０００ｍｍ／ｍｉｎの条件で押出成形して、ロッド
の長手方向に垂直な断面が楕円形であって、圧縮方向の
径（短径）が１８ｍｍ、圧縮方向に直行する横方向の径
（長径）が３２ｍｍの楕円形であり、ロッド長さが１ｍ
であるロッド状予備成形物を成形した。得られたロッド
状予備成形物をロール圧延により、圧延ロール温度４０
℃、圧力４４０ｋｇ／ｃｍの条件で圧延したところ、厚
さ０．１８ｍｍ、幅１５０ｍｍ、長さ５３ｍの連続シー
トを得た。得られたシートは、空気中３００℃で１分間
乾燥させ、シート状電極とした。Next, ethanol was added as a liquid lubricant so as to be 60% by weight based on the total amount of the mixture and ethanol, and kneaded to obtain a kneaded product. The kneaded material is extruded under the condition of 6000 mm / min. The cross section perpendicular to the longitudinal direction of the rod is elliptical, the diameter (short diameter) in the compression direction is 18 mm, and the diameter in the horizontal direction perpendicular to the compression direction. (Major axis) is 32mm elliptical, rod length is 1m
Was molded into a rod-shaped preform. The obtained rod-shaped preform is roll-rolled to a rolling roll temperature of 40.
When rolled under the conditions of ° C. and a pressure of 440 kg / cm, a continuous sheet having a thickness of 0.18 mm, a width of 150 mm and a length of 53 m was obtained. The obtained sheet was dried in air at 300 ° C. for 1 minute to obtain a sheet electrode.
【００４０】得られたシート状電極の引張強度は１２７
８ｍＮ／ｍｍ2、密度は０.５５ｇ／ｃｍ3および電気容
量は１１.７Ｆ／ｃｃとなった。結果を併せて表１に示
す。The tensile strength of the obtained sheet electrode was 127.
8 mN / mm 2 , density was 0.55 g / cm 3, and electric capacity was 11.7 F / cc. Table 1 also shows the results.
【００４１】[0041]
【実施例２、比較例１〜３】実施例１において、活性炭
の種類等を表１に示すものに変更し、表１に示す量で各
成分を用いて、電気二重層キャパシタ用電極（シート状
電極）を作製した。この電極を用いて、各種試験を行っ
た。結果を表１に示す。Example 2 and Comparative Examples 1 to 3 In Example 1, the type and the like of the activated carbon were changed to those shown in Table 1, and each component was used in an amount shown in Table 1 to form an electrode (sheet) for an electric double layer capacitor. Electrodes). Various tests were performed using this electrode. Table 1 shows the results.
【００４２】[0042]
【表１】 [Table 1]
【図１】図１は、本発明で使用するロッド状予備成形物
とその断面の斜視図を示す。図１（ａ）は、断面が長円
（楕円）形のロッド状予備成形物を示し、また図１
（ｂ）は、断面が六角形のロッド状予備成形物を示す。FIG. 1 shows a perspective view of a rod-shaped preform used in the present invention and a cross section thereof. FIG. 1A shows a rod-shaped preform having an elliptical (elliptical) cross section.
(B) shows a rod-shaped preform having a hexagonal cross section.
【図２】図２は、本発明の一態様を示すシート状電気二
重層キャパシタ用電極の断面を模式的に示した説明図で
ある。FIG. 2 is an explanatory diagram schematically showing a cross section of an electrode for a sheet-like electric double layer capacitor according to one embodiment of the present invention.
ｄ・・・・・・圧縮方向の最大長さ（長径）
ｄ0・・・・・・圧縮方向と直交する横方向の最大長さ
（短径）。d ...... compression direction of the maximum length (long diameter) d 0 Maximum lateral perpendicular to ...... compression direction length (minor axis).
Claims (4)
示す標準偏差値が０．４００〜０．６００であることを
特徴とする、電気二重層キャパシタ用活性炭。An activated carbon for an electric double layer capacitor, having an average particle size of 20 to 60 μm and a standard deviation value indicating a particle size distribution of 0.400 to 0.600.
性炭（ａ１）２５〜５０％と、 粒子径が２０μｍ以上〜４０μｍ未満の活性炭（ａ２）
１５〜５５％と、 粒子径が４０μｍ以上の活性炭（ａ３）２０〜５０％
（（ａ１）＋（ａ２）＋（ａ３）＝１００％）とからな
ることを特徴とする請求項１に記載の電気二重層キャパ
シタ用活性炭。2. The activated carbon according to claim 1, wherein the activated carbon has a particle size of less than 20 μm (a1) 25 to 50%, and the activated carbon has a particle size of 20 μm to less than 40 μm (a2).
15 to 55%, activated carbon (a3) having a particle diameter of 40 μm or more 20 to 50%
The activated carbon for an electric double layer capacitor according to claim 1, wherein (a1) + (a2) + (a3) = 100%.
導電性カーボンと、バインダーとを含有することを特徴
とする電気二重層キャパシタ用電極。3. The activated carbon according to claim 1, wherein:
An electrode for an electric double layer capacitor comprising conductive carbon and a binder.
電極中に、１０〜９５重量％の量で含まれていることを
特徴とする請求項３に記載の電気二重層キャパシタ用電
極。4. The electric double layer capacitor electrode according to claim 3, wherein the activated carbon is contained in the electric double layer capacitor electrode in an amount of 10 to 95% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002148150A JP2003347172A (en) | 2002-05-22 | 2002-05-22 | Active carbon for electric double-layer capacitor, and electrode for electric double-layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002148150A JP2003347172A (en) | 2002-05-22 | 2002-05-22 | Active carbon for electric double-layer capacitor, and electrode for electric double-layer capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003347172A true JP2003347172A (en) | 2003-12-05 |
Family
ID=29766847
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002148150A Pending JP2003347172A (en) | 2002-05-22 | 2002-05-22 | Active carbon for electric double-layer capacitor, and electrode for electric double-layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003347172A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8848338B2 (en) | 2006-09-01 | 2014-09-30 | W. L. Gore & Associates, Co., Ltd. | Electric double layer capacitor |
| JP2014232807A (en) * | 2013-05-29 | 2014-12-11 | 日本バルカー工業株式会社 | Electrode sheet for electric double layer capacitor |
| JP2017084838A (en) * | 2015-10-22 | 2017-05-18 | 株式会社キャタラー | Carbon material for power storage device, and power storage device |
-
2002
- 2002-05-22 JP JP2002148150A patent/JP2003347172A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8848338B2 (en) | 2006-09-01 | 2014-09-30 | W. L. Gore & Associates, Co., Ltd. | Electric double layer capacitor |
| JP2014232807A (en) * | 2013-05-29 | 2014-12-11 | 日本バルカー工業株式会社 | Electrode sheet for electric double layer capacitor |
| JP2017084838A (en) * | 2015-10-22 | 2017-05-18 | 株式会社キャタラー | Carbon material for power storage device, and power storage device |
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