JP2000344507A - Powdery activated carbon, activated carbon sheet and electric double layer capacitor - Google Patents
Powdery activated carbon, activated carbon sheet and electric double layer capacitorInfo
- Publication number
- JP2000344507A JP2000344507A JP11159244A JP15924499A JP2000344507A JP 2000344507 A JP2000344507 A JP 2000344507A JP 11159244 A JP11159244 A JP 11159244A JP 15924499 A JP15924499 A JP 15924499A JP 2000344507 A JP2000344507 A JP 2000344507A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- powdered activated
- particles
- particle size
- electrode
- 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
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]
【発明の属する技術分野】本発明は、粉末活性炭、活性
炭シート及び電気二重層キャパシタに関する。さらに詳
しくは、中心粒子径が１０μｍ以上５０μｍ以下であっ
て、中心粒子径の１／１０以下の大きさの粒子の割合が
６％以上１３％以下である粉末活性炭、該粉末活性炭及
びバインダーからなる混合物を成型せしめた活性炭シー
ト、及び該活性炭シートを電極とした電気二重層キャパ
シタに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powdered activated carbon, an activated carbon sheet and an electric double layer capacitor. More specifically, the powdered activated carbon has a center particle diameter of 10 μm or more and 50 μm or less, and the ratio of particles having a size of 1/10 or less of the center particle diameter is 6% or more and 13% or less, and is made of the powdered activated carbon and a binder. The present invention relates to an activated carbon sheet formed by molding a mixture and an electric double layer capacitor using the activated carbon sheet as an electrode.
【０００２】[0002]
【従来の技術】近年、分極性電極と電解質界面に生じる
電気二重層を利用してエネルギーを貯蔵する電気二重層
キャパシタの開発が広くなされている。電気二重層キャ
パシタ（以下、電気二重層キャパシタを単にキャパシタ
と略称する）は、アルミニウム等の金属箔あるいは導電
性ゴムのような集電体上に活性炭からなる２枚の電極を
セパレーターを介して対峠させ、電気二重層形成イオン
を含む電解液を注入した構造であり、ファラッド級の大
容量を有し、充放電サイクルにも優れることから、各種
電気機器のバックアップ電源、太陽電池と組み合わせた
発光ダイオードの電源、おもちゃ等の小型モーターの電
源、車載バッテリーなどの用途に多く使用されている。2. Description of the Related Art In recent years, electric double layer capacitors which store energy using an electric double layer generated at the interface between a polarizable electrode and an electrolyte have been widely developed. An electric double layer capacitor (hereinafter, the electric double layer capacitor is simply referred to as a capacitor) is a pair of two electrodes made of activated carbon formed on a current collector such as a metal foil such as aluminum or a conductive rubber via a separator. It has a structure in which an electrolyte containing ions forming an electric double layer is injected, and has a farad-class large capacity and excellent charge / discharge cycle, so it emits light in combination with a backup power supply for various electric devices and a solar cell. It is widely used for power supplies for diodes, power supplies for small motors such as toys, and in-vehicle batteries.
【０００３】かかるキャパシタの電極材料には、大きな
比表面積をもつ活性炭繊維や粉末活性炭などのカーボン
系材料が使用されることが多い。例えば、特開平２−２
４０９０９号及び特開平２−２４１０１２号公報に、活
性炭繊維をパルプ、炭素繊維に加え、バインダー及び分
散剤を用いて抄紙とした分極性電極が開示されており、
特開平４−２２０６２号公報に、特定の粒子径を持つ活
性炭粉末及びプラスチック粉末を混合し、板状に成型し
たキャパシタが開示されており、また、特開平８−１１
９６１５号公報には、繊維状活性炭、粉末活性炭及びバ
インダーからなる混合物を成型したシートを電極とする
キャパシタが開示されている。As the electrode material of such a capacitor, a carbon-based material such as activated carbon fiber or powdered activated carbon having a large specific surface area is often used. For example, Japanese Patent Application Laid-Open No. 2-2
Japanese Patent No. 40909 and JP-A-2-241012 disclose a polarizable electrode obtained by adding activated carbon fiber to pulp and carbon fiber, and using a binder and a dispersant to make paper.
JP-A-4-22062 discloses a capacitor formed by mixing activated carbon powder having a specific particle diameter and plastic powder and molding the mixture into a plate shape.
No. 9615 discloses a capacitor in which a sheet formed from a mixture of fibrous activated carbon, powdered activated carbon and a binder is used as an electrode.
【０００４】キャパシタに蓄電できる体積あたりのエネ
ルギー量を上げるためには高い比表面積の活性炭を高密
度で充填した電極を使用する必要がある。しかしなが
ら、活性炭の充填密度と比表面積とは逆比例する関係に
あるので、高い比表面積の活性炭を高密度で充填するの
は極めて困難である。高比表面積の粉末活性炭を高密度
で充填する方法として、特開平９−３２０９０６号公報
に、粉末活性炭にテフロン粉末等のバインダーを５〜１
０％程度混合した後に加圧成型する方法が提案されてい
る。また、特開平９−２８９０２３号公報に、フッ化ビ
ニリデン系共重合体をバインダーとし、Ｎ―メチルー２
―ピロリドンに均一に溶解した後に粉末活性炭を混合
し、ペースト状に加工しドクターブレードで塗布し加熱
・乾燥する方法が開示されている。In order to increase the amount of energy per volume that can be stored in a capacitor, it is necessary to use an electrode filled with activated carbon having a high specific surface area at a high density. However, since the packing density of the activated carbon is in inverse proportion to the specific surface area, it is extremely difficult to fill the activated carbon having a high specific surface area at a high density. Japanese Patent Application Laid-Open No. 9-320906 discloses a method of filling powdered activated carbon with a high specific surface area at a high density.
A method of pressure molding after mixing about 0% has been proposed. JP-A-9-289023 discloses that a vinylidene fluoride copolymer is used as a binder and N-methyl-2
-Disclosed is a method in which powdered activated carbon is mixed after being uniformly dissolved in pyrrolidone, processed into a paste, applied with a doctor blade, heated and dried.
【０００５】従来、活性炭を粉砕してキャパシタ用活性
炭とするには、主としてボールミルあるいは振動ボール
ミルによる方法が実施されている。このようにして得ら
れる電気二重層キャパシタに使用される活性炭としては
中心粒子径が３〜４０μｍであって、中心粒子径の１／
１０以下の大きさの粒子の割合は５％以下であった。Conventionally, a method using a ball mill or a vibrating ball mill is mainly used to pulverize activated carbon into activated carbon for a capacitor. The activated carbon used for the electric double layer capacitor thus obtained has a central particle diameter of 3 to 40 μm and is 1/1/1 of the central particle diameter.
The ratio of particles having a size of 10 or less was 5% or less.
【０００６】活性炭の粒度分布をシャープにする場合に
は風力分球機が併用されている。ボールミルで粉砕した
場合には分布がブロードになりやすく、そのために充填
密度が大きくなりやすい傾向にあるが、電極に成型を行
った場合の活性炭の充填密度は実用上十分なレベルまで
向上しなかった。またこの時の中心粒子径の１／１０以
下の大きさの粒子の割合は５％以下であった。ボールミ
ルを使用し、粉砕時間を長くすると小さな粒子は増加す
るが、中心粒子径も小さくなるために電極に成型した場
合の充填密度は依然として大きくならない。[0006] In order to sharpen the particle size distribution of activated carbon, an air sieving machine is also used. When crushed with a ball mill, the distribution tends to be broad and the packing density tends to increase, but the packing density of activated carbon when the electrode is molded has not been improved to a practically sufficient level. . At this time, the ratio of particles having a size of 1/10 or less of the central particle diameter was 5% or less. When a pulverizing time is increased by using a ball mill, the number of small particles increases. However, since the center particle diameter also decreases, the packing density when molded into an electrode does not increase yet.
【０００７】[0007]
【発明が解決しようとする課題】高比表面積の粉末活性
炭を使用して高充填密度の活性炭電極を得るためには、
活性炭粉末にテフロン等のバインダーを混合し、加圧成
型するのが効果的である。しかしバインダーの量を増や
した場合にはバインダーにより活性炭表面が覆われるた
めに容量が低下し、バインダーを粉末活性炭に対し１０
％（重量％）以上添加した場合には活性炭の容量低下が
著しく、活性炭の充填密度が上がっても体積あたりの容
量は増加しなかった。またバインダーを多く使用した場
合にはキャパシタの内部抵抗が増大するという問題もあ
った。In order to obtain an activated carbon electrode having a high packing density using powdered activated carbon having a high specific surface area,
It is effective to mix activated carbon powder with a binder such as Teflon and press-mold. However, when the amount of the binder is increased, the capacity is reduced because the surface of the activated carbon is covered with the binder, and the amount of the binder is reduced by 10 to the activated carbon powder.
% (% By weight), the capacity of the activated carbon decreased significantly, and the capacity per volume did not increase even if the packing density of the activated carbon increased. Further, when a large amount of binder is used, there is a problem that the internal resistance of the capacitor increases.
【０００８】キャパシタの内部抵抗が増加する原因は、
バインダーが電気的な絶縁物であることにより、電極と
して使用する活性炭シートの電気抵抗が低下するためで
あり、また、バインダーが粉末活性炭間に多く充填され
ることにより、電解質イオンの通路が減少し、イオンの
運動が妨げられるためである。バインダーの量は少ない
程よいが、あまり少ないと粉末活性炭を捕捉する力が弱
く、加圧した場合でも電極の密度は上がらない傾向にあ
る。したがって本発明の目的は、少ないバインダー量で
成型した場合でも高充填密度を達成できる粉末活性炭を
提供することにある。The cause of the increase in the internal resistance of the capacitor is as follows.
This is because the electric resistance of the activated carbon sheet used as an electrode is reduced by the fact that the binder is an electrical insulator, and the passage of electrolyte ions is reduced by the fact that the binder is largely filled between the activated carbon powders. This is because the movement of ions is hindered. The smaller the amount of the binder, the better. However, if the amount is too small, the power for capturing the powdered activated carbon is weak, and the density of the electrode does not tend to increase even when pressure is applied. Accordingly, an object of the present invention is to provide a powdered activated carbon that can achieve a high packing density even when molded with a small amount of a binder.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、上記目的
を達成するため鋭意検討を重ね、本発明に到達した。す
なわち、本発明は、中心粒子径が１０μｍ以上５０μｍ
以下であって、中心粒子径の１／１０以下の大きさの粒
子の割合が６％以上１３％以下である粉末活性炭であ
る。また、本発明のもう一つの発明は、上記記載の粉末
活性炭及びバインダーからなる混合物を成型せしめた活
性炭シートであり、本発明の別の発明は、上記記載の活
性炭シートを電極とした電気二重層キャパシタである。Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and have reached the present invention. That is, in the present invention, the center particle diameter is 10 μm or more and 50 μm
Powder activated carbon in which the ratio of particles having a size of 1/10 or less of the central particle diameter is 6% or more and 13% or less. Further, another invention of the present invention is an activated carbon sheet formed by molding a mixture comprising the above-described powdered activated carbon and a binder, and another invention of the present invention provides an electric double layer using the above-described activated carbon sheet as an electrode. It is a capacitor.
【００１０】[0010]
【発明の実施の形態】本発明の粉末活性炭の中心粒子径
及び中心粒子径の１／１０以下の大きさの粒子の割合
は、あまり小さくても、また、あまり大きくても電極中
の活性炭密度及び体積あたりの容量が小さくなるので、
中心粒子径は１０μｍ以上５０μｍ以下、好ましくは１
３μｍ以上４４μｍ以下の粉末活性炭が、また、中心粒
子径の１／１０以下の大きさの粒子の割合は６％以上１
３％以下の活性炭が使用される。BEST MODE FOR CARRYING OUT THE INVENTION In the powdered activated carbon of the present invention, even if the center particle diameter and the ratio of particles having a size of 1/10 or less of the center particle diameter are too small or too large, the density of the activated carbon in the electrode is small. And since the capacity per volume becomes smaller,
The center particle diameter is 10 μm or more and 50 μm or less, preferably 1 μm or less.
Activated carbon powder of 3 μm or more and 44 μm or less, and the ratio of particles having a size of 1/10 or less of the central particle diameter is 6% or more and
Up to 3% of activated carbon is used.
【００１１】このような活性炭粉末を製造する方法はと
くに限定されないが、例えば、本発明の粉末活性炭を得
るためには二つの粒度分布を有する粉末活性炭を均一混
合してもよいし、あるいは粉末活性炭に高速で圧縮と混
合を繰り返してもよい。本発明者らが検討したところに
よると、粉末活性炭に高速で圧縮と混合を繰り返した場
合の方が粉末活性炭の中に占める細かな粒子の割合が増
加し、活性炭密度を高くすることができるので、好まし
い。高速で圧縮と混合を繰り返すには、例えば後述する
ホソカワミクロン株式会社から商品名ＡＭＳ―３０Ｓで
市販されている粒子複合化装置を使用すればよい。The method for producing such activated carbon powder is not particularly limited. For example, in order to obtain the powdered activated carbon of the present invention, powdered activated carbon having two particle size distributions may be uniformly mixed, or powdered activated carbon may be obtained. The compression and mixing may be repeated at high speed. According to the investigations by the present inventors, the ratio of fine particles in powdered activated carbon increases when powdered activated carbon is repeatedly compressed and mixed at a high speed, and the activated carbon density can be increased. ,preferable. In order to repeat the compression and mixing at a high speed, for example, a particle composite apparatus commercially available from Hosokawa Micron Corporation under the trade name AMS-30S may be used.
【００１２】また、二つの粒度分布を有する粉末活性炭
を混合した後に高速で圧縮と混合を繰り返してもよい。
本発明の粉末活性炭を使用することにより電極中の活性
炭の充填密度は５％〜１３％程度向上する。活性炭の吸
着性能は低下しないためにキャパシタの体積あたりの容
量も同等に向上する。また、内部抵抗が増大しないとい
う効果も発現する。Further, after mixing powdered activated carbon having two particle size distributions, compression and mixing may be repeated at a high speed.
By using the powdered activated carbon of the present invention, the packing density of the activated carbon in the electrode is improved by about 5% to 13%. Since the adsorption performance of the activated carbon does not decrease, the capacity per volume of the capacitor is also improved. Also, an effect that the internal resistance does not increase is exhibited.
【００１３】粉末活性炭の中心粒子径および粒度分布を
測定するには遠心沈降法あるいはレーザー回折法が一般
的に使用されるが、測定精度が高いという点でレーザー
回折型粒度分布計を使用するのが好ましい。A centrifugal sedimentation method or a laser diffraction method is generally used to measure the central particle diameter and the particle size distribution of the powdered activated carbon. However, a laser diffraction type particle size distribution meter is used because the measurement accuracy is high. Is preferred.
【００１４】本発明の活性炭粉末をシートに成型するに
は、活性炭粉末１００重量部に対し、テフロン、ポリビ
ニリデンフルオライド（ＰＶＤＦ）などのバインダー５
〜１０重量部を混合し、ロールプレスなどで圧縮成型す
る。成型温度はバインダーの種類に応じて適宜選択すれ
ばよいが、通常は室温程度で実施される。加熱して冷却
プレスする方法によってもよい。To form the activated carbon powder of the present invention into a sheet, a binder 5 such as Teflon or polyvinylidene fluoride (PVDF) is added to 100 parts by weight of the activated carbon powder.
-10 parts by weight are mixed and compression-molded by a roll press or the like. The molding temperature may be appropriately selected according to the type of the binder, but is usually carried out at about room temperature. A method of heating and cooling press may be used.
【００１５】一般的な傾向として、中心粒子径が小さい
場合にはより多くのバインダーが必要になる。この理由
は活性炭粒子が小さくなることにより活性炭の見かけの
表面積（活性炭粒子の外表面の面積）が増大するためで
あると推定される。小さな粒子が多い粉末活性炭におい
ては中心粒子直径が１０μｍ以下である場合には５〜１
０％のバインダー量では活性炭粉末をバインダーにより
十分に捕捉することができない。本発明の粉末活性炭は
従来の粉末活性炭と比較して微粉の量が増加しているた
め、とくにその傾向が大きい。As a general tendency, when the central particle diameter is small, more binder is required. This is presumed to be because the apparent surface area of the activated carbon (the area of the outer surface of the activated carbon particles) increases as the activated carbon particles become smaller. In the case of powdered activated carbon having many small particles, if the center particle diameter is 10 μm or less, 5 to 1
If the binder amount is 0%, the activated carbon powder cannot be sufficiently captured by the binder. The powdered activated carbon of the present invention has a particularly large tendency because the amount of the fine powder is increased as compared with the conventional powdered activated carbon.
【００１６】本発明の粉末活性炭を走査電子顕微鏡を使
用して観察すると、粉末活性炭中に存在する細かな粒子
は大きな粒子の周囲に付着した状態で存在する。したが
って、粉末活性炭を５〜１０％のバインダーと混合し電
極として成型した場合、大きな粒子の周りに小さな粒子
が存在する状態で最密充填の状態が達成されていると考
えられる。このため中心となる粒子が大きい場合と小さ
い場合とでは必要となる粒子の大きさが変化する。When the powdered activated carbon of the present invention is observed using a scanning electron microscope, fine particles present in the powdered activated carbon are present in a state of being attached around large particles. Therefore, when powdered activated carbon is mixed with a binder of 5 to 10% and molded as an electrode, it is considered that a close-packed state is achieved in a state where small particles exist around large particles. Therefore, the required particle size changes depending on whether the central particle is large or small.
【００１７】本発明の粉末活性炭を使用すれば、成型時
の活性炭の密度が０．６５ｇ／ｃｃ以上、とくに好まし
くは０．６７ｇ／ｃｃ以上の電極を作製することができ
る。従来の粉末活性炭を使用した場合には０．６３ｇ／
ｃｃ程度の密度にしか成型が困難であったが、本発明の
粉末活性炭を使用することにより、充填密度を大きく向
上させることができる。When the powdered activated carbon of the present invention is used, an electrode having an activated carbon density of 0.65 g / cc or more, particularly preferably 0.67 g / cc or more, can be produced. When conventional powdered activated carbon is used, 0.63 g /
Although molding was difficult only to a density of about cc, the use of the powdered activated carbon of the present invention can greatly improve the packing density.
【００１８】本発明に使用される活性炭は１ｇあたり３
００ｍ２／ｇ以上の大きな比表面積を有し、高い吸着性
能を示す材料であれば高範囲に使用できる。活性炭の原
料としては、椰子殻、木材あるいはフェノール樹脂等の
炭化物あるいは石炭が使用される。なかでも、椰子殻を
原料とする活性炭は粉砕と粒度調整が容易であり、さら
に高速で圧縮と混合を繰り返すことにより中心粒子径は
ほとんど変化せずに小さな粒子のみが増加しやすく、充
填密度が上がりやすいという点で本発明の効果を最も顕
著に発揮でき、好ましい。これらの活性炭は、水蒸気あ
るいは二酸化炭素により高温であるいは、塩化亜鉛、リ
ン酸、水酸化カリウム等により薬品により賦活された活
性炭でもよい。The activated carbon used in the present invention is 3 g / g.
A material having a large specific surface area of at least 00 m 2 / g and exhibiting high adsorption performance can be used in a wide range. As a raw material of the activated carbon, coconut shell, wood, carbide such as phenolic resin or coal is used. Above all, activated carbon made from coconut shell is easy to pulverize and adjust the particle size, and by repeating compression and mixing at high speed, the center particle diameter hardly changes and only small particles tend to increase, and the packing density is increased. The effect of the present invention can be most remarkably exhibited in that it is easily raised, which is preferable. These activated carbons may be activated carbons activated by steam or carbon dioxide at a high temperature or activated by zinc chloride, phosphoric acid, potassium hydroxide or the like.
【００１９】前述したように、キャパシタは、アルミニ
ウム等の金属箔あるいは導電性ゴムのような集電体上に
活性炭からなる２枚の電極をセパレーターを介して対峠
させ、電気二重層形成イオンを含む電解液を注入した構
造であり、該電解液としては、硫酸水溶液などの水溶液
系電解液を使用する場合と、プロピレンカーボネート、
γ―ブチロラクトン、アセトニトリル、ジメチルホルム
アミドのような有機溶媒にテトラノルマルブチルアンモ
ニウムテトラフルオロボレート等の電解質を溶解した有
機電解液を使用する場合がある。有機電解液系キャパシ
タは耐電圧が２．５Ｖ程度と高く、キャパシタの蓄電エ
ネルギー量は電圧の二乗に比例するため、高エネルギー
密度のキャパシタを作る場合には有機電解液を使用する
のが好ましい。As described above, in the capacitor, two electrodes made of activated carbon are passed through a separator on a metal foil such as aluminum or a current collector such as conductive rubber via a separator, and ions forming an electric double layer are formed. It has a structure in which an electrolytic solution containing is injected, as the electrolytic solution, when using an aqueous electrolytic solution such as a sulfuric acid aqueous solution, propylene carbonate,
An organic electrolyte in which an electrolyte such as tetra-n-butylammonium tetrafluoroborate is dissolved in an organic solvent such as γ-butyrolactone, acetonitrile, or dimethylformamide may be used. An organic electrolytic solution-based capacitor has a high withstand voltage of about 2.5 V and the amount of stored energy of the capacitor is proportional to the square of the voltage. Therefore, when a capacitor having a high energy density is produced, it is preferable to use an organic electrolytic solution.
【００２０】本発明の粉末活性炭をシートに成型し、該
シートを使用してボタン型キャパシタを作製した例を図
１に示す。図１において、１は正極、２は負極、３はス
テンレス蓋、４はステンレスケース、５は封口体、６は
セパレーター、７は電解液である。以下、実施例により
本発明を具体的に説明するが本発明はこれらに限定され
るものではない。FIG. 1 shows an example in which the powdered activated carbon of the present invention is formed into a sheet, and a button-type capacitor is manufactured using the sheet. In FIG. 1, 1 is a positive electrode, 2 is a negative electrode, 3 is a stainless steel lid, 4 is a stainless steel case, 5 is a sealing body, 6 is a separator, and 7 is an electrolyte. Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.
【００２１】[0021]
【実施例】参考実験例 椰子殻を乾留した炭化物を４〜１０メッシュ（粒径１．
７ｍｍ以上、４．７５ｍｍ以下）に整粒して粒状活性炭
の原料とした。この原料炭化物をプロパン燃焼ガスを用
いて９００℃で４時間賦活した後、同一組成のガス中で
３００℃以下まで冷却した。この活性炭の灰分は２．５
重量％であった。この活性炭を濃度１０重量％、温度５
０℃の塩酸水溶液で繰り返し洗浄を行った。その後水洗
浄を行い、１５０℃で１２時間乾燥を行った。この活性
炭の灰分は０．３重量％であって、電気二重層キャパシ
タ用活性炭の電極として使用可能なレベルまで低下して
いた。この活性炭のベンゼン吸着量は５０％、ヨード吸
着性能は１７００ｍｇ／ｇであった。またこの活性炭の
容量は２７Ｆ（ファラッド）／ｇであった。容量の測定
には電解液として１Ｍ（Ｃ２Ｈ５）４ＢＦ４のプロピレ
ンカーボネート（ＰＣ）溶液を使用した。EXAMPLES Reference Experimental Example 4 to 10 meshes of carbonized carbonized coconut shell (particle size 1.
(7 mm or more and 4.75 mm or less) to obtain a raw material for granular activated carbon. This raw material carbide was activated at 900 ° C. for 4 hours using propane combustion gas, and then cooled to 300 ° C. or lower in a gas having the same composition. The ash content of this activated carbon is 2.5
% By weight. This activated carbon was used at a concentration of
Washing was repeatedly performed with a hydrochloric acid aqueous solution at 0 ° C. Thereafter, washing with water was performed, and drying was performed at 150 ° C. for 12 hours. The ash content of this activated carbon was 0.3% by weight, and was reduced to a level usable as an electrode of activated carbon for electric double layer capacitors. The activated carbon had a benzene adsorption amount of 50% and an iodine adsorption performance of 1700 mg / g. The capacity of this activated carbon was 27 F (farad) / g. For the measurement of the capacity, a propylene carbonate (PC) solution of 1 M (C 2 H 5 ) 4 BF 4 was used as an electrolytic solution.
【００２２】この活性炭をボールミルに入れ１２時間粉
砕を行った。この粉末活性炭の中心粒子径（５０％Ｄ）
および粒度分布をレーザー回折型粒度分布計（島津製作
所製ＳＡＬＤ―３０００Ｓ）を使用し測定した。中心粒
子直径は４５μｍ、中心粒子径が１／１０以下の粒子の
割合は５％であった。中心粒子径の１／１０の粒子の割
合はその値に最も近い測定値の上下二つの値から比例計
算によって算定した。This activated carbon was put into a ball mill and pulverized for 12 hours. Center particle diameter of this powdered activated carbon (50% D)
The particle size distribution was measured using a laser diffraction type particle size distribution meter (SALD-3000S manufactured by Shimadzu Corporation). The center particle diameter was 45 μm, and the ratio of particles having a center particle diameter of 1/10 or less was 5%. The proportion of particles having a diameter of 1/10 of the central particle diameter was calculated by proportional calculation from the upper and lower values of the measured value closest to the value.
【００２３】実施例１ 参考実験例で得た粉末活性炭を、高速で圧縮と混合を行
う粒子複合化装置（ホソカワミクロン株式会社製ＡＭＳ
―３０Ｓ）を使用し、回転数１１００ｒｐｍで３０分間
圧縮と混合を行った。インナーピースと回転容器との間
は８ｍｍとした。該粒子複合化装置による圧縮と混合の
原理を簡単に説明する。まず、該装置に粉末活性炭を投
入し、５００〜２５００ｒｐｍ程度の速さで高速回転さ
せる。粉末活性炭は遠心力により容器内壁に固定され
る。中心軸に固定されたインナーピースと回転する容器
の間を粉末活性炭は高速で通過し、この時に圧縮力を受
ける。Example 1 A particle composite apparatus (AMS manufactured by Hosokawa Micron Corporation) for compressing and mixing the powdered activated carbon obtained in the reference experimental example at a high speed.
Using -30S), compression and mixing were performed at a rotation speed of 1100 rpm for 30 minutes. The distance between the inner piece and the rotating container was 8 mm. The principle of compression and mixing by the particle composite device will be briefly described. First, powdered activated carbon is charged into the apparatus and rotated at a high speed of about 500 to 2500 rpm. The powdered activated carbon is fixed to the inner wall of the container by centrifugal force. The powdered activated carbon passes between the inner piece fixed to the center shaft and the rotating container at a high speed, and receives a compressive force at this time.
【００２４】インナーピースの後には粉末活性炭を回転
容器から剥ぎ取るためのスクレーパーが設置してあり、
圧縮された粉末活性炭は直後に攪拌混合される。この作
業を高速で繰り返す。この装置で処理された粉末活性炭
は中心粒子直径４３μｍ、１／１０以下の粒子は７．５
％に増加していた。細かな粒子が増加した理由は高速の
圧縮と混合により粉末活性炭の中で割れやすい部分が選
択的に破損したためではないかと考えられる。After the inner piece, there is provided a scraper for stripping the powdered activated carbon from the rotary container.
The compacted powdered activated carbon is immediately stirred and mixed. This operation is repeated at high speed. The powdered activated carbon treated by this apparatus has a central particle diameter of 43 μm, and particles of 1/10 or less are 7.5.
% Had increased. It is considered that the reason for the increase in fine particles is that the fragile portion in the powdered activated carbon was selectively damaged by high-speed compression and mixing.
【００２５】該装置で粉末活性炭を処理する前と処理し
た後の粉末活性炭の状態を走査電子顕微鏡で観察した。
図２と図３に処理前の粉末活性炭の状態を各々倍率１０
００倍及び２０００倍で示し、図４と図５に処理後の粉
末活性炭の状態を各々倍率１０００倍及び２０００倍で
示した。処理後は処理前と比較して小さな粒子が格段に
増加していることが明瞭である。この結果はレーザー回
折型粒度分布計での測定結果と一致していた。また、小
さな粒子が大きな粒子の周りに付着した状態で存在して
いる様子も明瞭である。The state of the powdered activated carbon before and after the treatment of the powdered activated carbon with the apparatus was observed with a scanning electron microscope.
2 and 3 show the state of the powdered activated carbon before treatment at a magnification of 10 respectively.
4 and 5 show the states of the powdered activated carbon after the treatment at magnifications of 1000 and 2000, respectively. It is clear that small particles are significantly increased after the treatment as compared to before the treatment. This result was consistent with the measurement result obtained with the laser diffraction type particle size distribution meter. It is also clear that small particles are present around large particles in a state of being attached.
【００２６】この粉末活性炭に重量比で７．５％のテフ
ロン７Ｊとデンカブラック７．５％を加え均一に混合
し、ロールプレスで圧縮成型してシートに成型した。該
シートを打ち抜き、直径２０ｍｍ、重さ１００ｍｇの活
性炭シートを得た。該シートの厚さから活性炭の充填密
度を測定したところ、０．７８ｇ／ｃｃであり、この値
から換算した電極中の活性炭密度は０．６８ｇ／ｃｃで
あった。該シート２枚とセパレーターとして硝子繊維ペ
ーパーを使用し、電解液として１Ｍ（Ｃ２Ｈ５） ４ＢＦ
４のＰＣ溶液を使用してボタン型キャパシタを作製し
た。２．３Ｖ定電圧充電を３０分間行い、４ｍＡ定電流
放電により容量を測定したところ、成型活性炭電極の単
位体積あたりの容量は１８．４Ｆ／ｃｃであった。結果
を表１に示す。The powdered activated carbon has a weight ratio of 7.5% Tef.
Add Ron 7J and 7.5% Denka Black and mix uniformly
Then, compression molding was performed by a roll press to form a sheet. The
The sheet was punched out and had a diameter of 20 mm and a weight of 100 mg.
A charcoal sheet was obtained. The packing density of the activated carbon is determined from the thickness of the sheet.
When the degree was measured, it was 0.78 g / cc.
The activated carbon density in the electrode calculated from is 0.68 g / cc.
there were. Two sheets and a glass fiber paper as a separator
1M (C2H5) 4BF
4Of button type capacitor using PC solution
Was. Charge at 2.3V constant voltage for 30 minutes, 4mA constant current
When the capacity was measured by discharging,
The capacity per unit volume was 18.4 F / cc. result
Are shown in Table 1.
【００２７】比較例１ 参考実験例で得た処理前の粉末活性炭を使用した場合の
電極密度は０．７２ｇ／ｃｃであった（電極中の活性炭
の密度０．６３ｇ／ｃｃ）。この成型活性炭を実施例１
と同様な方法で評価したところ、処理前の活性炭を使用
した場合の容量は１７．０Ｆ／ｃｃであった。この容量
は従来の電気二重層キャパシタの標準的な容量であり、
この値を容量の大小を検討する場合の指標とした。容量
の増加率は電極中の活性炭の密度の向上率に比例してい
た。小さな粒子の増加率は２．５％であったが容量は
７．６％も大幅に向上していた。結果を表１に示す。Comparative Example 1 The electrode density was 0.72 g / cc when the powdered activated carbon before treatment obtained in the reference experimental example was used (the density of activated carbon in the electrode was 0.63 g / cc). Example 1
When the evaluation was performed in the same manner as in the above, the capacity when the activated carbon before the treatment was used was 17.0 F / cc. This capacity is the standard capacity of conventional electric double layer capacitors,
This value was used as an index when considering the magnitude of the capacity. The increase rate of the capacity was proportional to the increase rate of the density of the activated carbon in the electrode. The increase rate of the small particles was 2.5%, but the capacity was greatly improved by 7.6%. Table 1 shows the results.
【００２８】実施例２ １５分処理を行った以外は実施例１と同様にして粉末活
性炭を得た。該粉末活性炭の中心粒子径は４４μｍで、
１／１０以下の粒子は６．５％であった。この粉末活性
炭を使用して実施例１と同様にして電極を作製した。電
極中の活性炭の密度は０．６７ｇ／ｃｃで、容量は１
８．１Ｆ／ｃｃであり、容量は６．５％向上した。結果
を表１に示す。Example 2 A powdered activated carbon was obtained in the same manner as in Example 1 except that the treatment was performed for 15 minutes. The central particle diameter of the powdered activated carbon is 44 μm,
6.5% of the particles were 1/10 or less. Using this powdered activated carbon, an electrode was produced in the same manner as in Example 1. The density of the activated carbon in the electrode was 0.67 g / cc and the capacity was 1
It was 8.1 F / cc, and the capacity was improved by 6.5%. Table 1 shows the results.
【００２９】実施例３ ６０分間処理を行った以外は実施例１と同様にして粉末
活性炭を得た。該粉末活性炭の中心粒子径は４３μｍ
で、１／１０以下の粒子は９．０％であった。この粉末
活性炭を使用して実施例１と同様にして電極を作製し
た。電極中の活性炭の密度は０．７０ｇ／ｃｃ、容量は
１８．９Ｆ／であり、容量は１１％向上した。結果を表
１に示す。Example 3 A powdered activated carbon was obtained in the same manner as in Example 1 except that the treatment was performed for 60 minutes. The central particle diameter of the powdered activated carbon is 43 μm
The ratio of particles of 1/10 or less was 9.0%. Using this powdered activated carbon, an electrode was produced in the same manner as in Example 1. The density of the activated carbon in the electrode was 0.70 g / cc, the capacity was 18.9 F /, and the capacity was improved by 11%. Table 1 shows the results.
【００３０】実施例４ １２０分処理を行った以外は実施例１と同様にして粉末
活性炭を得た。該粉末活性炭の中心粒子径は４０μｍ
で、１／１０以下の粒子は１１％であった。電極中の活
性炭密度は０．７１ｇ／ｃｃで、容量は１９．２Ｆ／ｃ
ｃであり、容量は１２％向上しており、小さな粒子の割
合の増加に伴い、容量が向上した。結果を表１に示す。Example 4 A powdered activated carbon was obtained in the same manner as in Example 1 except that the treatment was performed for 120 minutes. The center particle diameter of the powdered activated carbon is 40 μm
The ratio of particles having a size of 1/10 or less was 11%. The activated carbon density in the electrode was 0.71 g / cc, and the capacity was 19.2 F / c.
c, the capacity was improved by 12%, and the capacity was improved as the proportion of small particles was increased. Table 1 shows the results.
【００３１】実施例５ 参考実験例で得た粉末活性炭をボールミルを使用し、さ
らに２４時間粉砕を行った。この活性炭の中心粒子径は
５μｍであった。参考実験例で得た粉末活性炭と上記粉
砕した粉末活性炭を１：１（重量比）の割合でボールミ
ルに入れ、２時間混合した。得られた粉末活性炭の中心
粒子径は１６μｍで、１／１０以下の粒子は７％であっ
た。この粉末活性炭を使用した電極中の活性炭密度は
０．６６ｇ／ｃｃ、容量は１７．８Ｆ／ｃｃであり、容
量は５％向上した。結果を表１に示す。Example 5 The powdered activated carbon obtained in the Reference Experimental Example was further ground for 24 hours using a ball mill. The center particle diameter of this activated carbon was 5 μm. The powdered activated carbon obtained in the reference experimental example and the pulverized powdered activated carbon were put into a ball mill at a ratio of 1: 1 (weight ratio) and mixed for 2 hours. The center particle diameter of the obtained powdered activated carbon was 16 μm, and particles of 1/10 or less were 7%. The activated carbon density in the electrode using this powdered activated carbon was 0.66 g / cc, the capacity was 17.8 F / cc, and the capacity was improved by 5%. Table 1 shows the results.
【００３２】実施例６ 実施例５で得た粉末活性炭を実施例４と同様にして高速
で圧縮と混合を１２０分間行った。中心粒子径は１３μ
ｍで、１／１０以の粒子は１３％に増加した。この粉末
活性炭を使用した電極中の活性炭密度は０．７２ｇ／ｃ
ｃ、容量は１９．４Ｆ／ｃｃであり、容量は１３％向上
した。結果を表１に示す。Example 6 The powdered activated carbon obtained in Example 5 was compressed and mixed at a high speed for 120 minutes in the same manner as in Example 4. The center particle diameter is 13μ
At m, 1/10 or more particles increased to 13%. The activated carbon density in the electrode using this powdered activated carbon is 0.72 g / c.
c, the capacity was 19.4 F / cc, and the capacity was improved by 13%. Table 1 shows the results.
【００３３】実施例７ 参考実験例で得た粉末活性炭をさらに１７時間ボールミ
ルで粉砕し、中心粒子径が１２μｍ、１／１０以下粒子
が５％の粉末活性炭とした。この活性炭を実施例１と同
様にして３０分間高速で圧縮と混合を繰り返した。得ら
れた粉末活性炭は中心粒子径１０μｍ、１／１０以下の
粒子の割合は７％であった。この粉末活性炭の電極での
密度は０．６７ｇ／ｃｃ、容量は１８．１Ｆ／ｃｃであ
った。容量は６．５％向上した。結果を表１に示す。Example 7 The powdered activated carbon obtained in the Reference Experimental Example was further pulverized by a ball mill for 17 hours to obtain powdered activated carbon having a center particle diameter of 12 μm and 1/10 or less particles of 5%. Compression and mixing of this activated carbon were repeated at a high speed for 30 minutes in the same manner as in Example 1. The obtained powdered activated carbon had a center particle diameter of 10 μm and a ratio of particles having a particle size of 1/10 or less was 7%. The density of the powdered activated carbon at the electrode was 0.67 g / cc, and the capacity was 18.1 F / cc. Capacity increased by 6.5%. Table 1 shows the results.
【００３４】比較例２ 参考実験例で得た粉末活性炭を使用し、さらに３４時間
ボールミルで粉砕を行い、中心粒径３μｍの粉末活性炭
とした。この粉末活性炭を参考実験例で得た粉末活性炭
に１：１（重量比）の割合で混合した。中心粒子径は１
３μｍで、１／１０以下の粒子の割合は１４％であっ
た。この活性炭を使用して電極を成型した。活性炭密度
は０．６０ｇ／ｃｃ、容量は１６．２Ｆ／ｃｃであっ
た。容量は４．７％低下した。結果を表１に示す。Comparative Example 2 The powdered activated carbon obtained in the Reference Experimental Example was further pulverized with a ball mill for 34 hours to obtain powdered activated carbon having a central particle diameter of 3 μm. This powdered activated carbon was mixed with the powdered activated carbon obtained in the reference example at a ratio of 1: 1 (weight ratio). Central particle size is 1
At 3 μm, the percentage of particles less than 1/10 was 14%. An electrode was formed using this activated carbon. The activated carbon density was 0.60 g / cc, and the capacity was 16.2 F / cc. The capacity dropped 4.7%. Table 1 shows the results.
【００３５】比較例３ 参考実験例で得た粉末活性炭をさらに２０時間ボールミ
ルで粉砕を行い、中心粒子径９μｍの粉末活性炭とし
た。この活性炭を実施例３と同様にして６０分間圧縮と
混合を繰り返した。得られた粉末活性炭の中心粒子径は
８μｍで、１／１０以下の粒子は８％であった。この粉
末活性炭の電極中の活性炭密度は０．５７ｇ／ｃｃ、容
量は１５．４Ｆ／ｃｃと低下した。中心粒子径が１０μ
ｍ以下の場合には活性炭の密度が向上しなかった。結果
を表１に示す。Comparative Example 3 The powdered activated carbon obtained in the reference experimental example was further pulverized by a ball mill for 20 hours to obtain powdered activated carbon having a central particle diameter of 9 μm. This activated carbon was subjected to compression and mixing for 60 minutes in the same manner as in Example 3. The center particle diameter of the obtained powdered activated carbon was 8 μm, and particles of 1/10 or less were 8%. The activated carbon density in the electrode of the powdered activated carbon was reduced to 0.57 g / cc, and the capacity was reduced to 15.4 F / cc. Central particle size is 10μ
m or less, the density of the activated carbon did not improve. Table 1 shows the results.
【００３６】比較例４ 参考実験例で得た粉末活性炭をさらに１０時間ボールミ
ルで粉砕し、中心粒子径６０μｍ、１／１０以下の粒子
の割合が５％の粉末活性炭とした。この活性炭を実施例
１と同様に処理し、中心粒子径５５μｍ、１／１０以下
の粒子の割合が８％の粉末活性炭を得た。この粉末活性
炭の電極中の密度は０．５７ｇ／ｃｃ、容量は１５．４
Ｆ／ｃｃと低下した。中心粒子直径が５０μｍ以上の場
合には活性炭の密度が向上しなかった。結果を表１に示
す。Comparative Example 4 The powdered activated carbon obtained in the Reference Experimental Example was further pulverized with a ball mill for 10 hours to obtain a powdered activated carbon having a center particle diameter of 60 μm and a ratio of particles of 1/10 or less of 5%. This activated carbon was treated in the same manner as in Example 1 to obtain a powdered activated carbon having a central particle diameter of 55 μm and a ratio of particles of 1/10 or less of 8%. The density of the powdered activated carbon in the electrode was 0.57 g / cc, and the capacity was 15.4.
F / cc. When the center particle diameter was 50 μm or more, the density of the activated carbon did not improve. Table 1 shows the results.
【００３７】[0037]
【表１】 [Table 1]
【００３８】実施例８ フェノール樹脂を硬化・乾留した炭化物を４〜１０メッ
シュに整粒して活性炭の原料とした。この原料炭化物を
プロパン燃焼ガスを使用し９００℃で８時間賦活した。
この活性炭のヨード吸着性能は２０００ｍｇ／ｇ、ベン
ゼン吸着量は６０％であった。この活性炭のキャパシタ
としての容量は２９Ｆ／ｇであった。この活性炭をボー
ルミルを使用し１９時間粉砕を行った。得られた粉末活
性炭は中心粒子径３５μｍ、１／１０の粒子の割合は５
％であった。この粉末活性炭を使用し実施例１と同様な
方法で電極を作製した。活性炭の密度は０．６２ｇ／ｃ
ｃで、容量は１８．０Ｆ／ｃｃであった。この粉末活性
炭を実施例１と同様な方法で高速で圧縮と混合を行い、
中心粒子径３４μｍ、１／１０の粒子の割合が７％の粉
末活性炭を得た。この活性炭の電極中での密度は０．６
５ｇ／ｃｃで、容量は１８．９Ｆ／ｃｃであった。容量
は５％向上した。フェノール樹脂活性炭の場合も容量は
向上したが、椰子殻活性炭の方が容量の向上が大きかっ
た。Example 8 A carbide obtained by curing and carbonizing a phenol resin was sized to 4 to 10 mesh to obtain a raw material for activated carbon. This raw material carbide was activated at 900 ° C. for 8 hours using propane combustion gas.
The iodine adsorption performance of this activated carbon was 2000 mg / g, and the benzene adsorption amount was 60%. The capacity of this activated carbon as a capacitor was 29 F / g. This activated carbon was ground using a ball mill for 19 hours. The obtained powdered activated carbon had a central particle diameter of 35 μm, and the ratio of 1/10 particles was 5
%Met. Using this powdered activated carbon, an electrode was produced in the same manner as in Example 1. The density of activated carbon is 0.62g / c
At c, the capacity was 18.0 F / cc. This powdered activated carbon was compressed and mixed at a high speed in the same manner as in Example 1,
Powdered activated carbon having a center particle diameter of 34 μm and a ratio of 1/10 particles of 7% was obtained. The density of this activated carbon in the electrode is 0.6
At 5 g / cc, the capacity was 18.9 F / cc. Capacity increased by 5%. The phenolic resin activated carbon also improved the capacity, but the coconut shell activated carbon improved the capacity more.
【００３９】[0039]
【発明の効果】本発明により、中心粒子径が１０μｍ以
上５０μｍ以下で、中心粒子径の１／１０以下の大きさ
の粒子の割合が６％以上１３％以下の粉末活性炭を提供
することができる。本発明の粉末活性炭はバインダーと
混合してシートに成型し、該シートを電極としてセパレ
ータ及び電解液と組み合わせ、容量の大きいキャパシタ
に作製することができる。また、本発明の活性炭粉末
は、キャパシタの他、各種電極、シートにも好適に使用
することができる。According to the present invention, it is possible to provide a powdered activated carbon having a center particle diameter of 10 μm or more and 50 μm or less and a proportion of particles having a size of 1/10 or less of the center particle diameter of 6% or more and 13% or less. . The powdered activated carbon of the present invention can be mixed with a binder and molded into a sheet, and the sheet can be used as an electrode in combination with a separator and an electrolytic solution to produce a capacitor having a large capacity. The activated carbon powder of the present invention can be suitably used for various electrodes and sheets in addition to capacitors.
【図１】本発明の粉末活性炭を成型して作製したボタン
型キャパシタの断面図である。FIG. 1 is a sectional view of a button-type capacitor manufactured by molding the powdered activated carbon of the present invention.
【図２】処理前の粉末活性炭を１０００倍の走査電子顕
微鏡で観察した写真である。FIG. 2 is a photograph obtained by observing a powdered activated carbon before treatment with a scanning electron microscope (× 1000).
【図３】処理前の粉末活性炭を２０００倍の走査電子顕
微鏡で観察した写真である。FIG. 3 is a photograph obtained by observing a powdered activated carbon before treatment with a scanning electron microscope at a magnification of 2000 times.
【図４】本発明の粉末活性炭を１０００倍の走査電子顕
微鏡で観察した写真である。FIG. 4 is a photograph of the powdered activated carbon of the present invention observed with a scanning electron microscope at a magnification of 1000 times.
【図５】本発明の粉末活性炭を２０００倍の走査電子顕
微鏡で観察した写真である。FIG. 5 is a photograph obtained by observing the powdered activated carbon of the present invention with a scanning electron microscope at 2000 times.
１ 正極 ２ 負極 ３ ステンレス蓋 ４ ステンレスケース ５ 封口体 ６ セパレーター ７ 電解液 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Stainless steel lid 4 Stainless steel case 5 Sealing body 6 Separator 7 Electrolyte
Claims (4)
であって、中心粒子径の１／１０以下の大きさの粒子の
割合が６％以上１３％以下である粉末活性炭。1. A powdered activated carbon having a central particle diameter of 10 μm or more and 50 μm or less and a ratio of particles having a size of 1/10 or less of the central particle diameter of 6% or more and 13% or less.
する活性炭である請求項１記載の粉末活性炭。2. The powdered activated carbon according to claim 1, wherein the powdered activated carbon is an activated carbon mainly made of coconut shell.
インダーからなる混合物を成型せしめた活性炭シート。3. An activated carbon sheet formed by molding a mixture comprising the powdered activated carbon according to claim 1 and a binder.
た電気二重層キャパシタ。4. An electric double layer capacitor using the activated carbon sheet according to claim 3 as an electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11159244A JP2000344507A (en) | 1999-06-07 | 1999-06-07 | Powdery activated carbon, activated carbon sheet and electric double layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11159244A JP2000344507A (en) | 1999-06-07 | 1999-06-07 | Powdery activated carbon, activated carbon sheet and electric double layer capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000344507A true JP2000344507A (en) | 2000-12-12 |
Family
ID=15689508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11159244A Pending JP2000344507A (en) | 1999-06-07 | 1999-06-07 | Powdery activated carbon, activated carbon sheet and electric double layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000344507A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004189586A (en) * | 2002-11-29 | 2004-07-08 | Honda Motor Co Ltd | Activated carbon, polarizable electrode for electric double-layer capacitor, and electric double-layer capacitor using the same |
| KR100479188B1 (en) * | 2001-02-06 | 2005-03-25 | 엔이씨 도낀 가부시끼가이샤 | Electric double layer capacitor with improved activated carbon electrodes |
| JP2005158818A (en) * | 2003-11-20 | 2005-06-16 | Tdk Corp | Electrochemical capacitor electrode, manufacturing method therefor, electrochemical capacitor and manufacturing method therefor |
| WO2010150534A1 (en) * | 2009-06-23 | 2010-12-29 | クラレケミカル株式会社 | Flow-through capacitor, method for producing deionized water, and device for producing deionized water |
| JP2011176043A (en) * | 2010-02-23 | 2011-09-08 | Calgon Carbon Japan Kk | Activated carbon for electric double layer capacitor |
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1999
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100479188B1 (en) * | 2001-02-06 | 2005-03-25 | 엔이씨 도낀 가부시끼가이샤 | Electric double layer capacitor with improved activated carbon electrodes |
| US7092239B2 (en) | 2001-02-06 | 2006-08-15 | Nec Tokin Corporation | Electric double layer capacitor with improved activated carbon electrodes |
| JP2004189586A (en) * | 2002-11-29 | 2004-07-08 | Honda Motor Co Ltd | Activated carbon, polarizable electrode for electric double-layer capacitor, and electric double-layer capacitor using the same |
| JP2005158818A (en) * | 2003-11-20 | 2005-06-16 | Tdk Corp | Electrochemical capacitor electrode, manufacturing method therefor, electrochemical capacitor and manufacturing method therefor |
| JP4608871B2 (en) * | 2003-11-20 | 2011-01-12 | Ｔｄｋ株式会社 | Electrode for electrochemical capacitor and manufacturing method thereof, and electrochemical capacitor and manufacturing method thereof |
| US8848338B2 (en) | 2006-09-01 | 2014-09-30 | W. L. Gore & Associates, Co., Ltd. | Electric double layer capacitor |
| WO2010150534A1 (en) * | 2009-06-23 | 2010-12-29 | クラレケミカル株式会社 | Flow-through capacitor, method for producing deionized water, and device for producing deionized water |
| JPWO2010150534A1 (en) * | 2009-06-23 | 2012-12-06 | クラレケミカル株式会社 | Liquid-permeable capacitor, deionized water production method, and deionized water production apparatus |
| JP5687620B2 (en) * | 2009-06-23 | 2015-03-18 | クラレケミカル株式会社 | Liquid-permeable capacitor, deionized water production method, and deionized water production apparatus |
| JP2011176043A (en) * | 2010-02-23 | 2011-09-08 | Calgon Carbon Japan Kk | Activated carbon for electric double layer capacitor |
| US20130133923A1 (en) * | 2010-04-29 | 2013-05-30 | Oû Skeleton Technologies | A carbon composite electrode for the electric double-layer capacitor |
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