JPH11135380A - Activated carbon for electric double layer capacitor and its manufacture - Google Patents
Activated carbon for electric double layer capacitor and its manufactureInfo
- Publication number
- JPH11135380A JPH11135380A JP10157027A JP15702798A JPH11135380A JP H11135380 A JPH11135380 A JP H11135380A JP 10157027 A JP10157027 A JP 10157027A JP 15702798 A JP15702798 A JP 15702798A JP H11135380 A JPH11135380 A JP H11135380A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- electric double
- double layer
- layer capacitor
- mesophase
- 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、電気二重層キャパ
シタ用活性炭及びその製造方法に関するものである。The present invention relates to activated carbon for electric double layer capacitors and a method for producing the same.
【０００２】[0002]
【従来の技術】固体面が電解質溶液に接触すると、該固
体面に対して正または負イオンの選択的吸着が起こり、
固体面が正または負に荷電する。一方、溶液側では反対
電荷の対イオンが多くなる。この結果、固体面と電解質
溶液との界面に正負の電荷が対向して配列され、前記正
負の電荷による電気二重層が形成される。前記電気二重
層は、前記固体面を電極とすることによりキャパシタと
して利用できることが知られており、このようなキャパ
シタは電気二重層キャパシタと呼ばれている。2. Description of the Related Art When a solid surface contacts an electrolyte solution, selective adsorption of positive or negative ions occurs on the solid surface,
The solid surface is positively or negatively charged. On the other hand, on the solution side, counter ions of the opposite charge increase. As a result, positive and negative charges are arranged facing each other at the interface between the solid surface and the electrolyte solution, and an electric double layer is formed by the positive and negative charges. It is known that the electric double layer can be used as a capacitor by using the solid surface as an electrode, and such a capacitor is called an electric double layer capacitor.
【０００３】前記電気二重層キャパシタでは、前記固体
電極に電界を印加したときの静電容量は前記電極の表面
積に比例する。そこで、前記電気二重層キャパシタで
は、一般に、活性炭のような比表面積の大きな物質を電
極とし、該電極に電解液を含浸させている。そして、前
記電気二重層キャパシタは、前記電解液が含浸された電
極をセパレータで分離し、セパレータの両側の電極にそ
れぞれ集電部材を取着した構成となっている。In the electric double layer capacitor, the capacitance when an electric field is applied to the solid electrode is proportional to the surface area of the electrode. Therefore, in the electric double layer capacitor, generally, a substance having a large specific surface area such as activated carbon is used as an electrode, and the electrode is impregnated with an electrolytic solution. The electric double layer capacitor has a configuration in which the electrodes impregnated with the electrolytic solution are separated by a separator, and current collecting members are attached to the electrodes on both sides of the separator.
【０００４】前記電気二重層キャパシタは、ファラッド
級の大容量を有し、充放電サイクル特性に優れることか
ら、電気機器のバックアップ電源等の用途に使用されて
いる。前記電気二重層キャパシタは、さらに車載バッテ
リーの代替として使用することが検討されている。[0004] The electric double layer capacitor has a farad-class large capacity and is excellent in charge / discharge cycle characteristics, and is therefore used for applications such as a backup power supply for electric equipment. The use of the electric double layer capacitor as a substitute for a vehicle-mounted battery is being studied.
【０００５】前記電気二重層キャパシタは、例えば、図
１に示す様に、活性炭からなる一対の分極性電極１，１
をセパレータ２を介して対向させて設け、該分極性電極
１にテトラアルキルアンモニウム塩等の有機溶媒溶液を
電解液として含浸させた構成となっている。図１示の電
気二重層キャパシタは、セパレータ２を介して対向する
分極性電極１，１がアルミニウム製容器３に収容されて
いる。アルミニウム製容器３は、アルミニウム製蓋体５
で閉蓋されていて、容器３及び蓋体５はそれぞれ分極性
電極１，１に接触して各分極性電極１に対する集電部材
となっている。前記構成の電気二重層キャパシタでは、
例えば活性炭粒子をテトラフルオロエチレン等の結着剤
と混合して成形した分極性電極１が用いられる。また、
前記構成の電気二重層キャパシタでは、活性炭繊維等が
分極性電極１に用いられることもある。As shown in FIG. 1, for example, the electric double layer capacitor includes a pair of polarizable electrodes 1 and 1 made of activated carbon.
Are provided facing each other with a separator 2 interposed therebetween, and the polarizable electrode 1 is impregnated with an organic solvent solution such as a tetraalkylammonium salt as an electrolytic solution. In the electric double layer capacitor shown in FIG. 1, the polarizable electrodes 1 and 1 facing each other via a separator 2 are accommodated in an aluminum container 3. The aluminum container 3 includes an aluminum lid 5.
The container 3 and the lid 5 are in contact with the polarizable electrodes 1 and 1 respectively, and serve as current collecting members for the respective polarizable electrodes 1. In the electric double layer capacitor having the above configuration,
For example, a polarizable electrode 1 formed by mixing activated carbon particles with a binder such as tetrafluoroethylene is used. Also,
In the electric double layer capacitor having the above configuration, activated carbon fiber or the like may be used for the polarizable electrode 1.
【０００６】前記電気二重層キャパシタでは、分極性電
極１の前記集電部材に近い部分の電荷は該集電部材によ
り容易に取り出せる。しかし、該集電部材から離れた部
分の荷電は取り出されるまでに分極性電極１の内部抵抗
により低減する。このため、電気二重層キャパシタ全体
としての有効な静電容量が少なくなるという問題があ
る。In the electric double layer capacitor, the electric charge in the portion of the polarizable electrode 1 close to the current collecting member can be easily taken out by the current collecting member. However, the charge at the portion remote from the current collecting member is reduced by the internal resistance of the polarizable electrode 1 before being taken out. Therefore, there is a problem that the effective capacitance of the entire electric double layer capacitor is reduced.
【０００７】前記問題を解決するために、活性炭粒子の
内部構造を改良して分極性電極１の内部抵抗を低減しよ
うとする試みがなされている。例えば、活性炭粒子を用
いる分極性電極では該活性炭粒子にファーネスブラック
等の導電フィラーを混合することが行われている。ま
た、活性炭繊維を用いる分極性電極では、特開昭６１−
１８７３２２号公報記載のように、活性炭繊維の内部を
黒鉛とし、繊維外層を活性炭とするもの等が提案されて
いる。また、本発明者らは、活性炭粒子を導電フィラー
と混合して前記分極性電極を構成するときに、易黒鉛化
性樹脂を炭化し、得られた炭化物をアルカリ賦活するこ
とにより、粒子の表面から内部に向けて黒鉛の積層構造
が形成された活性炭粒子を用いることを先に提案してい
る（特願平８−１３２０５０号明細書参照）。[0007] In order to solve the above problems, attempts have been made to improve the internal structure of the activated carbon particles to reduce the internal resistance of the polarizable electrode 1. For example, in a polarizable electrode using activated carbon particles, a conductive filler such as furnace black is mixed into the activated carbon particles. In addition, a polarizable electrode using activated carbon fiber is disclosed in
As described in Japanese Patent No. 187322, there has been proposed a material in which the inside of activated carbon fiber is made of graphite and the outer layer of the fiber is made of activated carbon. Further, the present inventors, when forming the polarizable electrode by mixing the activated carbon particles with a conductive filler, by carbonizing the graphitizable resin and alkali-activating the obtained carbide, the surface of the particles. It has been previously proposed to use activated carbon particles having a graphite laminated structure from inside to inside (see Japanese Patent Application No. 8-132050).
【０００８】しかしながら、前記の様に活性炭粒子の内
部構造を改良しても、前記分極性電極の内部抵抗を低減
する効果は、十分に満足できるものではなかった。However, even if the internal structure of the activated carbon particles is improved as described above, the effect of reducing the internal resistance of the polarizable electrode has not been sufficiently satisfactory.
【０００９】[0009]
【発明が解決しようとする課題】従って、本発明は、か
かる不都合を解消して、電気二重層キャパシタの分極性
電極を形成したときに該分極性電極の内部抵抗を低減す
ることができる活性炭を提供することを目的とする。SUMMARY OF THE INVENTION Accordingly, the present invention is to provide an activated carbon capable of solving such disadvantages and reducing the internal resistance of the polarizable electrode when the polarizable electrode of the electric double layer capacitor is formed. The purpose is to provide.
【００１０】また、本発明の目的は、前記活性炭を用い
る分極性電極を提供することにもある。Another object of the present invention is to provide a polarizable electrode using the activated carbon.
【００１１】また、本発明の目的は、前記活性炭を用い
る電気二重層キャパシタを提供することにもある。Another object of the present invention is to provide an electric double layer capacitor using the activated carbon.
【００１２】さらに、本発明の目的は、前記活性炭の製
造方法を提供することにもある。Still another object of the present invention is to provide a method for producing the activated carbon.
【００１３】[0013]
【課題を解決するための手段】本発明者らは、活性炭粒
子を前記導電フィラー及び結着剤と混合してなる前記電
気二重層キャパシタの分極性電極の内部構造について検
討した。この結果、前記導電フィラーは活性炭粒子の周
囲に配されて活性炭粒子同士を電気的に接続する働きを
しているとの知見を得た。また、活性炭粒子間の電荷の
受け渡しの大部分は前記導電フィラーを経由して行われ
ているとの知見を得た。Means for Solving the Problems The present inventors have studied the internal structure of the polarizable electrode of the electric double layer capacitor obtained by mixing activated carbon particles with the conductive filler and the binder. As a result, it has been found that the conductive filler is disposed around the activated carbon particles and functions to electrically connect the activated carbon particles to each other. In addition, it has been found that the majority of charge transfer between activated carbon particles is performed via the conductive filler.
【００１４】従って、前記分極性電極の内部抵抗を低減
するには、活性炭粒子の内部構造を改良して活性炭粒子
自体の抵抗を低くするよりも、活性炭粒子間の抵抗を低
くする方が有効であると考えられる。Therefore, in order to reduce the internal resistance of the polarizable electrode, it is more effective to lower the resistance between the activated carbon particles than to improve the internal structure of the activated carbon particles to lower the resistance of the activated carbon particles themselves. It is believed that there is.
【００１５】ところが、前記導電フィラーは略球状で、
その直径は約２００Åであり、前記活性炭粒子の約１／
５００である。このために、前記導電フィラーは、前記
活性炭粒子と点接触するに過ぎず、接触面積が少ないの
で、活性炭粒子との間で十分な電気的な接続効率が得ら
れない。そこで、本発明者らは、活性炭粒子表面の導電
性を改良することにより、前記導電フィラーと前記活性
炭粒子との電気的な接続効率が向上され、ひいては活性
炭粒子間の抵抗を低減できることを見出した。However, the conductive filler is substantially spherical.
Its diameter is about 200 ° and about 1 / of the activated carbon particles.
500. For this reason, the conductive filler only makes point contact with the activated carbon particles and has a small contact area, so that sufficient electrical connection efficiency with the activated carbon particles cannot be obtained. Therefore, the present inventors have found that by improving the conductivity of the activated carbon particles, the electrical connection efficiency between the conductive filler and the activated carbon particles is improved, and the resistance between the activated carbon particles can be reduced. .
【００１６】本発明者らにより先に出願されている特願
平８−１３２０５０号明細書記載の活性炭粒子は、粒子
の表面から内部に向けて黒鉛の積層構造が形成されてい
る。前記活性炭粒子によれば、表面に導電性を有する黒
鉛が露出しているので、該黒鉛に前記導電性フィラーが
接触することにより活性炭粒子間の抵抗を低くすること
ができる。しかし、前記明細書記載の活性炭粒子では、
前記黒鉛の積層構造が粒子表面から内部に向けて形成さ
れているので、表面に露出する黒鉛は全体の１０〜２０
％に過ぎず、さらに改良が望まれる。The activated carbon particles described in the specification of Japanese Patent Application No. 8-13050 previously filed by the present inventors have a laminated structure of graphite from the surface of the particles toward the inside. According to the activated carbon particles, since the conductive graphite is exposed on the surface, the resistance between the activated carbon particles can be reduced by bringing the conductive filler into contact with the graphite. However, in the activated carbon particles described in the above specification,
Since the graphite laminated structure is formed from the particle surface toward the inside, the graphite exposed on the surface is 10 to 20% in total.
%, And further improvement is desired.
【００１７】本発明は前記目的を達成するために、かか
る検討結果に鑑みてなされたものであり、本発明の電気
二重層キャパシタ用活性炭は、該活性炭粒子の少なくと
も一部の表面が該表面に沿って形成された黒鉛の積層構
造層により被覆されていることを特徴とする。尚、本明
細書において、「黒鉛の積層構造層」との用語は、６員
炭素環が二次元的に連なった層が積み重なり、層と層と
がファン・デア・ワールス力により結合している構造を
意味する。The present invention has been made in view of the above-described results in order to achieve the above object. The activated carbon for an electric double layer capacitor of the present invention has at least a part of the surface of the activated carbon particles on the surface. It is characterized by being covered with a laminated structure layer of graphite formed along. In the present specification, the term “graphite laminated structure layer” refers to a layer in which six-membered carbon rings are two-dimensionally connected to each other, and the layers are joined by van der Waals force. Means structure.
【００１８】本発明の活性炭によれば、粒子の表面が導
電性を有する黒鉛の積層構造層により被覆されている。
従って、本発明の活性炭を導電フィラー及び結着剤と混
合して電気二重層キャパシタの分極性電極を構成したと
きに、該活性炭粒子の周囲に配された導電フィラーが前
記黒鉛と接触する確率が高くなり、該活性炭粒子間の電
荷の受け渡しを容易に行うことができる。According to the activated carbon of the present invention, the surfaces of the particles are covered with a laminated structure layer of graphite having conductivity.
Therefore, when the activated carbon of the present invention is mixed with a conductive filler and a binder to form a polarizable electrode of an electric double layer capacitor, the probability that the conductive filler disposed around the activated carbon particles comes into contact with the graphite is reduced. As a result, charges can be easily transferred between the activated carbon particles.
【００１９】また、本発明の分極性電極は、前記粒子の
少なくとも一部の表面が黒鉛の積層構造層により被覆さ
れた活性炭と、導電性フィラーと、結着剤とからなるこ
とを特徴とする。Further, the polarizable electrode according to the present invention is characterized in that at least a part of the surface of the particles is made of activated carbon coated with a graphite laminated structure layer, a conductive filler, and a binder. .
【００２０】本発明の分極性電極によれば、前記の様に
粒子間の電荷の受け渡しを容易に行うことができる活性
炭が用いられているので、その内部抵抗を低減すること
ができる。According to the polarizable electrode of the present invention, since the activated carbon which can easily transfer charges between particles is used as described above, the internal resistance can be reduced.
【００２１】また、本発明の電気二重層キャパシタは、
セパレータを介して対向した一対の分極性電極と、各分
極性電極に設けられた集電部材と、電解液とからなる電
気二重層キャパシタにおいて、該分極性電極は粒子の少
なくとも一部の表面が黒鉛の積層構造層により被覆され
た活性炭と、導電性フィラーと、結着剤とからなること
を特徴とする。Further, the electric double layer capacitor of the present invention comprises:
A pair of polarizable electrodes facing each other with a separator interposed therebetween, a current collecting member provided on each polarizable electrode, and an electric double layer capacitor including an electrolytic solution, wherein the polarizable electrode has at least a part of the surface of particles. It is characterized by comprising activated carbon covered with a graphite laminated structure layer, a conductive filler, and a binder.
【００２２】本発明の電気二重層キャパシタによれば、
前記分極性電極が前記の様に粒子間の電荷の受け渡しを
容易に行うことができる活性炭により構成されているの
で、該分極性電極の内部抵抗が低減され、電荷を容易に
取り出すことができる。従って、本発明の電気二重層キ
ャパシタによれば、キャパシタ全体の有効な静電容量を
向上することができる。また、前記分極性電極を構成す
る活性炭粒子間の電荷の受け渡しが容易であるので、充
電する際に前記活性炭粒子に対する給電性能を安定化
し、キャパシタとしての静電容量自体を大きくすること
ができる。According to the electric double layer capacitor of the present invention,
Since the polarizable electrode is made of activated carbon which can easily transfer charges between particles as described above, the internal resistance of the polarizable electrode is reduced, and charges can be easily taken out. Therefore, according to the electric double layer capacitor of the present invention, the effective capacitance of the entire capacitor can be improved. In addition, since it is easy to transfer electric charges between the activated carbon particles constituting the polarizable electrode, the power supply performance to the activated carbon particles during charging can be stabilized, and the capacitance itself as a capacitor can be increased.
【００２３】本発明の電気二重層キャパシタ用活性炭
は、石油ピッチから抽出されるメゾフェース相を冷却、
固化したメゾフェース樹脂の表面を部分酸化して不融化
することによりメゾフェースピッチを得る工程と、該メ
ゾフェースピッチを不活性気体気流下５００〜９００℃
で加熱して炭化させる工程と、前記工程で得られた炭化
物を該炭化物１重量部に対して１．２〜２．４重量部の
アルカリ金属水酸化物と混合し、不活性気体気流下５５
０〜８５０℃で加熱してアルカリ賦活する工程とからな
ることを特徴とする製造方法により有利に製造すること
ができる。The activated carbon for an electric double layer capacitor of the present invention cools a mesophase extracted from petroleum pitch,
A step of obtaining a mesoface pitch by partially oxidizing the surface of the solidified mesoface resin to make it infusible, and forming the mesoface pitch in an inert gas stream at 500 to 900 ° C.
Heating and carbonizing the mixture, and mixing the carbide obtained in the above step with 1.2 to 2.4 parts by weight of an alkali metal hydroxide based on 1 part by weight of the carbide.
And a step of heating at 0 to 850 ° C. to activate the alkali.
【００２４】本発明の活性炭の製造方法では、メゾフェ
ースピッチを原料とする。メゾフェースピッチを得るに
は、まず、石油ピッチからメゾフェース相を抽出する。
前記石油ピッチは、原油からガソリン、灯油等を分留す
る過程で排出される残滓である。前記メゾフェース相は
前記石油ピッチの液相での炭化の進行に伴い多核−多環
芳香族分子が成長し、その一部または全部が液晶状態を
示す様になったものである。前記メゾフェース相は、冷
却すると固体状の樹脂となる。そこで、前記樹脂の表面
を部分酸化し、該表面の高分子を酸素で架橋させ、さら
に分子量を増大させて不融化することにより、メゾフェ
ースピッチが得られる。In the method for producing activated carbon of the present invention, mesophase pitch is used as a raw material. In order to obtain a mesophase pitch, first, a mesophase phase is extracted from a petroleum pitch.
The petroleum pitch is a residue discharged in the process of fractionating gasoline, kerosene and the like from crude oil. In the mesophase phase, polynuclear-polycyclic aromatic molecules grow with the progress of carbonization in the liquid phase of the petroleum pitch, and a part or all of the molecules show a liquid crystal state. The mesophase becomes a solid resin when cooled. Then, the surface of the resin is partially oxidized, the polymer on the surface is crosslinked with oxygen, and the molecular weight is further increased to render the resin infusible, thereby obtaining a mesoface pitch.
【００２５】次に前記メゾフェースピッチを前記条件下
に加熱して炭化すると、該メゾフェースピッチ表面の不
融化された部分の多核−多環芳香族分子が黒鉛化する。
この結果、表面が黒鉛の積層構造層により被覆された炭
化物が得られるものと考えられる。Next, when the mesophase pitch is heated and carbonized under the above conditions, the polynuclear-polycyclic aromatic molecules in the infusibilized portion on the surface of the mesophase pitch are graphitized.
As a result, it is considered that a carbide whose surface is covered with the graphite laminated structure layer is obtained.
【００２６】黒鉛の積層構造層を備える炭化物は、ポリ
塩化ビニル、タール等の易黒鉛化性樹脂を加熱して炭化
することによっても得られる。しかし、ポリ塩化ビニ
ル、タール等は低融点であるので、前記不融化のために
３００〜４００℃に加熱すると溶融してしまう。従っ
て、本発明はメゾフェースピッチを原料とすることが必
要であり、ポリ塩化ビニル、タール等の易黒鉛化性樹脂
は、本発明に適用することができない。A carbide having a graphite laminated structure layer can also be obtained by heating and carbonizing a graphitizable resin such as polyvinyl chloride or tar. However, since polyvinyl chloride and tar have a low melting point, they are melted when heated to 300 to 400 ° C. for infusibility. Therefore, in the present invention, it is necessary to use mesoface pitch as a raw material, and easily graphitizable resins such as polyvinyl chloride and tar cannot be applied to the present invention.
【００２７】また、前記炭化によれば、前記メゾフェー
スピッチから水素、側鎖等が脱離して、賦活により最終
製品の活性炭を得るために適した孔径の細孔が形成され
た炭化物が得られる。According to the carbonization, hydrogen, side chains and the like are desorbed from the mesophase pitch, and a carbonized material having pores suitable for obtaining activated carbon of a final product by activation is obtained. .
【００２８】次に、前記炭化物を前記条件下にアルカリ
賦活することにより、前記炭化のための加熱の際に焼結
して閉塞された細孔が開削され、その表面が黒鉛の積層
構造層により被覆された活性炭を得ることができる。Next, by activating the carbide under the above-mentioned conditions, pores which are sintered and closed at the time of heating for carbonization are cut out, and the surface thereof is formed by a graphite laminated structure layer. A coated activated carbon can be obtained.
【００２９】尚、本発明の製造方法によれば、ポリ塩化
ビニル等の塩素を含む易黒鉛化樹脂を使用しないので、
炭化の工程において塩素化合物を発生することが無い。According to the production method of the present invention, since a graphitizable resin containing chlorine such as polyvinyl chloride is not used,
No chlorine compound is generated in the carbonization process.
【００３０】また、本発明の製造方法では、得られた活
性炭は粒子状として電気二重層キャパシタの分極性電極
に用いられる。ここで、前記活性炭は、前記粒子状とす
るために、前記メゾフェース樹脂を溶融して紡糸したの
ち前記のように不融化してメゾフェースピッチ繊維と
し、該メゾフェースピッチ繊維に前記炭化させる工程と
前記アルカリ賦活する工程とを施したのち、生成物を粉
砕して粒子状としてもよい。また、前記活性炭は、前記
メゾフェース樹脂を微粒状に粉砕したのち前記のように
不融化してメゾフェースピッチを得て、該メゾフェース
ピッチ繊維に前記炭化させる工程と前記アルカリ賦活す
る工程とを施して粒子状活性炭としてもよい。In the production method of the present invention, the obtained activated carbon is used in the form of particles for a polarizable electrode of an electric double layer capacitor. Here, the activated carbon, in order to form the particles, the mesoface resin is melted and spun and then infusibilized as described above to form mesoface pitch fibers, and the step of carbonizing the mesoface pitch fibers. After the step of activating the alkali, the product may be pulverized into particles. Further, the activated carbon is subjected to a step of pulverizing the mesophase resin into fine particles and then infusing as described above to obtain a mesoface pitch, and the step of carbonizing the mesoface pitch fibers and the step of alkali activation. It may be a particulate activated carbon.
【００３１】[0031]
【発明の実施の形態】次に、添付の図面を参照しながら
本発明の実施の形態についてさらに詳しく説明する。図
１は本発明の電気二重層キャパシタの一実施態様を示す
説明的断面図であり、図２は本実施形態の活性炭の粒子
構造を示す電子顕微鏡写真の摸写図であり、図３は従来
の活性炭の粒子構造を示す電子顕微鏡写真の摸写図であ
る。また、図４は、図２及び図３に示す活性炭粒子を用
いた分極性電極の内部抵抗及び静電容量を示すグラフで
あり、図５は、本実施形態の活性炭の炭化温度と該活性
炭を用いた分極性電極の静電容量の関係を示すグラフで
あり、図６は、本実施形態の活性炭のアルカリ賦活に用
いるアルカリ金属水酸化物の量と該活性炭を用いた分極
性電極の静電容量の関係を示すグラフである。Next, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. FIG. 1 is an explanatory sectional view showing an embodiment of the electric double layer capacitor of the present invention, FIG. 2 is an electron micrograph showing the particle structure of the activated carbon of the present embodiment, and FIG. FIG. 5 is a mimetic diagram of an electron micrograph showing the particle structure of activated carbon of Example 1. FIG. 4 is a graph showing the internal resistance and the capacitance of the polarizable electrode using the activated carbon particles shown in FIGS. 2 and 3, and FIG. 5 shows the carbonization temperature of the activated carbon of this embodiment and the activated carbon. FIG. 6 is a graph showing the relationship between the capacitances of the polarizable electrodes used. FIG. 6 shows the amount of the alkali metal hydroxide used for the alkali activation of the activated carbon of the present embodiment and the capacitance of the polarizable electrodes using the activated carbon. It is a graph which shows the relationship of capacity.
【００３２】本実施態様の電気二重層キャパシタは、図
１示のように、活性炭からなる一対の分極性電極１，１
をセパレータ２を介して対向させて設けた構成となって
いる。分極性電極１には、テトラアルキルアンモニウム
塩等を有機溶媒に溶解させた溶液が電解液として含浸さ
れている。図１示の電気二重層キャパシタは、セパレー
タ２を介して対向する分極性電極１，１をアルミニウム
製容器３に収容されている。アルミニウム製容器３は、
パッキン４を介してアルミニウム製蓋体５により閉蓋さ
れるようになっている。容器３及び蓋体５はそれぞれ分
極性電極１，１に接触して各分極性電極１に対する集電
部材となるとともに、外部回路に対する接続端子を兼ね
ている。As shown in FIG. 1, the electric double layer capacitor of this embodiment has a pair of polarizable electrodes 1 and 1 made of activated carbon.
Are provided facing each other with the separator 2 interposed therebetween. The polarizable electrode 1 is impregnated with a solution obtained by dissolving a tetraalkylammonium salt or the like in an organic solvent as an electrolytic solution. In the electric double layer capacitor shown in FIG. 1, the polarizable electrodes 1 and 1 facing each other via a separator 2 are accommodated in an aluminum container 3. Aluminum container 3
The lid is closed by an aluminum lid 5 via a packing 4. The container 3 and the lid 5 respectively contact the polarizable electrodes 1 and 1 to serve as current collecting members for the polarizable electrodes 1 and also serve as connection terminals for external circuits.
【００３３】本実施形態では、前記分極性電極１は、粒
子の表面が黒鉛の積層構造層により被覆された活性炭粒
子を、ファーネスブラック等の導電性フィラー及びテト
ラフルオロエチレン等の結着剤と混合し、成形したもの
である。In this embodiment, the polarizable electrode 1 is obtained by mixing activated carbon particles whose surfaces are coated with a graphite laminated structure layer with a conductive filler such as furnace black and a binder such as tetrafluoroethylene. And molded.
【００３４】次に、前記活性炭粒子の製造方法について
説明する。Next, a method for producing the activated carbon particles will be described.
【００３５】前記活性炭粒子を製造するときには、ま
ず、原油の分留残滓である石油ピッチからメゾフェース
相を抽出し、次にこれを冷却、固化しメゾフェース樹脂
を得る。固化したメゾフェース樹脂は、その融点以上に
加熱、溶融して紡糸することにより繊維とされ、該繊維
を３５０〜４００℃で加熱することによりその表面が部
分酸化されて不融化された繊維状のメゾフェースピッチ
が得られる。前記繊維状のメゾフェースピッチとして
は、例えばペトカ社から市販されているものがある。
本実施形態では、前記メゾフェースピッチを加熱するこ
とにより炭化し、得られた炭化物をアルカリ賦活して活
性炭繊維とし、さらに該活性炭繊維を粉砕して微粒子と
する。また、前記の様に固化したメゾフェース樹脂を粉
砕して微粒子にした後、不融化し、炭化及びアルカリ賦
活を行ってもよい。When producing the activated carbon particles, first, a mesophase phase is extracted from petroleum pitch, which is a fractionated residue of crude oil, and then cooled and solidified to obtain a mesophase resin. The solidified mesophase resin is heated to above its melting point, melted and spun into fibers, and by heating the fibers at 350 to 400 ° C., the surface is partially oxidized to make the fibers infusible and infusible. A face pitch is obtained. Examples of the fibrous mesoface pitch include those commercially available from Petka Corporation.
In the present embodiment, the mesoface pitch is carbonized by heating, and the obtained carbide is activated with alkali to form activated carbon fibers, and the activated carbon fibers are pulverized into fine particles. Further, the mesophase resin solidified as described above may be pulverized into fine particles, then infusibilized, and carbonized and alkali activated.
【００３６】前記メゾフェースピッチの炭化は、窒素等
の不活性気体気流下、５００〜９００℃で、好ましくは
５００〜８００℃で加熱することにより行う。前記メゾ
フェースピッチは、前記加熱により、水素、側鎖等が脱
離して、炭素骨格のみが残る炭化物となる。前記加熱温
度が５００℃未満では炭化が困難で電気二重層キャパシ
タの分極性電極として用いたときには静電容量の劣化が
著しく、９００℃を超えると形成される細孔の孔径が電
気二重層キャパシタの分極性電極として用いるには過大
になる。The mesophase pitch is carbonized by heating at 500 to 900 ° C., preferably 500 to 800 ° C., in a stream of an inert gas such as nitrogen. The mesoface pitch becomes a carbide in which hydrogen, side chains, and the like are eliminated by the heating, leaving only a carbon skeleton. When the heating temperature is less than 500 ° C., carbonization is difficult, and when used as a polarizable electrode of an electric double layer capacitor, the capacitance is significantly deteriorated. It becomes too large to use as a polarizing electrode.
【００３７】前記加熱温度が８００℃を超えると得られ
た炭化物の炭素骨格が強固になり、該炭化物を賦活する
ためにより高温、より多量のアルカリ金属水酸化物を用
いるような厳しい条件が必要となる。前記のような厳し
い条件下に賦活を行うと、加熱に用いる炉が損傷し、炉
材が活性炭に混入する虞がある。従って、前記炭化は５
００〜８００℃で加熱することにより行うことが好まし
い。When the heating temperature exceeds 800 ° C., the carbon skeleton of the obtained carbide becomes strong, and severe conditions such as using a higher temperature and using a larger amount of an alkali metal hydroxide to activate the carbide are required. Become. If the activation is performed under such severe conditions, the furnace used for heating may be damaged, and the furnace material may be mixed into the activated carbon. Therefore, the carbonization is 5
It is preferable to carry out by heating at 00 to 800 ° C.
【００３８】また、前記加熱は不活性気体気流下で行わ
ないと、炭素骨格が酸化されて炭化物が得られない。If the heating is not carried out in an inert gas stream, the carbon skeleton is oxidized and no carbide can be obtained.
【００３９】前記炭化物の賦活は、該炭化物１重量部に
対して１．２〜２．４重量部、好ましくは１．２〜２．
２重量部の水酸化カリウムと混合し、窒素等の不活性気
体気流下５５０〜８５０℃で加熱して行うことにより、
最終製品の活性炭を得るために適した孔径の細孔が形成
される。前記アルカリ賦活には、前記水酸化カリウム以
外のアルカリ金属水酸化物を用いることが可能で、例え
ば水酸化ナトリウム、水酸化リチウム等を挙げることが
できるが、安価であることから水酸化カリウムが好まし
い。前記水酸化カリウムは、前記炭化物１重量部に対し
て１．２重量部未満では細孔の孔径を十分に大きくする
ことができず、また２．４重量部を超えると細孔が大き
くなり過ぎて、体積当りの静電容量が低下する。The activation of the carbide is 1.2 to 2.4 parts by weight, preferably 1.2 to 2.2 parts by weight, based on 1 part by weight of the carbide.
By mixing with 2 parts by weight of potassium hydroxide and heating at 550 to 850 ° C. under a stream of an inert gas such as nitrogen,
A pore having a pore size suitable for obtaining the activated carbon of the final product is formed. For the alkali activation, it is possible to use an alkali metal hydroxide other than the potassium hydroxide, for example, sodium hydroxide, lithium hydroxide, etc., but potassium hydroxide is preferred because it is inexpensive. . When the amount of the potassium hydroxide is less than 1.2 parts by weight with respect to 1 part by weight of the carbide, the pore diameter of the pores cannot be sufficiently increased, and when the amount exceeds 2.4 parts by weight, the pores become too large. Thus, the capacitance per volume decreases.
【００４０】前記水酸化カリウムは、前記炭化物１重量
部に対して２．２重量部を超えると細孔が大きくなって
体積当りの静電容量が低下する傾向があり、また、活性
炭の収量が低減する傾向がある。従って、前記水酸化カ
リウムは、前記炭化物１重量部に対して１．２〜２．２
重量部とすることが好ましい。When the amount of the potassium hydroxide exceeds 2.2 parts by weight with respect to 1 part by weight of the carbide, the pores tend to become large and the capacitance per unit volume tends to decrease. Tends to decrease. Therefore, the potassium hydroxide is 1.2 to 2.2 parts by weight based on 1 part by weight of the carbide.
It is preferable to use parts by weight.
【００４１】また、前記賦活は、加熱温度が５５０℃未
満では得られた活性炭の細孔の孔径を十分に大きくする
ことができず、該活性炭を分極性電極に用いたときに細
孔が目詰まりし、長期間に亘って使用したときに、静電
容量が低下する。一方、前記加熱温度が８５０℃を超え
ると、得られた活性炭の細孔の孔径が過大になり、該活
性炭の容積当たりの静電容量が小さくなる。また、前記
加熱温度が８５０℃を超えると、加熱に用いる炉が損傷
し、炉材が活性炭に混入する虞がある。Further, in the activation, if the heating temperature is lower than 550 ° C., the pore size of the pores of the obtained activated carbon cannot be made sufficiently large. When clogged, the capacitance decreases when used for a long period of time. On the other hand, when the heating temperature exceeds 850 ° C., the pore size of the obtained activated carbon becomes excessively large, and the capacitance per volume of the activated carbon becomes small. If the heating temperature exceeds 850 ° C., the furnace used for heating may be damaged, and the furnace material may be mixed into the activated carbon.
【００４２】また、前記加熱は不活性気体気流下で行わ
ないと、前記炭化物が酸化され、所望の活性炭が得られ
ないことがある。If the heating is not performed in an inert gas stream, the carbides may be oxidized and a desired activated carbon may not be obtained.
【００４３】次に、本発明の実施例について説明する。Next, an embodiment of the present invention will be described.
【００４４】[0044]
【実施例１】本実施例では、石油ピッチから得られたメ
ゾフェース樹脂を溶融、紡糸し、不融化して得られた繊
維状のメゾフェースピッチ（ペトカ社製）を、まず、窒
素気流下６５０℃の温度で１時間加熱して炭化物とし
た。次いで、前記炭化物１重量部に対して１．６重量部
の水酸化カリウムを混合し、窒素気流下８００℃の温度
で５時間加熱してアルカリ賦活を行って活性炭繊維を得
た。そして、得られた活性炭繊維を粉砕して微粒子とし
た。Example 1 In this example, a fibrous mesoface pitch (manufactured by Petka) obtained by melting, spinning, and infusing a mesoface resin obtained from petroleum pitch was first placed in a nitrogen stream 650. It was heated at a temperature of ° C. for 1 hour to form a carbide. Next, 1.6 parts by weight of potassium hydroxide was mixed with 1 part by weight of the carbide, and the mixture was heated at a temperature of 800 ° C. for 5 hours in a nitrogen stream to perform alkali activation to obtain activated carbon fibers. Then, the obtained activated carbon fiber was pulverized into fine particles.
【００４５】本実施例の活性炭の断面の電子顕微鏡写真
の摸写図を図２に示す。図２において、すじ状に表わさ
れている部分１１が黒鉛の積層構造層である。従って、
本実施例の活性炭１２は、その表面が一様に黒鉛の積層
構造層１１により被覆されていることが明らかである。FIG. 2 shows a schematic view of an electron micrograph of a cross section of the activated carbon of this embodiment. In FIG. 2, a portion 11 represented in a stripe shape is a graphite laminated structure layer. Therefore,
It is apparent that the surface of the activated carbon 12 of this embodiment is uniformly covered with the graphite laminated structure layer 11.
【００４６】次に、本実施例の活性炭を、導電性フィラ
ーとしてのファーネスブラック（電気化学社製、商品
名：デンカブラック）及び結着剤と混合し、圧粉成形し
て図１示の分極性電極１とした。Next, the activated carbon of the present example was mixed with furnace black (trade name: Denka Black, manufactured by Denki Kagaku) as a conductive filler and a binder, and the mixture was compacted and compacted as shown in FIG. Polar electrode 1 was used.
【００４７】本実施例では、活性炭：導電性フィラー：
結着剤の混合比を重量比で、８６：９：５としたもの、
９０：５：５としたもの、９３：２：５としたもの、９
５：０：５としたものの４種の分極性電極１を製造し、
各一対の分極性電極１，１をセパレーター２としてのガ
ラスフィルター（ＡＤＶＡＴＥＣ社製、商品名：ＧＡ−
１００）の両面に取着して容器３に収容した。そして、
テトラエチルアンモニウムテトラフロロボーレート
（〔（Ｃ2 Ｈ5 ）4 Ｎ〕+ ＢＦ4 - ）の１モル／リット
ルの炭酸プロピレン溶液を電解液として注入し、容器３
を蓋体５で閉蓋することにより４種の電気二重層キャパ
シタを形成した。In this embodiment, activated carbon: conductive filler:
A mixing ratio of the binder of 86: 9: 5 by weight,
90: 5: 5, 93: 2: 5, 9
5: 0: 5, four kinds of polarizable electrodes 1 were manufactured,
A glass filter (manufactured by ADVATEC, trade name: GA-
100) and housed in the container 3. And
Tetraethylammonium tetrafluoroethane baud rate ([(C 2 H 5) 4 N] + BF 4 -) 1 mole / liter propylene carbonate solution was injected as an electrolytic solution, a container 3
Was closed with a lid 5 to form four types of electric double layer capacitors.
【００４８】次に、前記４種の電気二重層キャパシタに
ついて、分極性電極１の内部抵抗及び単位容積当たりの
静電容量を測定した。結果を図４に示す。Next, the internal resistance and the capacitance per unit volume of the polarizable electrode 1 were measured for the four types of electric double layer capacitors. FIG. 4 shows the results.
【００４９】[0049]
【比較例１】本比較例では、ポリ塩化ビニル樹脂を、窒
素気流下６５０℃の温度で１時間加熱して炭化し、得ら
れた炭化物１重量部に対して１．６重量部の水酸化カリ
ウムを混合し、窒素気流下８００℃の温度で５時間加熱
してアルカリ賦活を行って活性炭を得た。Comparative Example 1 In this comparative example, a polyvinyl chloride resin was carbonized by heating at 650 ° C. for 1 hour in a nitrogen stream, and 1.6 parts by weight of hydroxylated resin was obtained with respect to 1 part by weight of the obtained carbide. Potassium was mixed and heated at a temperature of 800 ° C. for 5 hours in a nitrogen stream to activate the alkali to obtain activated carbon.
【００５０】本比較例の活性炭の断面の電子顕微鏡写真
の摸写図を図３に示す。図３では、黒鉛の積層構造層は
図２と同様に、すじ状の部分１１として表わされてい
る。従って、本比較例の活性炭１３では、黒鉛の積層構
造層１１は活性炭１３の表面から内部に向けて形成され
ており、活性炭１３の表面に露出している黒鉛が少ない
ことが明らかである。FIG. 3 shows a schematic view of an electron micrograph of a cross section of the activated carbon of this comparative example. In FIG. 3, the layered structure layer of graphite is represented as a streak-like portion 11 as in FIG. Therefore, in the activated carbon 13 of this comparative example, the graphite laminated structure layer 11 is formed from the surface of the activated carbon 13 toward the inside, and it is clear that the graphite exposed on the surface of the activated carbon 13 is small.
【００５１】次に、本比較例の活性炭を用いた以外は、
実施例１と同一にして、活性炭：導電性フィラー：結着
剤の混合比を重量比で、８６：９：５としたもの、９
０：５：５としたもの、９３：２：５としたもの、９
５：０：５としたものの４種の分極性電極１を製造し
た。次に、前記４種の分極性電極１を用い、実施例１と
同一にして、４種の電気二重層キャパシタを形成した。Next, except that the activated carbon of this comparative example was used,
The same as in Example 1 except that the mixing ratio of activated carbon: conductive filler: binder was 86: 9: 5 by weight, 9
0: 5: 5, 93: 2: 5, 9
Four types of polarizable electrodes 1 having a ratio of 5: 0: 5 were manufactured. Next, four types of electric double layer capacitors were formed using the four types of polarizable electrodes 1 in the same manner as in Example 1.
【００５２】次に、前記４種の電気二重層キャパシタに
ついて、分極性電極１の内部抵抗及び単位容積当たりの
静電容量を測定した。結果を図４に、前記実施例１の結
果と併せて示す。Next, the internal resistance and the capacitance per unit volume of the polarizable electrode 1 were measured for the four types of electric double layer capacitors. FIG. 4 shows the results together with the results of Example 1.
【００５３】図４から、実施例１の活性炭を用いる分極
性電極１によれば、導電性フィラーの量が等量であれ
ば、比較例１の活性炭を用いる分極性電極１よりも内部
抵抗が低くなり、この傾向は導電性フィラーの量が増え
るほど顕著になることが明らかである。また、実施例１
の活性炭を用いる分極性電極１によれば、導電性フィラ
ーの量が等量であれば、比較例１の活性炭を用いる分極
性電極１よりも静電容量が大きくなることが明らかであ
る。これは、明らかに、実施例１の活性炭粒子表面の導
電性が改良されている結果と考えることができる。FIG. 4 shows that the polarizable electrode 1 using activated carbon of Example 1 has a lower internal resistance than the polarizable electrode 1 using activated carbon of Comparative Example 1 if the amount of the conductive filler is equal. It is clear that this tendency becomes more pronounced as the amount of the conductive filler increases. Example 1
According to the polarizable electrode 1 using activated carbon, it is apparent that the capacitance is larger than that of the polarizable electrode 1 using activated carbon of Comparative Example 1 when the amount of the conductive filler is equal. This can clearly be attributed to the improved conductivity of the activated carbon particle surfaces of Example 1.
【００５４】[0054]
【実施例２】本実施例では、石油ピッチから得られたメ
ゾフェース樹脂を溶融、紡糸し、不融化して得られた繊
維状のメゾフェースピッチ（ペトカ社製）を、まず、窒
素気流下、それぞれ５００℃、６００℃、７００℃、７
５０℃、８００℃、８５０℃及び９００℃の温度で１時
間加熱して、７種の炭化物を得た。次いで、前記各炭化
物１重量部に対して１．６重量部の水酸化カリウムを混
合し、窒素気流下、それぞれ５５０℃、６５０℃、７５
０℃及び８００℃の範囲の温度で５時間加熱してアルカ
リ賦活を行って、２８種の活性炭繊維を得た。そして、
得られた各活性炭繊維を粉砕して微粒子とした。Example 2 In this example, a fibrous mesoface pitch (manufactured by Petka) obtained by melting, spinning, and infusing a mesoface resin obtained from petroleum pitch was first placed under a nitrogen stream. 500 ° C, 600 ° C, 700 ° C, 7 respectively
Heating at a temperature of 50 ° C., 800 ° C., 850 ° C., and 900 ° C. for 1 hour provided seven kinds of carbides. Next, 1.6 parts by weight of potassium hydroxide was mixed with 1 part by weight of each of the above-mentioned carbides, and the mixture was heated at 550 ° C., 650 ° C.
By heating at a temperature in the range of 0 ° C. and 800 ° C. for 5 hours to activate the alkali, 28 types of activated carbon fibers were obtained. And
Each of the obtained activated carbon fibers was pulverized into fine particles.
【００５５】次に、本実施例の各活性炭を、導電性フィ
ラーとしてのファーネスブラック（電気化学社製、商品
名：デンカブラック）及び結着剤と、活性炭：導電性フ
ィラー：結着剤＝８５：１０：５（重量比）となるよう
に混合し、圧粉成形して図１示の分極性電極１とした以
外は、実施例１と同一にして２８種の電気二重層キャパ
シタを製造した。Next, each activated carbon of the present example was prepared by using furnace black (manufactured by Denki Kagaku Co., trade name: Denka Black) as a conductive filler and a binder, and activated carbon: conductive filler: binder = 85. : 10: 5 (weight ratio), and 28 kinds of electric double layer capacitors were manufactured in the same manner as in Example 1 except that the polarizable electrode 1 shown in FIG. 1 was obtained by compacting. .
【００５６】次に、前記各電気二重層キャパシタを用い
て充放電を行い、前記各分極性電極１の単位容積当たり
の静電容量を測定した。結果を図５に示す。Next, charge / discharge was performed using each of the electric double layer capacitors, and the capacitance per unit volume of each of the polarizable electrodes 1 was measured. FIG. 5 shows the results.
【００５７】図５から、５００〜９００℃の範囲の温度
で炭化させ、５５０〜８００℃の範囲の温度でアルカリ
賦活した活性炭によれば、単位容積当たりの静電容量が
ファラッド級になることが判る。As shown in FIG. 5, according to the activated carbon carbonized at a temperature in the range of 500 to 900 ° C. and activated with alkali at a temperature in the range of 550 to 800 ° C., the capacitance per unit volume may become farad class. I understand.
【００５８】次に、前記各電気二重層キャパシタのう
ち、５００℃、６００℃、７００℃、７５０℃、８００
℃及び８５０℃の温度で炭化し、８００℃でアルカリ賦
活した活性炭を用いる６種の電気二重層キャパシタにつ
いて、初期静電容量に対し、３．５Ｖで充放電を１００
サイクル繰り返した後の静電容量維持率を測定した。結
果を下記表１に示す。Next, among the electric double layer capacitors, 500 ° C., 600 ° C., 700 ° C., 750 ° C., 800
Charging / discharging at 3.5 V with respect to the initial capacitance of six types of electric double layer capacitors using activated carbon carbonized at temperatures of 800 ° C. and 850 ° C. and activated at 800 ° C.
The capacitance retention after the cycle was repeated was measured. The results are shown in Table 1 below.
【００５９】[0059]
【表１】 [Table 1]
【００６０】表１から、炭化温度が７００℃から６００
℃、５００℃と低くなるにつれて、静電容量維持率が低
減することが明らかであり、炭化温度が５００℃未満の
ときには、静電容量維持率がさらに低減して静電容量の
劣化が著しくなる。As shown in Table 1, the carbonization temperature was from 700 ° C. to 600
It is evident that the capacitance retention rate decreases as the temperature decreases to 500 ° C. and 500 ° C. When the carbonization temperature is lower than 500 ° C., the capacitance retention rate further decreases, and the deterioration of the capacitance becomes remarkable. .
【００６１】[0061]
【実施例３】本実施例では、石油ピッチから得られたメ
ゾフェース樹脂を溶融、紡糸し、不融化して得られた繊
維状のメゾフェースピッチ（ペトカ社製）を、まず、窒
素気流下、それぞれ５００℃、６００℃、７００℃、７
５０℃、８００℃及び８５０℃の温度で１時間加熱し
て、６種の炭化物を得た。次いで、前記各炭化物１重量
部に対して、５００℃で炭化した炭化物にはそれぞれ、
１．２重量部、１．４重量部、１．６重量部、１．８重
量部及び２．０重量部の水酸化カリウムを混合し、他の
炭化物にはそれぞれ１．２重量部、１．４重量部、１．
６重量部、１．８重量部及び２．０重量部、２．２重量
部、２．４重量部の水酸化カリウムを混合し、窒素気流
下８００℃の温度で５時間加熱してアルカリ賦活を行っ
て、４０種の活性炭繊維を得た。そして、得られた各活
性炭繊維を粉砕して微粒子とした。Example 3 In this example, a fibrous mesoface pitch (manufactured by Petka) obtained by melting, spinning, and infusing a mesoface resin obtained from petroleum pitch was first placed under a nitrogen stream. 500 ° C, 600 ° C, 700 ° C, 7 respectively
Heating at 50 ° C., 800 ° C. and 850 ° C. for 1 hour resulted in six carbides. Next, for 1 part by weight of each of the above-mentioned carbides,
1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight and 2.0 parts by weight of potassium hydroxide were mixed, and 1.2 parts by weight, 1 part by weight and .4 parts by weight;
6 parts by weight, 1.8 parts by weight, 2.0 parts by weight, 2.2 parts by weight, and 2.4 parts by weight of potassium hydroxide are mixed and heated at a temperature of 800 ° C. for 5 hours in a nitrogen stream to activate the alkali. To obtain 40 types of activated carbon fibers. Each of the obtained activated carbon fibers was pulverized into fine particles.
【００６２】次に、本実施例の各活性炭を、導電性フィ
ラーとしてのファーネスブラック（電気化学社製、商品
名：デンカブラック）及び結着剤と、活性炭：導電性フ
ィラー：結着剤＝８５：１０：５（重量比）となるよう
に混合し、圧粉成形して図１示の分極性電極１とした以
外は、実施例１と同一にして４０種の電気二重層キャパ
シタを製造した。Next, each of the activated carbons of the present embodiment was prepared by using furnace black (manufactured by Denki Kagaku Co., trade name: Denka Black) as a conductive filler and a binder, and activated carbon: conductive filler: binder = 85. : 10: 5 (weight ratio) and 40 kinds of electric double layer capacitors were manufactured in the same manner as in Example 1 except that the mixture was pressed and compacted to obtain the polarizable electrode 1 shown in FIG. .
【００６３】次に、前記各電気二重層キャパシタを用い
て充放電を行い、前記分極性電極１の単位容積当たりの
静電容量を測定した。結果を図６に示す。Next, charge / discharge was performed using each of the electric double layer capacitors, and the capacitance per unit volume of the polarizable electrode 1 was measured. FIG. 6 shows the results.
【００６４】図６から、５００〜８５０℃の範囲の温度
で炭化させ、得られた炭化物１重量部に対して１．２〜
２．４重量部の水酸化カリウムを混合してアルカリ賦活
した活性炭によれば、単位容積当たりの静電容量がファ
ラッド級になることが判る。FIG. 6 shows that carbonization was performed at a temperature in the range of 500 to 850 ° C., and 1.2 to 1 part by weight of the obtained carbide.
According to activated carbon mixed with 2.4 parts by weight of potassium hydroxide and alkali-activated, the capacitance per unit volume is found to be farad class.
【００６５】次に、前記各電気二重層キャパシタのう
ち、６００℃の温度で炭化した炭化物に対し、得られた
炭化物１重量部当り１．２重量部、１．４重量部、１．
６重量部、２．０重量部、２．２重量部、２．４重量部
の水酸化カリウムを混合し、窒素気流下８００℃の温度
で５時間加熱してアルカリ賦活を行ったときの活性炭の
収率を表２に示す。Next, of the electric double layer capacitors, 1.2 parts by weight, 1.4 parts by weight, 1 part by weight, and 1 part by weight of the obtained carbonized carbonized carbide at a temperature of 600 ° C.
Activated carbon obtained by mixing 6 parts by weight, 2.0 parts by weight, 2.2 parts by weight, and 2.4 parts by weight of potassium hydroxide and heating at 800 ° C. for 5 hours in a nitrogen stream to carry out alkali activation. Are shown in Table 2.
【００６６】[0066]
【表２】 [Table 2]
【００６７】表２から、炭化物１重量部当りに混合する
水酸化カリウムの量が多くなるほど活性炭の収率が低下
し、水酸化カリウムが炭化物１重量部当り２．４重量部
を超えると、さらに活性炭の収率の低下が著しくなる。From Table 2, it can be seen that as the amount of potassium hydroxide mixed per 1 part by weight of carbide increases, the yield of activated carbon decreases, and when potassium hydroxide exceeds 2.4 parts by weight per 1 part by weight of carbide, The yield of activated carbon significantly decreases.
【図１】本発明の電気二重層キャパシタの一実施態様を
示す説明的断面図。FIG. 1 is an explanatory sectional view showing one embodiment of an electric double layer capacitor of the present invention.
【図２】本実施形態の活性炭の粒子構造を示す電子顕微
鏡写真の摸写図。FIG. 2 is a simulated view of an electron micrograph showing the particle structure of the activated carbon of the present embodiment.
【図３】従来の活性炭の粒子構造を示す電子顕微鏡写真
の摸写図。FIG. 3 is a schematic view of an electron micrograph showing the particle structure of a conventional activated carbon.
【図４】図２及び図３に示す活性炭粒子を用いた分極性
電極の内部抵抗及び静電容量を示すグラフ。FIG. 4 is a graph showing the internal resistance and capacitance of a polarizable electrode using the activated carbon particles shown in FIGS. 2 and 3.
【図５】本実施形態の活性炭の炭化温度と該活性炭を用
いた分極性電極の静電容量の関係を示すグラフ。FIG. 5 is a graph showing the relationship between the carbonization temperature of the activated carbon of the present embodiment and the capacitance of a polarizable electrode using the activated carbon.
【図６】本実施形態の活性炭のアルカリ賦活に用いるア
ルカリ金属水酸化物の量と該活性炭を用いた分極性電極
の静電容量の関係を示すグラフ。FIG. 6 is a graph showing the relationship between the amount of an alkali metal hydroxide used for alkali activation of activated carbon of the present embodiment and the capacitance of a polarizable electrode using the activated carbon.
１…分極性電極、 ２…セパレータ、 ３，５…集電部
材、 １１…黒鉛の積層構造、 １２…活性炭。DESCRIPTION OF SYMBOLS 1 ... Polarizable electrode, 2 ... Separator, 3,5 ... Current collection member, 11 ... Laminated structure of graphite, 12 ... Activated carbon.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 野口 実 埼玉県和光市中央１丁目４番１号 株式会 社本田技術研究所内 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Minoru Noguchi 1-4-1 Chuo, Wako-shi, Saitama Pref.
Claims (8)
た粒子であって、該粒子の少なくとも一部の表面が該表
面に沿って形成された黒鉛の積層構造層により被覆され
ていることを特徴とする電気二重層キャパシタ用活性
炭。1. A particle obtained by pulverizing activated carbon or activated carbon fiber, wherein at least a part of the surface of the particle is covered with a laminated structure layer of graphite formed along the surface. Activated carbon for electric double layer capacitors.
であって、粒子の少なくとも一部の表面が該表面に沿っ
て形成された黒鉛の積層構造層により被覆された活性炭
と、導電性フィラーと、結着剤とからなることを特徴と
する分極性電極。2. A polarizable electrode used for an electric double layer capacitor, wherein at least a part of the surface of the particle is activated carbon covered with a graphite laminated structure layer formed along the surface; And a binder.
電極と、各分極性電極に設けられた集電部材と、電解液
とからなる電気二重層キャパシタにおいて、該分極性電
極は粒子の少なくとも一部の表面が該表面に沿って形成
された黒鉛の積層構造層により被覆された活性炭と、導
電性フィラーと、結着剤とからなることを特徴とする電
気二重層キャパシタ。3. An electric double layer capacitor comprising a pair of polarizable electrodes facing each other with a separator interposed therebetween, a current collecting member provided on each polarizable electrode, and an electrolytic solution. An electric double layer capacitor comprising: activated carbon, a part of which is covered with a graphite laminated structure layer formed along the surface; a conductive filler; and a binder.
を冷却、固化したメゾフェース樹脂の表面を部分酸化し
て不融化することによりメゾフェースピッチを得る工程
と、該メゾフェースピッチを不活性気体気流下５００〜
９００℃で加熱して炭化させる工程と、前記工程で得ら
れた炭化物を該炭化物１重量部に対して１．２〜２．４
重量部のアルカリ金属水酸化物と混合し、不活性気体気
流下５５０〜８５０℃で加熱してアルカリ賦活する工程
とからなることを特徴とする電気二重層キャパシタ用活
性炭の製造方法。4. A step of cooling the mesophase extracted from petroleum pitch and partially oxidizing and solidifying the surface of the solidified mesophase resin to obtain a mesoface pitch, and subjecting the mesoface pitch to an inert gas stream. 500 ~
A step of heating at 900 ° C. to carbonize, and the carbide obtained in the step is 1.2 to 2.4 with respect to 1 part by weight of the carbide.
Mixing with a part by weight of an alkali metal hydroxide and heating at 550 to 850 ° C. in an inert gas stream to activate the alkali.
のちその表面を部分酸化し不融化してメゾフェースピッ
チ繊維とし、該メゾフェースピッチ繊維に前記炭化させ
る工程と前記アルカリ賦活する工程とを施したのち、生
成物を粉砕して粒子状活性炭を得ることを特徴とする請
求項４記載の電気二重層キャパシタ用活性炭の製造方
法。5. A step of melting and spinning the mesophase resin and partially oxidizing and infusing the surface thereof to form mesoface pitch fibers, and subjecting the mesoface pitch fibers to the carbonizing step and the alkali activating step. 5. The method for producing activated carbon for an electric double layer capacitor according to claim 4, wherein the product is pulverized to obtain particulate activated carbon.
のちその表面を部分酸化し不融化してメゾフェースピッ
チを得ることを特徴とする請求項４または請求項５記載
の電気二重層キャパシタ用活性炭の製造方法。6. The activated carbon for an electric double layer capacitor according to claim 4, wherein the mesophase resin is pulverized into fine particles, and then the surface is partially oxidized and made infusible to obtain a mesophase pitch. Manufacturing method.
とを特徴とする請求項４乃至請求項６のいずれかの項記
載の電気二重層キャパシタ用活性炭の製造方法。7. The method for producing activated carbon for an electric double layer capacitor according to claim 4, wherein the carbonization is heated at 500 to 800 ° C.
重量部に対して１．２〜２．２重量部を混合することを
特徴とする請求項４乃至請求項７のいずれかの項記載の
電気二重層キャパシタ用活性炭の製造方法。8. The method according to claim 1, wherein the alkali metal hydroxide is the carbide 1
The method for producing activated carbon for electric double layer capacitors according to any one of claims 4 to 7, wherein 1.2 to 2.2 parts by weight is mixed with respect to part by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10157027A JPH11135380A (en) | 1997-09-01 | 1998-06-05 | Activated carbon for electric double layer capacitor and its manufacture |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-251357 | 1997-09-01 | ||
| JP25135797 | 1997-09-01 | ||
| JP10157027A JPH11135380A (en) | 1997-09-01 | 1998-06-05 | Activated carbon for electric double layer capacitor and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11135380A true JPH11135380A (en) | 1999-05-21 |
Family
ID=26484613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10157027A Pending JPH11135380A (en) | 1997-09-01 | 1998-06-05 | Activated carbon for electric double layer capacitor and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11135380A (en) |
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| WO2001013390A1 (en) * | 1999-08-10 | 2001-02-22 | Honda Giken Kogyo Kabushiki Kaisha | Method for producing activated carbon for electrode of electric double-layer capacitor |
| DE10039174B4 (en) * | 1999-08-10 | 2006-06-29 | Honda Giken Kogyo K.K. | Electrode for an electric double layer capacitor and slurry for forming the same |
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| EP1571127A3 (en) * | 2004-03-01 | 2006-09-27 | Mitsubishi Gas Chemical Company, Inc. | Production process for carbonized product and carbonized product obtained by the same process |
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| US7625543B2 (en) | 2004-03-01 | 2009-12-01 | Mitsubishi Gas Chemical Company, Inc. | Production process for carbonized product and carbonized product obtained by the same process |
| WO2006006218A1 (en) * | 2004-07-09 | 2006-01-19 | Osaka Gas Co., Ltd. | Active carbon for electric double layer capacitor, active carbon electrode for electric double layer capacitor and electric double layer capacitor utilizing the same |
| JP2006131464A (en) * | 2004-11-08 | 2006-05-25 | Jfe Chemical Corp | Porous carbon material, manufacturing method thereof and electric double layer capacitor |
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| CN108574078A (en) * | 2017-03-13 | 2018-09-25 | 浙江高铭节能科技有限公司 | A kind of valve-regulated iron-nickel storage battery and manufacturing method |
| CN108574078B (en) * | 2017-03-13 | 2023-09-01 | 浙江高铭节能科技有限公司 | Valve-controlled iron-nickel storage battery and manufacturing method thereof |
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