JPH10149957A - Manufacturing method of activated carbon for electrode of organic solvent-based electrical double layered capacitor - Google Patents
Manufacturing method of activated carbon for electrode of organic solvent-based electrical double layered capacitorInfo
- Publication number
- JPH10149957A JPH10149957A JP9222135A JP22213597A JPH10149957A JP H10149957 A JPH10149957 A JP H10149957A JP 9222135 A JP9222135 A JP 9222135A JP 22213597 A JP22213597 A JP 22213597A JP H10149957 A JPH10149957 A JP H10149957A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- activated carbon
- alkali activation
- activation treatment
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は有機溶媒系電解液を用い
る電気二重層コンデンサの分極性電極に用いられる活性
炭の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing activated carbon for use in a polarizable electrode of an electric double layer capacitor using an organic solvent-based electrolyte.
【０００２】[0002]
【従来の技術】電気二重層コンデンサは、ファラッド級
の大容量を有し、充放電サイクル特性にも優れることか
ら、電子機器のバックアップ電源、車載のバッテリーな
どの用途に使用されている。2. Description of the Related Art An electric double layer capacitor has a farad-class large capacity and excellent charge / discharge cycle characteristics, and is therefore used for applications such as backup power supplies for electronic equipment and in-vehicle batteries.
【０００３】この電気二重層コンデンサは、例えば図３
に示すように、活性炭からなる一対の分極性電極１，１
がセパレータ２を介して対向して設けられ、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てそれぞれ陽極および陰極とし
て作用するよう構成されている。図３示の電気二重層コ
ンデンサでは、セパレータ２を介して対向する分極性電
極１，１はアルミニウム製容器３に収容されると共に、
パッキン４を介してアルミニウム製容器３に取着される
アルミニウム製蓋体５で閉蓋するようになっている。前
記構成において、容器３及び蓋体５はそれぞれ分極性電
極１，１に接触し、容器３が分極性電極１に対する陰極
側集電部材、蓋体５が分極性電極１に対する陽極側集電
部材となっている。[0003] This electric double layer capacitor is, for example, shown in FIG.
As shown in the figure, a pair of polarizable electrodes 1 and 1 made of activated carbon are used.
Are provided opposite each other with a separator 2 interposed therebetween, and the polarizable electrode 1 is configured to be impregnated with an organic solvent solution such as a tetraalkylammonium salt as an electrolytic solution so as to function as an anode and a cathode, respectively. In the electric double layer capacitor shown in FIG. 3, the polarizable electrodes 1 and 1 facing each other via the separator 2 are accommodated in an aluminum container 3 and
The lid is closed by an aluminum lid 5 attached to the aluminum container 3 via the packing 4. In the above configuration, the container 3 and the lid 5 are in contact with the polarizable electrodes 1 and 1 respectively, and the container 3 is a cathode-side current collector for the polarizable electrode 1 and the lid 5 is an anode-side current collector for the polarizable electrode 1. It has become.
【０００４】このような電気二重層コンデンサの分極性
電極には、微細な細孔を有する活性炭が用いられている
が、電気二重層コンデンサをより小型化・軽量化・大容
量化するために、前記分極性電極の静電容量密度を高く
することができる活性炭が求められている。Activated carbon having fine pores is used for the polarizable electrode of such an electric double layer capacitor. However, in order to make the electric double layer capacitor smaller, lighter and larger in capacity, Activated carbon capable of increasing the capacitance density of the polarizable electrode is required.
【０００５】このため、前記分極性電極の静電容量密度
を高くすることができる活性炭を得るべく、活性炭の各
種特性について検討されており、例えば、「電極中の活
性炭重量当たりの静電容量密度と活性炭の比表面積とは
ほぼ直線的な比例関係にあり、活性炭電極上の電気二重
層の静電容量は、炭種や細孔特性に影響を受けず略一定
である」とする仮説が提言されている（電気化学，５
９，Ｎｏ．７，ｐ．６０７−６１３，１９９１）。Therefore, in order to obtain activated carbon capable of increasing the capacitance density of the polarizable electrode, various characteristics of the activated carbon have been studied. For example, "Capacitance density per weight of activated carbon in the electrode" has been studied. And the specific surface area of the activated carbon are almost linearly proportional, and the capacitance of the electric double layer on the activated carbon electrode is almost constant without being affected by the type of carbon and pore characteristics. (Electrochemistry, 5
9 , no. 7, p. 607-613, 1991).
【０００６】しかし、活性炭の電気二重層の静電容量と
して水銀電極などにより観測される値と、活性炭の比表
面積とから、該活性炭を用いる分極性電極の電気二重層
コンデンサの静電容量の理論値を求めると、該理論値は
該電気二重層コンデンサの静電容量の実測値と一致しな
い。However, the theoretical value of the capacitance of the electric double layer capacitor of the polarizable electrode using the activated carbon is determined from the value observed by the mercury electrode or the like as the capacitance of the electric double layer of the activated carbon and the specific surface area of the activated carbon. When the value is obtained, the theoretical value does not match the actually measured value of the capacitance of the electric double layer capacitor.
【０００７】例えば、図３示のようにセパレータ２を挟
んで一対の分極性電極１，１を備える構成となっている
該電気二重層コンデンサの静電容量をＣ0 とし、分極性
電極１，１の静電容量をＣ1 ，Ｃ2 とすると、 １／Ｃ0 ＝１／Ｃ1 ＋１／Ｃ2 ・・・（１） と表せる。ここで、水銀電極により観測される活性炭の
電気二重層の静電容量は、２０μＦ／ｃｍ2 程度である
から、１５００ｍ2 ／ｃｃの比表面積を有する活性炭の
電気二重層の静電容量は、 ２０（μＦ／ｃｍ2 ）×１５００（ｍ2 ／ｃｃ）＝３０
０（Ｆ／ｃｃ） となる。そこで、（１）式でＣ1 ，Ｃ2 にそれぞれ３０
０（Ｆ／ｃｃ）を代入してＣ0 を求めると、Ｃ0 ＝１５
０（Ｆ／ｃｃ）となる。Ｃ0 は２容積分の分極性電極１
に対する静電容量であるので、前記電気二重層コンデン
サの理論的静電容量は前記Ｃ0 の値を２で除して７５Ｆ
／ｃｃとなるはずである。For example, as shown in FIG. 3, the electric double layer capacitor having a pair of polarizable electrodes 1 and 1 with a separator 2 interposed therebetween has a capacitance C 0 , Assuming that the capacitance of 1 is C 1 and C 2 , it can be expressed as 1 / C 0 = 1 / C 1 + 1 / C 2 (1). Here, the capacitance of the electric double layer of activated carbon observed by the mercury electrode is about 20 μF / cm 2 , and thus the capacitance of the electric double layer of activated carbon having a specific surface area of 1500 m 2 / cc is 20 (ΜF / cm 2 ) × 1500 (m 2 / cc) = 30
0 (F / cc). Therefore, in equation (1), C 1 and C 2 are each set to 30.
0 If (F / cc) by substituting seek C 0, C 0 = 15
0 (F / cc). C 0 is a polarizable electrode 1 for 2 volumes
, The theoretical capacitance of the electric double layer capacitor is 75 F by dividing the value of C 0 by 2.
/ Cc.
【０００８】ところが、前記電気二重層コンデンサの静
電容量は実際には１３Ｆ／ｃｃ程度にしかならない。ま
た、同じ比表面積を有する活性炭同士でも、それを用い
た電気二重層コンデンサの静電容量が全く異なる場合も
ある。However, the capacitance of the electric double layer capacitor is actually only about 13 F / cc. Even between activated carbons having the same specific surface area, the electric double layer capacitor using the same may have completely different capacitances.
【０００９】そこで、本発明者らは、前記仮説が、分析
の限界が約１０オングストロームであるチッ素ガス吸着
によるＢＥＴ法で計測された比表面積に基づいてなされ
ていることに着目し、前記仮説を検証すべく、透過型電
子顕微鏡の画像を用いて１０オングストローム未満の微
細な細孔も分析できる特殊な画像分析を行い、比表面積
の異なる電極用活性炭について静電容量密度と比表面積
の関係を調べたところ、両者の間には直線的な比例関係
は存在せず、静電容量を左右する要素が他に存在すると
の結論が得られた。The present inventors have focused on the hypothesis based on the specific surface area measured by the BET method using nitrogen gas adsorption, which has a limit of analysis of about 10 angstroms, and focused on the hypothesis. In order to verify the relationship between the capacitance density and the specific surface area of activated carbon for electrodes with different specific surface areas, we conducted a special image analysis that can analyze fine pores of less than 10 angstroms using transmission electron microscope images. Upon examination, it was concluded that there was no linear proportional relationship between the two, and that there were other factors that affected the capacitance.
【００１０】本発明者らは、この知見に基づいてさらに
検討を重ねた結果、活性炭の細孔分布の最頻値を前記有
機溶媒が溶媒和した前記電解液イオンの吸着に適した孔
径とすることにより、電気二重層コンデンサの分極性電
極に用いたときに、容積当たりの静電容量密度に優れた
活性炭が得られることを見出し、このような電気二重層
コンデンサ電極用活性炭については既に特許出願してい
る（特願平８−４６９１２号明細書参照）。前記明細書
記載の活性炭は、塩化ビニル系樹脂を焼成して得られた
炭化物を、４００〜１０００℃の範囲の温度に１〜２０
時間保持することにより１段階でアルカリ賦活するもの
であり、細孔分布の最頻値が前記有機溶媒が溶媒和した
前記電解液イオンの吸着に適した１０〜２０オングスト
ロームの範囲となっている。As a result of further studies based on this finding, the present inventors have determined that the mode of the pore distribution of activated carbon is a pore size suitable for the adsorption of the electrolyte ions solvated by the organic solvent. As a result, it has been found that when used as a polarizable electrode of an electric double layer capacitor, an activated carbon having an excellent capacitance density per volume can be obtained, and such activated carbon for an electric double layer capacitor electrode has already been applied for a patent. (See Japanese Patent Application No. 8-46912). The activated carbon described in the above specification is obtained by calcining a carbide obtained by calcining a vinyl chloride resin at a temperature in the range of 400 to 1000 ° C for 1 to 20 ° C.
By holding for a time, alkali activation is performed in one step, and the mode of pore distribution is in the range of 10 to 20 Å suitable for adsorption of the electrolyte ions solvated with the organic solvent.
【００１１】なお、前記最頻値とは、細孔の孔径の度数
分布において、相対頻度の最も大きい度数を示す孔径の
値をいう。また、前記孔径の度数分布は、活性炭の透過
型電子顕微鏡の画像をもとに、これを二値化して得られ
た画像のフーリエ変換により得られるパワースペクトル
から求められる。The mode is the value of the pore diameter that indicates the frequency with the highest relative frequency in the frequency distribution of the pore diameter of the pores. Further, the frequency distribution of the pore diameter is obtained from a power spectrum obtained by Fourier transform of an image obtained by binarizing an activated carbon image based on a transmission electron microscope image.
【００１２】このような活性炭によれば、細孔分布の最
頻値が前記範囲にあるので、電極密度が高く、容積当た
りの静電容量密度に特に優れた分極性電極を形成するこ
とができ、該分極性電極によりエネルギー密度の高い電
気二重層コンデンサを構成することができる。According to such activated carbon, since the mode of the pore distribution is in the above-mentioned range, it is possible to form a polarizable electrode having a high electrode density and a particularly excellent capacitance density per volume. An electric double layer capacitor having a high energy density can be constituted by the polarizable electrode.
【００１３】しかしながら、前記のように電極密度を大
きくすることができるような条件で賦活処理を行った活
性炭を用いた分極性電極は、充放電の繰り返しにより静
電容量が低下しやすいとの不都合がある。[0013] However, the polarizable electrode using activated carbon which has been activated under the condition that the electrode density can be increased as described above has a disadvantage that the capacitance is apt to decrease due to repeated charge and discharge. There is.
【００１４】[0014]
【発明が解決しようとする課題】従って、本発明は大き
な電極密度を備えると共に、充放電の繰り返しによる静
電容量の低下が少ない分極性電極を得ることができる活
性炭を製造する方法を提供することを目的とする。SUMMARY OF THE INVENTION Accordingly, the present invention provides a method for producing an activated carbon capable of obtaining a polarizable electrode having a large electrode density and having a small decrease in capacitance due to repeated charging and discharging. With the goal.
【００１５】[0015]
【課題を解決するための手段】前記目的を達成するため
に、本発明の有機溶媒系電気二重層コンデンサ電極用活
性炭の製造方法は、易黒鉛化性有機物を焼成して炭化さ
せたのち、得られた炭化物に対してアルカリ賦活処理を
行う活性炭の製造方法において、前記アルカリ賦活処理
は、第１の範囲の温度による第１のアルカリ賦活処理
と、第２の範囲の温度であって第１のアルカリ賦活処理
より高い温度による第２のアルカリ賦活処理とからな
り、前記いずれか一方のアルカリ賦活処理の後、他方の
アルカリ賦活処理を行うことを特徴とする。In order to achieve the above object, a method for producing activated carbon for an organic solvent-based electric double layer capacitor electrode according to the present invention comprises a step of firing and carbonizing an easily graphitizable organic substance. In the method for producing activated carbon in which an alkali activation treatment is performed on the obtained carbide, the alkali activation treatment includes a first alkali activation treatment at a temperature in a first range and a first alkali activation treatment at a temperature in a second range. The second alkali activation treatment is performed at a higher temperature than the alkali activation treatment, and after any one of the alkali activation treatments, the other alkali activation treatment is performed.
【００１６】前記本発明によれば、易黒鉛化性有機物を
炭化させて得られた炭化物に対して、第１の範囲の温度
による第１のアルカリ賦活処理を行うことにより、微細
な細孔を確保することができる。このような活性炭は、
炭素密度が高いので電気二重層コンデンサの分極性電極
に用いたときに、その電極密度が高くなり、容積当たり
の静電容量密度を高くすることができる。According to the present invention, fine pores are formed by subjecting a carbide obtained by carbonizing a graphitizable organic substance to a first alkali activation treatment at a temperature in a first range. Can be secured. Such activated carbon is
Since the carbon density is high, when it is used for a polarizable electrode of an electric double layer capacitor, the electrode density increases, and the capacitance density per volume can be increased.
【００１７】また、本発明によれば、前記炭化物に対し
て、第２の範囲の温度による第２のアルカリ賦活処理を
行うことにより、表面の官能基が除去された活性炭が得
られ、かかる活性炭によれば、電気二重層コンデンサの
分極性電極として用いるときに充放電の繰り返しによる
静電容量の低下が抑制される。Further, according to the present invention, by performing a second alkali activation treatment on the carbide at a temperature in a second range, an activated carbon from which surface functional groups have been removed can be obtained. According to this, when used as a polarizable electrode of an electric double layer capacitor, a decrease in capacitance due to repetition of charging and discharging is suppressed.
【００１８】従って、本発明によれば、前記異なる温度
による２段階のアルカリ賦活処理を行うことにより、電
気二重層コンデンサの分極性電極に用いたときに、容積
当たりの静電容量密度が高く、しかも充放電の繰り返し
による静電容量の低下を抑制することができる活性炭を
得ることができる。Therefore, according to the present invention, by performing the two-stage alkali activation treatment at the different temperatures, when used for the polarizable electrode of the electric double layer capacitor, the capacitance density per volume is high, In addition, activated carbon capable of suppressing a decrease in capacitance due to repeated charge and discharge can be obtained.
【００１９】本発明において、前記両アルカリ賦活処理
の順序は特に限定されず、第１のアルカリ賦活処理の後
に第２のアルカリ賦活処理を行ってもよく、反対に第２
のアルカリ賦活処理の後に第１のアルカリ賦活処理を行
ってもよい。In the present invention, the order of the two alkali activation treatments is not particularly limited, and the second alkali activation treatment may be performed after the first alkali activation treatment.
The first alkali activation treatment may be performed after the alkali activation treatment.
【００２０】また、本発明は、前記いずれか一方のアル
カリ賦活処理の後、連続して他方のアルカリ賦活処理を
行うことを特徴とする。本発明によれば、前記両アルカ
リ賦活処理を連続して行うことにより、工程を簡略化し
て製造コストを低減することができる。Further, the present invention is characterized in that after any one of the above alkali activation treatments, the other alkali activation treatment is continuously performed. According to the present invention, by performing the two alkali activation treatments successively, the process can be simplified and the production cost can be reduced.
【００２１】アルカリ賦活処理では、通常、処理後に、
得られた活性炭を水洗、中和洗浄して、未反応の活性化
剤や夾雑物等を除去する後処理が行われる。そこで、本
発明において、前記両アルカリ賦活処理を連続して行う
とは、例えば第１のアルカリ賦活処理に連続して第２の
アルカリ賦活処理を行う場合には、前記第１のアルカリ
賦活処理の後で前記後処理を行わず、そのまま第２のア
ルカリ賦活処理を行うことを意味する。In the alkali activation treatment, usually, after the treatment,
The obtained activated carbon is washed with water and neutralized to carry out a post-treatment for removing unreacted activator, impurities and the like. Therefore, in the present invention, performing both the alkali activation treatments continuously means, for example, when performing the second alkali activation treatment following the first alkali activation treatment, This means that the second alkali activation treatment is directly performed without performing the post-treatment.
【００２２】本発明に用いる前記易黒鉛化性有機物と
は、比較的低温、例えば約８００℃以下の焼成処理によ
って容易に黒鉛構造が形成される有機化合物を包括的に
指称し、例えば、塩化ビニル系樹脂、ポリアクリロニト
リルなどの脂肪族系高分子化合物のほか、タール、メゾ
フェースピッチ、ポリイミドなどの芳香族系高分子化合
物を挙げることができるが、製造コストの面から塩化ビ
ニル系樹脂が好ましい。前記黒鉛構造の形成は、例え
ば、Ｘ線回折パターンにおいて、２θが２５°付近に明
白なピークを持つことによって確認できる。The graphitizable organic substance used in the present invention is a general term for an organic compound which can easily form a graphite structure by firing at a relatively low temperature, for example, at about 800 ° C. or less. Aromatic polymer compounds such as tar, mesophase pitch, and polyimide can be used in addition to aliphatic polymer compounds such as a resin and polyacrylonitrile, and vinyl chloride resins are preferable from the viewpoint of production cost. The formation of the graphite structure can be confirmed by, for example, having a clear peak at 25 around 25 ° in the X-ray diffraction pattern.
【００２３】前記易黒鉛化性有機物は前記の様に約８０
０℃以下の焼成処理によって黒鉛構造が形成されるが、
本発明では、該易黒鉛化性有機物を室温から７００℃未
満の温度まで加熱することにより行うことにより、前記
黒鉛構造が形成されると共に、前記賦活処理により活性
炭としたときに前記電気二重層コンデンサの分極性電極
に適した孔径となる微細孔を形成することができる。
尚、前記焼成温度が７００℃を超えると、得られた炭化
物の焼結により、形成された細孔が閉塞され、賦活処理
が難しくなる。The easily graphitizable organic material is about 80 as described above.
A graphite structure is formed by a firing treatment at 0 ° C. or lower,
In the present invention, the graphite structure is formed by heating the graphitizable organic material from room temperature to a temperature of less than 700 ° C., and the electric double layer capacitor is formed when activated carbon is obtained by the activation treatment. Micropores having a pore diameter suitable for the polarizable electrode can be formed.
If the firing temperature exceeds 700 ° C., the formed pores are blocked by sintering of the obtained carbide, and the activation treatment becomes difficult.
【００２４】前記易黒鉛化性有機物の焼成により得られ
た炭化物に対する前記第１のアルカリ賦活処理は、６０
０〜９５０℃の範囲の温度で行うことを特徴とする。前
記第１のアルカリ賦活処理は、６００℃未満では賦活が
進みにくく十分な静電容量が得られず、９５０℃を超え
ると、過賦活により細孔径が全体的に拡大して、得られ
る活性炭の密度が著しく低下する。前記第１のアルカリ
賦活処理は、製造コストの面から８００〜９００℃の範
囲、特に８６０℃前後の温度で行うことが好ましい。The first alkali activation treatment for the carbide obtained by calcining the graphitizable organic substance is carried out in 60
The process is performed at a temperature in the range of 0 to 950 ° C. In the first alkali activation treatment, activation is difficult to proceed at a temperature lower than 600 ° C., and a sufficient capacitance is not obtained. When the temperature exceeds 950 ° C., the pore diameter is entirely increased by overactivation, and the obtained activated carbon is activated. The density is significantly reduced. The first alkali activation treatment is preferably performed at a temperature in the range of 800 to 900 ° C, particularly around 860 ° C, from the viewpoint of manufacturing cost.
【００２５】前記第１のアルカリ賦活処理は前記範囲の
温度に１〜２０時間保持して行うことを特徴とする。前
記範囲の温度に保持する時間が１時間未満では充分な細
孔形成ができず、２０時間を超えると、過賦活により孔
径が拡大された細孔の数が多くなる。なお、前記範囲の
温度に保持する時間は、製造コストの面から２〜１０時
間、特に４時間前後とすることが好ましい。The first alkali activation treatment is carried out while maintaining the temperature in the above range for 1 to 20 hours. If the time for maintaining the temperature in the above range is less than 1 hour, sufficient pore formation cannot be performed, and if the time exceeds 20 hours, the number of pores whose pore diameter has been increased by overactivation increases. The time for maintaining the temperature in the above range is preferably 2 to 10 hours, particularly about 4 hours from the viewpoint of manufacturing cost.
【００２６】また、前記炭化物に対する前記第２のアル
カリ賦活処理は８００〜１０００℃の範囲で、しかも前
記第１のアルカリ賦活処理よりも高い温度で行うことを
特徴とする。前記第２のアルカリ賦活処理は８００℃未
満では前記第１のアルカリ賦活処理に対して十分な温度
差を設けることが難しくなり、表面官能基の除去や適度
な細孔径の拡大が困難となる。一方、１０００℃を超え
ると、短時間の処理でも過賦活となり、不要な密度低下
を招く。Further, the second alkali activation treatment for the carbide is performed at a temperature in the range of 800 to 1000 ° C. and at a temperature higher than that of the first alkali activation treatment. If the second alkali activation treatment is performed at a temperature lower than 800 ° C., it is difficult to provide a sufficient temperature difference with respect to the first alkali activation treatment, and it becomes difficult to remove surface functional groups and to appropriately expand the pore diameter. On the other hand, when the temperature exceeds 1000 ° C., even if the treatment is carried out for a short time, it is overactivated, which causes an unnecessary decrease in density.
【００２７】前記第２のアルカリ賦活処理は前記範囲の
温度まで昇温したのち直ちに降温するか、或いは前記範
囲の温度に２時間以内の範囲で保持することにより行
う。前記範囲の温度に保持する時間は、２時間を超える
と過賦活となる。なお、前記範囲の温度に保持する時間
は、製造コストの面から１時間以内、特に０．５時間前
後が好ましい。The second alkali activation treatment is carried out by raising the temperature to the above-mentioned range and then immediately lowering the temperature, or by maintaining the temperature in the above-mentioned range within a range of 2 hours. When the time for maintaining the temperature in the above range exceeds 2 hours, overactivation occurs. The time for maintaining the temperature in the above range is preferably within one hour from the viewpoint of manufacturing cost, and particularly preferably around 0.5 hour.
【００２８】本発明において、前記アルカリ賦活処理
は、活性化剤としてアルカリ金属水酸化物の１価の塩基
を用いて行うことにより、孔径２０オングストローム以
下の細孔を容易に形成することができる。前記アルカリ
金属水酸化物としては、水酸化リチウム、水酸化ナトリ
ウム、水酸化カリウム等を挙げることができるが、中で
も安価であることから水酸化カリウムが好ましい。In the present invention, pores having a pore diameter of 20 angstroms or less can be easily formed by performing the alkali activation treatment using a monovalent base of an alkali metal hydroxide as an activator. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like. Of these, potassium hydroxide is preferable because of its low cost.
【００２９】前記活性化剤による前記アルカリ賦活処理
は、炭化物１重量部に対してアルカリ金属水酸化物１〜
４重量部を用いることを特徴とする。炭化物１重量部に
対する活性化剤の割合が、１重量部未満であると賦活が
十分に進行せず、一方、４重量部を超えると、得られた
活性炭から電気二重層コンデンサの分極性電極を形成し
たときに、該分極性電極の体積当たりの静電容量密度が
低下する虞れがある。The alkali activating treatment with the activating agent is performed in such a manner that the alkali metal hydroxide 1 to 1 part by weight of the carbide is used.
It is characterized by using 4 parts by weight. If the ratio of the activator to 1 part by weight of the carbide is less than 1 part by weight, the activation does not proceed sufficiently, while if it exceeds 4 parts by weight, the polarizable electrode of the electric double layer capacitor is obtained from the obtained activated carbon. When formed, the capacitance density per volume of the polarizable electrode may be reduced.
【００３０】前記活性化剤の割合は、静電容量を確保す
るために、炭化物１重量部に対して１．５〜３重量部、
特に１．８〜２．２重量部とすることが好ましい。The ratio of the activator is 1.5 to 3 parts by weight with respect to 1 part by weight of carbide to secure the capacitance.
In particular, the content is preferably 1.8 to 2.2 parts by weight.
【００３１】また、本実施形態において、前記炭化物
は、前記アルカリ賦活の前に、粒径０．１〜３００μｍ
の範囲の粒子に粉砕することにより、粒子内の賦活を均
一に行うことができる。前記炭化物は、粒径が０．１μ
ｍ未満であると、得られた活性炭から電気二重層コンデ
ンサの分極性電極を形成したときに、自己放電特性が低
減することがある。また、粒径が３００μｍを超える
と、粒子内での賦活が均一に進行しにくくなる虞れがあ
る。前記炭化物は、粒子内の賦活をより均一に行うため
に、１〜１００μｍに粉砕しておくことが好ましい。In this embodiment, the carbide has a particle diameter of 0.1 to 300 μm before the alkali activation.
By crushing into particles in the range, activation in the particles can be performed uniformly. The carbide has a particle size of 0.1 μm.
If it is less than m, the self-discharge characteristic may be reduced when the polarizable electrode of the electric double layer capacitor is formed from the obtained activated carbon. On the other hand, when the particle size exceeds 300 μm, there is a possibility that activation within the particles does not easily progress uniformly. The carbide is preferably pulverized to 1 to 100 μm in order to more uniformly activate the particles.
【００３２】[0032]
【発明の実施の形態】次に、添付の図面を参照しながら
本発明の活性炭の製造方法の好適な実施形態についてさ
らに詳しく説明する。図１は塩化ビニル系樹脂の熱重量
測定のチャート、図２は塩化ビニル系樹脂の焼成温度と
時間との関係を示すグラフ、図３は電気二重層コンデン
サの一構成例の一部を切り欠いて示す説明的断面図であ
る。BEST MODE FOR CARRYING OUT THE INVENTION Next, a preferred embodiment of the method for producing activated carbon of the present invention will be described in more detail with reference to the accompanying drawings. FIG. 1 is a chart of the thermogravimetry of a vinyl chloride resin, FIG. 2 is a graph showing the relationship between the calcination temperature and time of the vinyl chloride resin, and FIG. FIG.
【００３３】本実施形態では、易黒鉛化性樹脂として製
造コストの点で有利な塩化ビニル系樹脂を用い、まず、
前記塩化ビニル系樹脂を焼成して炭化させる。In this embodiment, a vinyl chloride resin which is advantageous in terms of production cost is used as the graphitizable resin.
The vinyl chloride resin is fired and carbonized.
【００３４】図１に示すように、塩化ビニル系樹脂は、
室温から次第に昇温していくと、約２５０℃に始まり約
３５０℃で終了する１段目の重量減少と、約４２０℃に
始まり約５００℃で終了する２段目の重量減少との２段
階の重量減少を示す。図１の熱重量測定のチャートか
ら、前記塩化ビニル系樹脂を焼成する際には、１段目の
重量減少が始まる約２５０℃から２段目の重量減少が始
まる約４２０℃にかけて側鎖が脱離して活性炭の炭素骨
格が形成され、２段目の重量減少が始まる約４２０℃か
ら約７００℃までの間に塩素が脱離して細孔が形成され
るものと考えられる。As shown in FIG. 1, the vinyl chloride resin is
As the temperature gradually rises from room temperature, there are two stages, a first stage weight reduction starting at about 250 ° C. and ending at about 350 ° C., and a second stage weight reduction starting at about 420 ° C. and ending at about 500 ° C. Shows the weight loss. According to the thermogravimetry chart shown in FIG. 1, when the vinyl chloride resin is fired, the side chains are removed from about 250 ° C. at which the first stage weight loss starts to approximately 420 ° C. at which the second stage weight reduction starts. It is considered that the carbon skeleton of the activated carbon is formed by separation, and chlorine is eliminated from about 420 ° C. to about 700 ° C. at which the second stage of weight reduction starts to form pores.
【００３５】そして、約７００℃から約１０００℃の間
では、水素が脱離して微細孔が形成され、約１０００℃
から約２０００℃の間では炭素の焼結による細孔の閉塞
が起き約２０００℃を超えると炭素骨格の再配列により
細孔の緻密化が進行すると考えられる。従って、１００
０℃以上に加熱しても、得られた活性炭から電気二重層
コンデンサの分極性電極を形成したときに静電容量の向
上が望めない。At a temperature between about 700 ° C. and about 1000 ° C., hydrogen is desorbed to form micropores.
When the temperature is between about 2000 ° C. and about 2000 ° C., pores are blocked due to sintering of carbon. Therefore, 100
Even when heated to 0 ° C. or higher, no improvement in capacitance can be expected when the polarizable electrode of the electric double layer capacitor is formed from the obtained activated carbon.
【００３６】そこで、本実施形態では、前記塩化ビニル
系樹脂の焼成をチッ素ガス、アルゴンガスなどの不活性
ガス雰囲気下、室温から６００℃まで加熱することによ
り行う。前記塩化ビニル系樹脂の焼成は、前記１段階目
の重量減少開始温度（２５０℃）まではどのような昇温
速度でもよいが、１段階目の重量減少開始温度から２段
階目の重量減少終了温度（５００℃）までは、塩化ビニ
ルの溶解、分解反応が生じるために２０〜１５０℃／時
間、特に４０〜１００℃／時間の昇温速度で昇温するこ
とが好ましい。また、２段階目の重量減少終了温度から
６００℃までは、塩素原子が脱離するために１００〜３
００℃／時間、特に１５０〜２５０℃／時間の昇温速度
で昇温することが好ましい。また、処理分全体の温度を
均一にするために６００℃に０〜２４時間、特に０．５
〜５時間保持して焼成することが好ましい。In the present embodiment, the vinyl chloride resin is fired by heating from room temperature to 600 ° C. in an atmosphere of an inert gas such as nitrogen gas or argon gas. The calcination of the vinyl chloride resin may be performed at any heating rate up to the first-stage weight loss start temperature (250 ° C.), but the second-stage weight loss end is performed from the first-stage weight loss start temperature. Up to the temperature (500 ° C.), it is preferable to raise the temperature at a rate of 20 to 150 ° C./hour, particularly 40 to 100 ° C./hour in order to cause the dissolution and decomposition reaction of vinyl chloride. In addition, from the temperature at the end of weight reduction in the second stage to 600 ° C., 100 to 3
The temperature is preferably raised at a rate of 00 ° C./hour, particularly 150 to 250 ° C./hour. In addition, in order to make the temperature of the entire treatment portion uniform, the temperature is maintained at 600 ° C. for 0 to 24 hours, particularly 0.5 ° C.
It is preferable to hold and bake for up to 5 hours.
【００３７】そこで、前記塩化ビニル系樹脂の焼成は、
例えば図２に示すように、まず、室温から２５０℃まで
１時間で昇温し、２５０℃に０．５時間保持する。次い
で、２５０℃から５００℃まで５０℃／時の割合で昇温
し、さらに５００℃から６００℃まで２００℃／時の割
合で昇温して６００℃に１時間保持することにより、炭
化物が得られる。Therefore, the sintering of the vinyl chloride resin is performed as follows.
For example, as shown in FIG. 2, first, the temperature is raised from room temperature to 250 ° C. in one hour, and is maintained at 250 ° C. for 0.5 hour. Next, the temperature was raised from 250 ° C. to 500 ° C. at a rate of 50 ° C./hour, and further from 500 ° C. to 600 ° C. at a rate of 200 ° C./hour and maintained at 600 ° C. for 1 hour to obtain a carbide. Can be
【００３８】本実施形態では、次に、前記炭化物を粒径
０．１〜３００μｍ、好ましくは１〜１００μｍに粉砕
し、炭化物１重量部当たり１〜４重量部の水酸化カリウ
ムと混合したのち、不活性ガス気流中で加熱してアルカ
リ賦活することにより電気二重層コンデンサの分極性電
極に用いられる活性炭とする。In the present embodiment, the carbide is then pulverized to a particle size of 0.1 to 300 μm, preferably 1 to 100 μm, and mixed with 1 to 4 parts by weight of potassium hydroxide per 1 part by weight of the carbide. Activated carbon used for the polarizable electrode of the electric double layer capacitor is obtained by heating in an inert gas stream to activate the alkali.
【００３９】前記アルカリ賦活は、６００〜９５０℃の
範囲の温度に１〜２０時間保持する第１のアルカリ賦活
処理と、８００〜１０００℃の範囲、かつ前記第１のア
ルカリ賦活処理より高い温度で、該温度まで昇温したの
ち直ちに降温するか、或いは該温度に２時間以内の範囲
で保持する第２のアルカリ賦活処理とからなる。The alkali activation is carried out at a temperature in the range of 600 to 950 ° C. for 1 to 20 hours, and at a temperature in the range of 800 to 1000 ° C. and higher than that of the first alkali activation. Or a second alkali activation treatment in which the temperature is immediately lowered after the temperature is raised to the temperature, or the temperature is maintained within the range of 2 hours or less.
【００４０】前記アルカリ賦活処理は、第１のアルカリ
賦活処理の後で第２のアルカリ賦活処理を行ってもよ
く、反対に第２のアルカリ賦活処理の後で第１のアルカ
リ賦活処理を行ってもよい。また、前記アルカリ賦活処
理は、第１のアルカリ賦活処理に連続して第２のアルカ
リ賦活処理を行うか、第２のアルカリ賦活処理に連続し
て第１のアルカリ賦活処理を行うというように、前記両
アルカリ賦活処理を連続して行うようにしてもよい。In the alkali activation treatment, a second alkali activation treatment may be performed after the first alkali activation treatment, and conversely, the first alkali activation treatment may be performed after the second alkali activation treatment. Is also good. In addition, the alkali activation treatment may be such that a second alkali activation treatment is performed continuously with the first alkali activation treatment, or a first alkali activation treatment is performed continuously with the second alkali activation treatment. The two alkali activation treatments may be performed continuously.
【００４１】このようにして得られた活性炭は、ファー
ネスブラック等の導電材及びテトラフルオロエチレン等
の結着剤等と混合して成形され、図３に示す有機溶媒系
電気二重層コンデンサの分極性電極１として用いられ
る。The activated carbon thus obtained is mixed with a conductive material such as furnace black and a binder such as tetrafluoroethylene and molded. Used as an electrode 1.
【００４２】分極性電極１に含浸される電解質として
は、過塩素酸、６フッ化リン酸、４フッ化ホウ酸、トリ
フルオロアルキルスルホン酸、テトラフルオロメタンス
ルホン酸のテトラアルキルアンモニウム塩または過塩素
酸、６フッ化リン酸、４フッ化ホウ酸、トリフルオロア
ルキルスルホン酸、テトラフルオロメタンスルホン酸の
ジアルキルアミン塩等を挙げることができる。また、前
記電解質を溶解する有機溶媒としては、プロピレンカー
ボネート、ブチレンカーボネート、γ−ブチロラクト
ン、アセトニトリル、ジメチルホルムアミド、１，２−
ジメトキシエタン、スルホラン、ニトロエタン等を挙げ
ることができる。The electrolyte impregnated in the polarizable electrode 1 is perchloric acid, hexafluorophosphoric acid, tetrafluoroboric acid, trifluoroalkylsulfonic acid, tetraalkylammonium salt of tetrafluoromethanesulfonic acid or perchloric acid. Examples include acids, hexafluorophosphoric acid, tetrafluoroboric acid, trifluoroalkylsulfonic acid, and dialkylamine salts of tetrafluoromethanesulfonic acid. Further, as the organic solvent for dissolving the electrolyte, propylene carbonate, butylene carbonate, γ-butyrolactone, acetonitrile, dimethylformamide, 1,2-
Examples include dimethoxyethane, sulfolane, nitroethane, and the like.
【００４３】前記電解質は、前記有機溶媒に０．１〜３
モル／リットル、好ましくは０．５〜１．５モル／リッ
トルの濃度で溶解され、電解液として使用される。な
お、電解液中では、前記有機溶媒は前記電解質イオンに
溶媒和している状態にあると考えられる。The electrolyte is added to the organic solvent in an amount of 0.1 to 3
It is dissolved in a concentration of mol / l, preferably 0.5 to 1.5 mol / l, and used as an electrolyte. In the electrolyte, the organic solvent is considered to be in a state of being solvated with the electrolyte ions.
【００４４】また、セパレータ２としては、ポリエチレ
ン、ポリプロピレン等のポリオレフィン、ポリエステ
ル、ＰＶＤＦ、セルロース等のシート、またはガラスフ
ィルターが用いられる。As the separator 2, a sheet of polyolefin such as polyethylene or polypropylene, polyester, PVDF, cellulose or the like, or a glass filter is used.
【００４５】本実施形態の活性炭は、前記第１のアルカ
リ賦活処理により、その細孔分布が１０〜２０オングス
トロームの間に最頻値を有し、細孔の大部分が前記電気
二重層コンデンサの電解液中で前記有機溶媒が溶媒和し
ている前記電解質イオンを吸着しやすい大きさとなって
いる。従って、前記活性炭から電気二重層コンデンサの
分極性電極を形成することにより、電気二重層に寄与す
る細孔の割合が格段に大きくなり、前記分極性電極の容
積当たりの静電容量が向上する。The activated carbon of the present embodiment has a mode in which the pore distribution has a mode value of 10 to 20 angstroms due to the first alkali activation treatment, and most of the pores are of the electric double layer capacitor of the electric double layer capacitor. The size is such that the electrolyte ions, which are solvated by the organic solvent in the electrolyte, are easily adsorbed. Therefore, by forming the polarizable electrode of the electric double layer capacitor from the activated carbon, the ratio of the pores contributing to the electric double layer is significantly increased, and the capacitance per volume of the polarizable electrode is improved.
【００４６】しかも、前記活性炭は、前記第２のアルカ
リ賦活処理により、活性炭表面の官能基が除去されてい
るので、充放電の繰り返しによる静電容量の低減が抑制
される。In addition, since the activated carbon has a functional group on the surface of the activated carbon removed by the second alkali activation treatment, a reduction in capacitance due to repeated charging and discharging is suppressed.
【００４７】以下、実施例を挙げて本発明をさらに具体
的に説明するが、本発明は、これらの実施例に限定され
るものではない。なお、特に断らない限り、以下の部お
よび％は、重量基準である。Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The following parts and percentages are by weight unless otherwise specified.
【００４８】[0048]
【実施例１】 〔活性炭の作成〕塩化ビニル系樹脂（ＰＶＣ）をチッ素
ガス雰囲気下、図２示のようにして、室温から６００℃
まで加熱して焼成し、炭化させて得られた炭化物塊を粗
粉砕後、モーターグラインダーで１時間、さらに遊星ボ
ールミルで１時間粉砕し、粒径０．１〜３００μｍに微
粉砕した。この炭化物粉末２．５ｇとＫＯＨ５．０ｇ
〔ＫＯＨ／Ｃ（重量比）＝２〕とを乳鉢で混合し、ま
ず、管状電気炉中、チッ素ガス気流下で８６０℃に４時
間保持して第１のアルカリ賦活処理を行い、前記第１の
アルカリ賦活処理に連続して、さらに９５０℃に昇温
し、該温度に保持せずに直ちに放冷する第２のアルカリ
賦活処理を行って活性炭を得た後、得られた活性炭を水
に分散させ、塩酸で中和洗浄、ろ別後、５０℃で真空乾
燥し、電気二重層コンデンサの原料活性炭とした。Example 1 [Preparation of activated carbon] A vinyl chloride resin (PVC) was heated from room temperature to 600 ° C. in a nitrogen gas atmosphere as shown in FIG.
After heating and calcining, the carbide mass obtained by carbonization was coarsely pulverized, then pulverized for 1 hour with a motor grinder and further for 1 hour with a planetary ball mill, and finely pulverized to a particle size of 0.1 to 300 μm. 2.5 g of this carbide powder and 5.0 g of KOH
[KOH / C (weight ratio) = 2] was mixed in a mortar, and the mixture was first kept at 860 ° C. for 4 hours under a nitrogen gas flow in a tubular electric furnace to perform a first alkali activation treatment. Continuing with the alkali activation treatment of Step 1, the temperature is further raised to 950 ° C., and a second alkali activation treatment is carried out, in which the temperature is raised immediately without being kept at that temperature to obtain activated carbon. The mixture was neutralized and washed with hydrochloric acid, filtered, and dried in vacuo at 50 ° C. to obtain a raw material activated carbon for an electric double layer capacitor.
【００４９】〔充放電サイクル試験〕前記のようにして
得られた原料活性炭０．４２８ｇを、導電材としての粒
状のファーネスブラック（電気化学工業株式会社製、商
品名：デンカブラック）０．０４７ｇ、および結着材と
してのフッ素樹脂（三井デュポンフルオロケミカル株式
会社製、商品名：テフロン７Ｊ）０．０２５ｇと乳鉢で
混練りした後、プレスしてφ２０ｍｍのディスクに成形
し、さらに圧延して、２０ｍｍφのディスク２枚を打ち
抜き、分極性電極とした。[Charge / Discharge Cycle Test] 0.447 g of the raw material activated carbon obtained as described above was mixed with 0.047 g of granular furnace black (manufactured by Denki Kagaku Kogyo KK, trade name: Denka Black) as a conductive material, After kneading in a mortar with 0.025 g of a fluororesin (manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd., trade name: Teflon 7J) as a binder, the mixture was pressed to form a disc having a diameter of 20 mm, and further rolled to form a 20 mm φ Were punched out to obtain polarizable electrodes.
【００５０】この分極性電極を、ガラスフィルターをセ
パレータとし、メチルエチルピリジニウムテトラフルオ
ロボレイト（ＭＥＰＹ／ＢＦ4 ）のプロピレンカーボネ
ート溶液（２モル／リットル）を電解液として用いて試
験セルを組み立てた。A test cell was assembled using the polarizable electrode as a separator with a glass filter as a separator, using a propylene carbonate solution (2 mol / l) of methylethylpyridinium tetrafluoroborate (MEPY / BF 4 ) as an electrolyte.
【００５１】このセルで、充電終止電位３．５Ｖ、放電
終止電位０Ｖ、充放電電流５ｍＡで充放電を繰り返し行
い、電極中の活性炭の静電容量を測定した。電極密度、
重量および容積当たりの初期静電容量、充放電３０サイ
クル及び６０サイクル後の静電容量低下率を表１に示
す。In this cell, charge / discharge was repeated at a charge termination potential of 3.5 V, a discharge termination potential of 0 V, and a charge / discharge current of 5 mA, and the capacitance of activated carbon in the electrode was measured. Electrode density,
Table 1 shows the initial capacitance per weight and volume, and the capacitance reduction rate after 30 cycles and 60 cycles of charge and discharge.
【００５２】[0052]
【実施例２】実施例１において、前記第１のアルカリ賦
活処理に連続して、さらに９５０℃に昇温し、該温度に
０．５時間保持する第２のアルカリ賦活処理を行った以
外は、実施例１と全く同一にして活性炭を作成し、試験
セルを組み立てた。このセルで、実施例１と全く同一に
して充放電を繰り返し行い、電極中の活性炭の静電容量
を測定した。結果を表１に示す。Example 2 Example 1 was repeated except that, following the first alkali activation treatment, a second alkali activation treatment was performed in which the temperature was further raised to 950 ° C. and held at that temperature for 0.5 hour. Activated carbon was produced exactly as in Example 1, and a test cell was assembled. In this cell, charging and discharging were repeated in exactly the same manner as in Example 1, and the capacitance of activated carbon in the electrode was measured. Table 1 shows the results.
【００５３】[0053]
【実施例３】実施例１において、前記第１のアルカリ賦
活処理に連続して、さらに９５０℃に昇温し、該温度に
１．０時間保持する第２のアルカリ賦活処理を行った以
外は、実施例１と全く同一にして活性炭を作成し、試験
セルを組み立てた。このセルで、実施例１と全く同一に
して充放電を繰り返し行い、電極中の活性炭の静電容量
を測定した。結果を表１に示す。Example 3 Example 1 was repeated except that, following the first alkali activation treatment, the second alkali activation treatment was further performed by raising the temperature to 950 ° C. and maintaining the temperature for 1.0 hour. Activated carbon was produced exactly as in Example 1, and a test cell was assembled. In this cell, charging and discharging were repeated in exactly the same manner as in Example 1, and the capacitance of activated carbon in the electrode was measured. Table 1 shows the results.
【００５４】[0054]
【実施例４】実施例１において、前記第１のアルカリ賦
活処理に連続して、さらに９５０℃に昇温し、該温度に
２．０時間保持する第２のアルカリ賦活処理を行った以
外は、実施例１と全く同一にして活性炭を作成し、試験
セルを組み立てた。このセルで、実施例１と全く同一に
して充放電を繰り返し行い、電極中の活性炭の静電容量
を測定した。結果を表１に示す。Example 4 Example 1 was repeated except that, following the first alkali activation treatment, a second alkali activation treatment was performed in which the temperature was further raised to 950 ° C. and held at that temperature for 2.0 hours. Activated carbon was produced exactly as in Example 1, and a test cell was assembled. In this cell, charging and discharging were repeated in exactly the same manner as in Example 1, and the capacitance of activated carbon in the electrode was measured. Table 1 shows the results.
【００５５】[0055]
【実施例５】実施例１において、得られた炭素粉末を、
まず９５０℃に昇温したのち該温度に保持せずに放冷し
て第２のアルカリ賦活処理を行い、次に前記第２のアル
カリ賦活処理に連続して、さらに８６０℃まで放冷し、
該温度に４時間保持して第１のアルカリ賦活処理を行っ
た以外は、実施例１と全く同一にして活性炭を作成し、
試験セルを組み立てた。このセルで、実施例１と全く同
一にして充放電を繰り返し行い、電極中の活性炭の静電
容量を測定した。結果を表１に示す。Example 5 In Example 1, the obtained carbon powder was
First, after raising the temperature to 950 ° C., it is allowed to cool without holding at that temperature to perform a second alkali activation treatment, and then, after the second alkali activation treatment, is further allowed to cool to 860 ° C.
Activated carbon was prepared in exactly the same manner as in Example 1 except that the temperature was maintained at the temperature for 4 hours to perform the first alkali activation treatment.
The test cell was assembled. In this cell, charging and discharging were repeated in exactly the same manner as in Example 1, and the capacitance of activated carbon in the electrode was measured. Table 1 shows the results.
【００５６】尚、本実施例では、前記第２のアルカリ賦
活処理に際して実施例１の第２のアルカリ賦活処理と同
量のＫＯＨを炭化物粉末に混合しただけであり、前記第
１のアルカリ賦活処理に際しては新たなＫＯＨの混合は
行わなかった。In this embodiment, the same amount of KOH as that of the second alkali activation treatment of the first embodiment was mixed with the carbide powder during the second alkali activation treatment, and the first alkali activation treatment was performed. At that time, no new KOH was mixed.
【００５７】[0057]
【実施例６】実施例５において、まず９５０℃に０．５
時間保持する第２のアルカリ賦活処理を行い、次に前記
第２のアルカリ賦活処理に連続して、前記第１のアルカ
リ賦活処理を行った以外は、実施例１と全く同一にして
活性炭を作成し、試験セルを組み立てた。このセルで、
実施例１と全く同一にして充放電を繰り返し行い、電極
中の活性炭の静電容量を測定した。結果を表１に示す。Embodiment 6 In Embodiment 5, first, at 950.degree.
Activated carbon was prepared in exactly the same manner as in Example 1 except that a second alkali activation treatment for holding for a time was performed, and then the first alkali activation treatment was performed subsequently to the second alkali activation treatment. Then, a test cell was assembled. In this cell,
The charge and discharge were repeated in exactly the same manner as in Example 1, and the capacitance of the activated carbon in the electrode was measured. Table 1 shows the results.
【００５８】[0058]
【実施例７】実施例５において、まず９５０℃に２．０
時間保持する第２のアルカリ賦活処理を行い、次に前記
第２のアルカリ賦活処理に連続して、前記第１のアルカ
リ賦活処理を行った以外は、実施例１と全く同一にして
活性炭を作成し、試験セルを組み立てた。このセルで、
実施例１と全く同一にして充放電を繰り返し行い、電極
中の活性炭の静電容量を測定した。結果を表１に示す。Example 7 In Example 5, the temperature was first raised to 950 ° C.
Activated carbon was prepared in exactly the same manner as in Example 1 except that a second alkali activation treatment for holding for a time was performed, and then the first alkali activation treatment was performed subsequently to the second alkali activation treatment. Then, a test cell was assembled. In this cell,
The charge and discharge were repeated in exactly the same manner as in Example 1, and the capacitance of the activated carbon in the electrode was measured. Table 1 shows the results.
【００５９】[0059]
【比較例１】実施例１において、得られた炭素粉末を、
８６０℃に４時間保持して第１のアルカリ賦活処理を行
い、前記第２のアルカリ賦活処理を行わなかった以外
は、実施例１と全く同一にして活性炭を作成し、試験セ
ルを組み立てた。このセルで、実施例１と全く同一にし
て充放電を繰り返し行い、電極中の活性炭の静電容量を
測定した。結果を表１に示す。Comparative Example 1 The carbon powder obtained in Example 1 was
Activated carbon was prepared in exactly the same manner as in Example 1 except that the first alkali activation treatment was carried out at 860 ° C. for 4 hours and the second alkali activation treatment was not carried out, and a test cell was assembled. In this cell, charging and discharging were repeated in exactly the same manner as in Example 1, and the capacitance of activated carbon in the electrode was measured. Table 1 shows the results.
【００６０】[0060]
【比較例２】実施例１において、得られた炭素粉末を、
９５０℃に２．０時間保持して第２のアルカリ賦活処理
を行い、前記第１のアルカリ賦活処理を行わなかった以
外は、実施例１と全く同一にして活性炭を作成し、試験
セルを組み立てた。このセルで、実施例１と全く同一に
して充放電を繰り返し行い、電極中の活性炭の静電容量
を測定した。結果を表１に示す。Comparative Example 2 The carbon powder obtained in Example 1 was
Activated carbon was prepared in exactly the same manner as in Example 1 except that the second alkali activation treatment was performed at 950 ° C. for 2.0 hours, and the first alkali activation treatment was not performed, and a test cell was assembled. Was. In this cell, charging and discharging were repeated in exactly the same manner as in Example 1, and the capacitance of activated carbon in the electrode was measured. Table 1 shows the results.
【００６１】[0061]
【表１】 [Table 1]
【００６２】表１から、本発明の各実施例で得られた活
性炭から形成された分極性電極によれば、電極密度及び
初期静電容量は第１のアルカリ賦活処理のみしか行わな
い比較例１と同等であり、しかも充放電を繰り返した後
の静電容量の低下率は比較例１及び第２のアルカリ賦活
処理のみしか行わない比較例２の両者よりも優れてお
り、顕著な効果を奏することが明らかである。As shown in Table 1, according to the polarizable electrode formed from the activated carbon obtained in each of the examples of the present invention, the electrode density and the initial electrostatic capacity were changed in Comparative Example 1 in which only the first alkali activation treatment was performed. And the rate of decrease in capacitance after repeated charge / discharge is superior to both Comparative Example 1 and Comparative Example 2 in which only the second alkali activation treatment is performed, exhibiting a remarkable effect. It is clear that.
【図面の簡単な説明】[Brief description of the drawings]
【図１】塩化ビニル系樹脂の熱重量測定のチャート。FIG. 1 is a chart of a thermogravimetric measurement of a vinyl chloride resin.
【図２】塩化ビニル系樹脂の焼成温度と時間との関係を
示すグラフ。FIG. 2 is a graph showing the relationship between the sintering temperature and time of a vinyl chloride resin.
【図３】電気二重層コンデンサの一構成例の一部を切り
欠いて示す説明的断面図。FIG. 3 is an explanatory cross-sectional view showing a part of a configuration example of the electric double-layer capacitor in a cutaway manner.
１…分極性電極、 ２…セパレータ、 ３，５…集電部
材。DESCRIPTION OF SYMBOLS 1 ... Polarizable electrode, 2 ... Separator, 3,5 ... Current collecting member.
Claims (3)
ち、得られた炭化物に対してアルカリ賦活処理を行う活
性炭の製造方法において、 前記アルカリ賦活処理は、第１の範囲の温度による第１
のアルカリ賦活処理と、第２の範囲の温度であって第１
のアルカリ賦活処理より高い温度による第２のアルカリ
賦活処理とからなり、前記いずれか一方のアルカリ賦活
処理の後、他方のアルカリ賦活処理を行うことを特徴と
する有機溶媒系電気二重層コンデンサ電極用活性炭の製
造方法。1. A method for producing activated carbon, comprising firing an easily graphitizable organic substance and carbonizing the same, and then subjecting the obtained carbide to an alkali activation treatment, wherein the alkali activation treatment is performed at a temperature in a first range. First
Alkali activation treatment, and a first temperature range of the second range
A second alkali activation treatment at a temperature higher than the alkali activation treatment of the above, and after performing one of the alkali activation treatments, performing the other alkali activation treatment for an organic solvent-based electric double layer capacitor electrode Method for producing activated carbon.
方のアルカリ賦活処理の後、連続して他方のアルカリ賦
活処理を行うことを特徴とする請求項１記載の有機溶媒
系電気二重層コンデンサ電極用活性炭の製造方法。2. The organic solvent-based electric double layer capacitor electrode according to claim 1, wherein in the alkali activation treatment, after one of the alkali activation treatments, the other is activated continuously. Production method for activated carbon.
であることを特徴とする請求項１または請求項２記載の
有機溶媒系電気二重層コンデンサ電極用活性炭の製造方
法。3. The method according to claim 1, wherein the easily graphitizable organic substance is a vinyl chloride resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22213597A JP3406486B2 (en) | 1996-09-17 | 1997-08-19 | Method for producing activated carbon for organic solvent-based electric double layer capacitor electrode |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26509596 | 1996-09-17 | ||
| JP8-265095 | 1996-09-17 | ||
| JP22213597A JP3406486B2 (en) | 1996-09-17 | 1997-08-19 | Method for producing activated carbon for organic solvent-based electric double layer capacitor electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10149957A true JPH10149957A (en) | 1998-06-02 |
| JP3406486B2 JP3406486B2 (en) | 2003-05-12 |
Family
ID=26524703
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22213597A Expired - Fee Related JP3406486B2 (en) | 1996-09-17 | 1997-08-19 | Method for producing activated carbon for organic solvent-based electric double layer capacitor electrode |
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| Country | Link |
|---|---|
| JP (1) | JP3406486B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0984471A2 (en) * | 1998-09-03 | 2000-03-08 | Ngk Insulators, Ltd. | Electric double layer capacitor and method for producing the same |
| JP2008207982A (en) * | 2007-02-26 | 2008-09-11 | Kansai Coke & Chem Co Ltd | Method of highly purifying activated carbon |
| JP2012101948A (en) * | 2010-11-05 | 2012-05-31 | Kansai Coke & Chem Co Ltd | Method for producing activated carbon |
-
1997
- 1997-08-19 JP JP22213597A patent/JP3406486B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0984471A2 (en) * | 1998-09-03 | 2000-03-08 | Ngk Insulators, Ltd. | Electric double layer capacitor and method for producing the same |
| EP0984471A3 (en) * | 1998-09-03 | 2004-02-04 | Ngk Insulators, Ltd. | Electric double layer capacitor and method for producing the same |
| JP2008207982A (en) * | 2007-02-26 | 2008-09-11 | Kansai Coke & Chem Co Ltd | Method of highly purifying activated carbon |
| JP4579939B2 (en) * | 2007-02-26 | 2010-11-10 | 関西熱化学株式会社 | Method for purifying activated carbon |
| JP2012101948A (en) * | 2010-11-05 | 2012-05-31 | Kansai Coke & Chem Co Ltd | Method for producing activated carbon |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3406486B2 (en) | 2003-05-12 |
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