JP3559408B2 - SOLID ACTIVE CARBON, PROCESS FOR PRODUCING THE SAME, AND ELECTRIC DOUBLE LAYER CAPACITOR USING THE SAME - Google Patents
SOLID ACTIVE CARBON, PROCESS FOR PRODUCING THE SAME, AND ELECTRIC DOUBLE LAYER CAPACITOR USING THE SAME Download PDFInfo
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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
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Description
【０００１】
【発明が属する技術分野】
本発明は、一般的な活性炭として脱臭装置、有害ガス除去装置、溶剤回収等の吸着材に広く利用できる固形状活性炭及びその製造方法に関し、さらにこれを用いた電気二重層コンデンサに関するものである。
【０００２】
【従来の技術】
電気二重層コンデンサは、図１に示すように二つの活性炭からなる電極１、１間に電解質２を配置し、両者の界面に生じる電気二重層を利用したコンデンサであり、上記電極１として固形状活性炭が用いられている。また、この他にも電池の電極部材や脱臭装置、有害ガス除去装置、溶剤回収等の吸着材や各種用途に固形状活性炭が用いられているが、これらの固形状活性炭の製造方法は以下の通りである。
【０００３】
炭素化合物を炭化処理して得られた炭化物に、一次賦活処理を施して炭素基材とし、該炭素基材にバインダーを加えて成形体とし、該成形体を炭化処理した後に、二次賦活を施して板状活性炭を得る（特開平８−８３７３６号公報参照）。
【０００４】
活性炭粉末あるいは活性炭繊維と、粒状ないし粉末状フェノール樹脂と、粉末状ないし繊維状熱可塑性樹脂との混合物を成型し、非酸化性雰囲気中で熱処理を行うことにより固体活性炭を得る（特開平７−９９１４１号公報参照）。
【０００５】
フェノール樹脂成形体を発泡、炭化、賦活した多孔質炭素成型体またはメソピッチを発泡、炭化、賦活して多孔質成形体を得る（特開平２−２９７９１５号公報参照）。
【０００６】
活性炭微粒子のみ、あるいはカーボン微粒子とカーボン繊維又は活性炭粉末とメソカーボンを混合して加圧焼結して固体カーボンを得る（特開平３−１３２００９号公報参照）。
【０００７】
活性炭粉末と粉末状フェノール樹脂の混合物を射出成形して熱処理することにより固体活性炭／カーボン複合体を得る（特開平６−４５１８９号公報参照）。
【０００８】
硬化型球状フェノール樹脂を炭化して得た球状炭化物と熱反応型球状フェノール樹脂とを混合し、金型に充填し、加圧下で加熱硬化させ、不活性雰囲気で熱処理した後、賦活する（特開平６−６９０７５号、特開平６−６９０７６号、特開平６−６９０７７号公報参照）。
【０００９】
【発明が解決しょうとする課題】
このような従来の製造方法による固形状の活性炭では、活性炭成分を多くするほど比表面積が増大して吸着能力が高くなるが、その反面強度が低下することから、所定の強度を得るために、活性炭の比率を低くせざるを得なかった。
【００１０】
そのため、この固形状活性炭を電極に用いて電気二重層コンデンサを形成した場合、静電容量が低く、しかも内部抵抗が高いという不都合があった。
【００１１】
即ち、活性炭は多数の細孔を有しており比表面積が大きいため、電気二重層コンデンサの電極に用いた場合、電解質との界面に生じる電気二重層の電荷を多くすることができ、静電容量を高めることができる。ところが、上記のように従来の固形状活性炭では活性炭の比率が低いため、静電容量を高くできないのである。
【００１２】
また、従来の固形状活性炭は、活性炭の比率が低いことから、脱臭装置、有害ガス除去装置、溶剤回収等の吸着材として用いた場合に、吸着能力が低く、機械的強度が低いという不都合があった。
【００１３】
具体的には、従来の製造方法による固形状活性炭では、嵩密度が０．５ｇ／ｃｍ３ 以上で、強度が３００ｇｆ／ｍｍ２ 以上で、かつ比表面積が５００ｍ２ ／ｇ以上のものができなかった。
【００１４】
しかも、従来の製造方法では、固形状活性炭を大量生産できないことから、製造コストが高いという問題点もあった。
【００１５】
【発明の目的】
本発明は、前記課題を解決せんとしてなされたもので、その目的は、比表面積が大きくても、強度の高い固形状活性炭を得て、電気二重層コンデンサの電極として用いた場合の静電容量を高くすることにある。
【００１６】
【課題を解決するための手段】
本発明は、活性炭粉末及び／又は活性炭繊維と、ポリビニルブチラール（以下ＰＶＢ）単体あるいはＰＶＢ及びメソフェーズ系カーボンの熱処理による炭化物とを含有し、嵩密度が０．５ｇ／ｃｍ3 以上、ＢＥＴ法による比表面積が５００ｍ2 ／ｇ以上、かつ３点曲げ強さが３００ｇｆ／ｍｍ2 以上の固形状活性炭としたことを特徴とする。
【００１８】
さらに本発明の固形状活性炭は、活性炭粉末及び／又は活性炭繊維と、ＰＶＢ単体あるいはＰＶＢ及びメソフェーズ系カーボンとの混合物を成形した後、得られた成形体を大気中でエージング処理を行い、その後、非酸化性雰囲気下で熱処理する工程から製造する。
【００１９】
なお、上記製造方法において、活性炭粉末及び／又は活性炭繊維１００重量部に対し、ＰＶＢを３０〜２００重量部、メソフェーズ系カーボンを０〜１００重量部の範囲で混合することが好ましい。これは、活性炭粉末及び／又は活性炭繊維１００重量部に対し、ＰＶＢが２００重量部を越えるとエージング中の変形が大きくなり、３０重量部以下だと基板強度が極端に低下するためであり、またメソフェーズ系カーボンが１００重量％を超えると固形状活性炭の特性が悪くなるためである。
【００２０】
また、上記ＰＶＢ及びメソフェーズ系カーボンは熱処理によって炭化されることから、最終的な固形状活性炭は、５０重量％以上の活性炭粒子と、これらを結合する５０重量％以下のＰＶＢの炭化物、又はこれに加えてメソフェーズ系カーボンの炭化物（カーボン）との複合体から構成されることになる。このとき、活性炭の比率を５０重量％以上と高くできるため、例えば電気二重層コンデンサの電極として用いた場合、静電容量を大きくし、内部抵抗を小さくできる。
【００２１】
さらに本発明におけるＰＶＢは成形用のバインダーとしても作用し、活性炭の比率を５０重量％以上と高くしても成形時の保形性を高くし、良好に乾式プレス成形、ロール成形を行うことができる。そして、得られた成形体を大気中１５０℃〜３００℃の温度でエージング処理を行うことでＰＶＢが架橋し高強度化するために、少量で固形状活性炭の基板強度を高く保つことができ、しかも活性炭の特性を最大限に引き出せる。また、メソフェーズ系カーボンをこれに加えると、ＰＶＢの内部架橋が更に進行し、強度がより高くなる。
【００２２】
さらに、非酸化性雰囲気下で６００℃〜１２００℃にて熱処理を行うことで、ＰＶＢ及びメソフェーズ系カーボンの成分を炭化させ、嵩密度が０．５ｇ／ｃｍ３ 以上で、ＢＥＴ法による比表面積が５００ｍ２ ／ｇ以上で、ＪＩＳ規格の３点曲げ強さが３００ｇｆ／ｍｍ２ 以上である固形状活性炭を得ることができる。
【００２３】
また、本発明は、上記成形体を複数枚積層した後、大気中１５０℃〜３００℃の温度でエージング処理を行い、非酸化性雰囲気下で６００℃〜１２００℃の温度で熱処理することもできる。
【００２４】
上記ポリビニルブチラール（ＰＶＢ）は、一般に市販されているものであればいずれでも良いが、重合度が１５００を超えると乾式成形時の成形性が悪くなるため、重合度１５００以下が望ましい。
【００２５】
また、上記メソフェーズ系カーボンとは以下のようなものである。即ち、有機化合物である炭素原料を加熱すると、含有する低分子化合物が１００℃から蒸発し始める。４００℃を超えると、熱分解反応によりＣ−Ｃ結合が解裂し、分解反応により結合が解裂し、分解低分子量化合物が生成留出する。一方、炭化系内では、有機化合物の結合の解裂により生成したラジカルの再結合、重縮合、環化、脱水素、脱アルキル、芳香族化などの反応が進行して、きわめて重質の芳香族炭化水素が生成する。液相の粘度は、炭化系構成成分の芳香族化、分子量の増加とともに増大し、最終的には固体炭素体となる（液相炭化）。この過程で芳香族分子の規則的な集積が進めば、一種の液晶が形成され、この液晶がメソフェーズと呼ばれる。
【００２６】
また、本発明の固形状活性炭は、脱臭装置、有害ガス除去装置、溶剤回収装置等に吸着材として使用することができる。
【００２７】
特に、本発明では、上記固形状活性炭を分極性電極に用いて、電気二重層コンデンサを構成したことを特徴とし、この電気二重層コンデンサは電極の比表面積が大きいため静電容量を高くすることができる。
【００２８】
【実施例】
実施例１
活性炭粉末（ヤシガラ系、ＢＥＴ値２０００ｍ２ ／ｇ）、ＰＶＢ、を表１の比率で調合し、高速混合攪拌機にて攪拌した。この粉体を４０メッシュパスし、成形用粉体とした。
【００２９】
前記、活性炭粉末の比表面積は、最終静電容量に応じて決定すればよく、限定されるものではないが、電気二重層コンデンサー用の電極に使用するには１５００ｍ２ ／ｇ〜２５００ｍ２ ／ｇの間が望ましい。また、前記ポリビニルブチラールは一般に市販されているものであればいずれでも良いが、重合度が１５００を超えると、乾式成形時の成形性が悪くなるため、重合度１５００以下が望ましい。
【００３０】
得られた粉体を乾式プレス成形、或いは乾式ロール成形して７０×５０×１（ｍｍ）の成形体を得た。この時の成形温度は室温〜６０℃とした。ここで成形温度を限定したのは、６０℃を超えると金型やロールへの成形体の付着が激しくなり、連続成形できなくなるためである。得られた成形体を大気中で表１に示す温度、時間でエージング処理を行い、次いで真空中で表１に示す温度にて熱処理を行い、ＰＶＢを炭化させて活性炭とカーボンの複合体である活性炭基板を作製した。
【００３１】
得られた固体状活性炭基板を図１に示す簡易二重層コンデンサの電極１として用いた時の静電容量を測定した。また、得られた固形状活性炭基板の嵩密度、ＪＩＳ規格の３点曲げ強さ、比表面積（ＢＥＴ法）を測定した結果は表１に示す通りである。
【００３２】
この結果より、ＰＶＢ量が３０重量部未満（Ｎｏ．１）では嵩密度、強度が低いためハンドリングに支障をきたし、一方２００重量部を超えると（Ｎｏ．２３）、エージングにて割れ又は変形が生じ、製品化のためには後処理が必要であった。また、エージングをしない（Ｎｏ．４）か、エージング温度が１５０℃未満（Ｎｏ．５）又は３００℃を超えるもの（Ｎｏ．２０）では、強度が低かった。さらに、熱処理温度が６００℃未満（Ｎｏ．９）では嵩密度が低く、１２００℃を超えると（Ｎｏ．１４）活性炭自身の焼結が進行するために、活性炭自身が持つ細孔が潰れて比表面積が低下し、静電容量が落ちることがわかる。
【００３３】
したがって、ＰＶＢ量は３０〜２００重量部、エージング温度は１５０〜３００℃、熱処理温度は６００〜１２００℃の範囲としておけば、得られた固形状活性炭の嵩密度を０．５ｇ／ｃｍ３ 以上、３点曲げ強さを３００ｇｆ／ｍｍ２ 以上、比表面積を５００ｍ２ ／ｇ以上と高くできることがわかる。
【００３４】
【表１】
実施例２
活性炭粉末（ヤシガラ系、ＢＥＴ値２０００ｍ２ ／ｇ）、ＰＶＢ、メソフェーズカーボンを表２〜８の比率で調合し、高速混合攪拌機にて攪拌した。この粉体を４０メッシュパスし、成形用粉体とした。
【００３６】
前記、活性炭粉末の比表面積は、最終静電容量に応じて決定すればよく、限定されるものではないが、電気二重層コンデンサー用の電極に使用するには１５００ｍ２ ／ｇ〜２５００ｍ２ ／ｇの間が望ましい。また、前記ＰＶＢは一般に市販されているものであればいずれでも良いが、重合度が１５００を超えると、乾式成形時の成形性が悪くなるため、重合度１５００以下が望ましい。
【００３７】
得られた粉体を乾式プレス成形、或いは乾式ロール成形して７０×５０×１（ｍｍ）の成形体を得た。この時の成形温度は室温〜６０℃とした。ここで成形温度を限定したのは、６０℃を超えると金型やロールへの成形体の付着が激しくなり、連続成形できなくなるためである。得られた成形体を大気中で表２〜８に示す温度で４８時間エージング処理を行い、次いで真空中で表２〜８に示す温度にて熱処理を行い、ＰＶＢならびにメソフェーズ系カーボンを炭化させて活性炭とカーボンの複合体である活性炭基板を作製した。
【００３８】
得られたの固形状活性炭基板を図１に示す簡易二重層コンデンサの電極１として用いた時の静電容量を測定した。また、固形状活性炭基板の嵩密度、ＪＩＳ規格の３点曲げ強さ、比表面積（ＢＥＴ法）を測定した結果は表２〜表８に示す通りである。
【００３９】
この結果より、活性炭粉末にＰＶＢを３０〜２００重量部の範囲で添加し、さらにメソフェーズ系カーボンを１００重量部以下の範囲で添加すると強度がさらに向上することが判った。そして、求める静電容量、強度にあわせて、メソフェーズカーボンの量を調製することで種々の特性の固形状活性炭を得ることができる。
【００４０】
また、実施例１と同様に、ＰＶＢ量が３０〜２００重量部の範囲外であり、エージング温度が１５０〜３００℃の範囲外であり、熱処理温度が６００〜１２００℃の範囲外であるもの（表２〜６のＮｏ．１〜１０８）は、嵩密度０．５ｇ／ｃｍ３ 以上、３点曲げ強さを３００ｇｆ／ｍｍ２ 以上、比表面積を５００ｍ２ ／ｇ以上と高くでき、そうでないもの（表７、８のＮｏ．１０９〜１４１）では、いずれかの特性が低くなることがわかる。
【００４１】
【表２】
【表３】
【表４】
【表５】
【表６】
【表７】
【表８】
【発明の効果】
以上のように本発明によれば、活性炭粉末及び／又は活性炭繊維と、ＰＶＢとの混合物に、必要に応じてメソフェーズ系カーボンも添加し、大気中でエージング処理を行い、非酸化性雰囲気で熱処理し、上記ＰＶＢ及びメソフェーズ系カーボンを炭化して固形状活性炭を構成したことによって、活性炭成分の比率を高くしても好適に製造することができ、比表面積と強度の高い固形状活性炭を歩留りよく得ることができ、吸着材としては機械的強度の向上が図れ、さらに吸着能力を向上させることができる。
【００４９】
特に、この固形状活性炭を電極に用いて電気二重層コンデンサを構成すると静電容量を高くすることができる。
【図面の簡単な説明】
【図１】一般的な電気二重層コンデンサを示す概略図である。
【符号の説明】
１：電極
２：電解質[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a solid activated carbon that can be widely used as an adsorbent such as a deodorizing device, a harmful gas removing device, and a solvent recovery device as a general activated carbon, a method for producing the same, and an electric double layer capacitor using the same.
[0002]
[Prior art]
The electric double layer capacitor is a capacitor using an electric double layer generated at an interface between two
[0003]
The carbide obtained by carbonizing the carbon compound is subjected to a primary activation treatment to obtain a carbon substrate, a binder is added to the carbon substrate to form a molded body, and after the carbonized carbonized body, a secondary activation is performed. To obtain a plate-like activated carbon (see JP-A-8-83736).
[0004]
A mixture of activated carbon powder or activated carbon fiber, a granular or powdery phenolic resin, and a powdery or fibrous thermoplastic resin is molded and heat-treated in a non-oxidizing atmosphere to obtain a solid activated carbon (Japanese Patent Laid-Open No. 7-1995). 99141).
[0005]
A porous carbon molded body obtained by foaming, carbonizing and activating a phenolic resin molded body or a porous molded body is obtained by foaming, carbonizing and activating meso pitch (see Japanese Patent Application Laid-Open No. 2-297915).
[0006]
Activated carbon fine particles alone, or carbon fine particles and carbon fiber or activated carbon powder and mesocarbon are mixed and sintered under pressure to obtain solid carbon (see JP-A-3-132009).
[0007]
A mixture of activated carbon powder and a powdery phenol resin is injection-molded and heat-treated to obtain a solid activated carbon / carbon composite (see JP-A-6-45189).
[0008]
A spherical carbide obtained by carbonizing a curable spherical phenolic resin and a heat-reactive spherical phenolic resin are mixed, filled into a mold, heat-cured under pressure, heat-treated in an inert atmosphere, and then activated. See JP-A-6-69075, JP-A-6-69076 and JP-A-6-69077.
[0009]
[Problems to be solved by the invention]
In the solid activated carbon according to such a conventional production method, the specific surface area increases as the amount of the activated carbon component increases, and the adsorption capacity increases, but on the other hand, since the strength decreases, in order to obtain a predetermined strength, The ratio of activated carbon had to be reduced.
[0010]
Therefore, when an electric double layer capacitor is formed using this solid activated carbon as an electrode, there is a disadvantage that the capacitance is low and the internal resistance is high.
[0011]
That is, since activated carbon has a large number of pores and a large specific surface area, when it is used for an electrode of an electric double layer capacitor, the electric charge of the electric double layer generated at the interface with the electrolyte can be increased, and the electrostatic charge can be increased. Capacity can be increased. However, as described above, the capacitance of conventional solid activated carbon cannot be increased because the ratio of activated carbon is low.
[0012]
In addition, conventional solid activated carbon has a low ratio of activated carbon, and therefore, when used as an adsorbent for a deodorizer, a harmful gas remover, a solvent recovery, etc., there is a disadvantage that the adsorption capacity is low and the mechanical strength is low. there were.
[0013]
Specifically, a solid activated carbon produced by a conventional production method cannot have a bulk density of 0.5 g / cm 3 or more, a strength of 300 gf / mm 2 or more, and a specific surface area of 500 m 2 / g or more. Was.
[0014]
In addition, the conventional production method has a problem that the production cost is high because solid activated carbon cannot be mass-produced.
[0015]
[Object of the invention]
The present invention has been made in order to solve the above-mentioned problems, and its object is to obtain a solid activated carbon having a high strength even when the specific surface area is large, and to obtain a capacitance when used as an electrode of an electric double layer capacitor. Is to raise the
[0016]
[Means for Solving the Problems]
The present invention contains activated carbon powder and / or activated carbon fiber, and polyvinyl butyral (hereinafter referred to as PVB) alone or a carbide obtained by heat-treating PVB and mesophase-based carbon, and has a bulk density of 0.5 g / cm 3 or more, and a BET method. The solid activated carbon has a surface area of 500 m 2 / g or more and a three-point bending strength of 300 gf / mm 2 or more.
[0018]
Furthermore, after the solid activated carbon of the present invention is formed by molding activated carbon powder and / or activated carbon fiber and a mixture of PVB alone or PVB and mesophase-based carbon, the obtained molded body is subjected to an aging treatment in the air, and thereafter, It is manufactured from the step of heat treatment in a non-oxidizing atmosphere.
[0019]
In addition, in the said manufacturing method, it is preferable to mix 30-200 weight part of PVB and 0-100 weight part of mesophase-type carbon with respect to 100 weight part of activated carbon powder and / or activated carbon fiber. This is because, when PVB exceeds 200 parts by weight, deformation during aging becomes large, and when it is 30 parts by weight or less, the substrate strength is extremely reduced with respect to 100 parts by weight of activated carbon powder and / or activated carbon fiber. If the content of the mesophase carbon exceeds 100% by weight, the properties of the solid activated carbon deteriorate.
[0020]
Further, since the PVB and the mesophase-based carbon are carbonized by heat treatment, the final solid activated carbon is made up of 50% by weight or more of activated carbon particles and 50% by weight or less of a PVB carbide or a combination thereof. In addition, it is composed of a composite of mesophase-based carbon and carbide (carbon). At this time, since the ratio of activated carbon can be as high as 50% by weight or more, for example, when used as an electrode of an electric double layer capacitor, the capacitance can be increased and the internal resistance can be reduced.
[0021]
Furthermore, the PVB in the present invention also acts as a binder for molding, and increases the shape retention during molding even when the ratio of activated carbon is increased to 50% by weight or more, and enables good dry press molding and roll molding. it can. Then, the obtained molded body is subjected to aging treatment at a temperature of 150 ° C. to 300 ° C. in the air, so that the PVB is cross-linked to increase the strength, so that the substrate strength of the solid activated carbon can be kept high in a small amount, Moreover, the properties of activated carbon can be maximized. Further, when mesophase-based carbon is added thereto, the internal crosslinking of PVB further proceeds, and the strength becomes higher.
[0022]
Furthermore, by performing a heat treatment at 600 to 1200 ° C. in a non-oxidizing atmosphere, the components of PVB and mesophase-based carbon are carbonized, the bulk density is 0.5 g / cm 3 or more, and the specific surface area by the BET method is increased. Solid activated carbon having a 500 m 2 / g or more and a JIS standard three-point bending strength of 300 gf / mm 2 or more can be obtained.
[0023]
Further, in the present invention, after laminating a plurality of the above-mentioned molded bodies, aging treatment may be performed at a temperature of 150 ° C. to 300 ° C. in the air, and heat treatment may be performed at a temperature of 600 ° C. to 1200 ° C. in a non-oxidizing atmosphere. .
[0024]
The polyvinyl butyral (PVB) may be any commercially available one, but if the degree of polymerization exceeds 1500, the moldability during dry molding deteriorates. Therefore, the degree of polymerization is desirably 1500 or less.
[0025]
The above-mentioned mesophase-based carbon is as follows. That is, when the carbon raw material, which is an organic compound, is heated, the contained low molecular compound starts to evaporate from 100 ° C. When the temperature exceeds 400 ° C., the C—C bond is cleaved by the thermal decomposition reaction, the bond is cleaved by the decomposition reaction, and the decomposed low molecular weight compound is produced and distilled. On the other hand, in a carbonized system, reactions such as recombination, polycondensation, cyclization, dehydrogenation, dealkylation, and aromatization of radicals generated by the cleavage of the bond of an organic compound progress, resulting in extremely heavy aromatics. Group hydrocarbons are produced. The viscosity of the liquid phase increases with the aromatization of the carbonized constituents and the increase in the molecular weight, and eventually becomes a solid carbon body (liquid phase carbonization). If regular accumulation of aromatic molecules progresses in this process, a kind of liquid crystal is formed, and this liquid crystal is called a mesophase.
[0026]
Further, the solid activated carbon of the present invention can be used as an adsorbent in a deodorizing device, a harmful gas removing device, a solvent collecting device, and the like.
[0027]
In particular, the present invention is characterized in that the solid activated carbon is used for a polarizable electrode to constitute an electric double layer capacitor, and the electric double layer capacitor has a large specific surface area of the electrode and thus has a high capacitance. Can be.
[0028]
【Example】
Example 1
Activated carbon powder (coconut ash, BET value 2000 m 2 / g) and PVB were blended at the ratio shown in Table 1 and stirred with a high-speed mixing stirrer. This powder was passed through a 40 mesh to obtain a molding powder.
[0029]
The specific surface area of activated carbon powder may be determined according to a final capacitance, but are not limited, to use the electrode for an electric double layer capacitor is 1500m 2 / g~2500m 2 / g Is desirable. The polyvinyl butyral may be any commercially available one, but if the degree of polymerization exceeds 1500, the moldability during dry molding deteriorates. Therefore, the degree of polymerization is preferably 1500 or less.
[0030]
The obtained powder was subjected to dry press molding or dry roll molding to obtain a molded body of 70 × 50 × 1 (mm). The molding temperature at this time was from room temperature to 60 ° C. The reason why the molding temperature is limited here is that if the temperature exceeds 60 ° C., the molded article is strongly attached to a mold or a roll, and continuous molding cannot be performed. The obtained molded body is subjected to aging treatment in air at the temperature and time shown in Table 1, and then heat-treated at a temperature shown in Table 1 in vacuum to carbonize PVB to obtain a composite of activated carbon and carbon. An activated carbon substrate was prepared.
[0031]
The capacitance when the obtained solid activated carbon substrate was used as the
[0032]
From this result, when the PVB amount is less than 30 parts by weight (No. 1), handling is hindered due to low bulk density and strength, while when it exceeds 200 parts by weight (No. 23), cracking or deformation due to aging occurs. Post-treatment was required for commercialization. In the case where aging was not performed (No. 4) or the aging temperature was lower than 150 ° C. (No. 5) or higher than 300 ° C. (No. 20), the strength was low. Further, when the heat treatment temperature is lower than 600 ° C. (No. 9), the bulk density is low, and when it exceeds 1200 ° C. (No. 14), the sintering of the activated carbon itself proceeds, so that the pores of the activated carbon itself are crushed and the It can be seen that the surface area decreases and the capacitance decreases.
[0033]
Therefore, if the amount of PVB is 30 to 200 parts by weight, the aging temperature is 150 to 300 ° C., and the heat treatment temperature is 600 to 1200 ° C., the bulk density of the obtained solid activated carbon is 0.5 g / cm 3 or more, It can be seen that the three-point bending strength can be increased to 300 gf / mm 2 or more and the specific surface area can be increased to 500 m 2 / g or more.
[0034]
[Table 1]
Example 2
Activated carbon powder (coconut ash, BET value: 2000 m 2 / g), PVB, and mesophase carbon were mixed at a ratio shown in Tables 2 to 8, and stirred with a high-speed mixing stirrer. This powder was passed through a 40 mesh to obtain a molding powder.
[0036]
The specific surface area of activated carbon powder may be determined according to a final capacitance, but are not limited, to use the electrode for an electric double layer capacitor is 1500m 2 / g~2500m 2 / g Is desirable. The PVB may be any commercially available PVB, but if the degree of polymerization exceeds 1500, the moldability during dry molding deteriorates. Therefore, the degree of polymerization is preferably 1500 or less.
[0037]
The obtained powder was subjected to dry press molding or dry roll molding to obtain a molded body of 70 × 50 × 1 (mm). The molding temperature at this time was from room temperature to 60 ° C. The reason why the molding temperature is limited here is that if the temperature exceeds 60 ° C., the molded article is strongly attached to a mold or a roll and continuous molding cannot be performed. The obtained molded body is subjected to aging treatment in the atmosphere at the temperature shown in Tables 2 to 48 for 48 hours, and then heat-treated in vacuum at the temperature shown in Tables 2 to 8 to carbonize PVB and mesophase carbon. An activated carbon substrate, which is a composite of activated carbon and carbon, was prepared.
[0038]
The capacitance when the obtained solid activated carbon substrate was used as the
[0039]
From these results, it was found that the strength was further improved when PVB was added to the activated carbon powder in a range of 30 to 200 parts by weight and mesophase-based carbon was added in a range of 100 parts by weight or less. By adjusting the amount of mesophase carbon according to the required capacitance and strength, solid activated carbon having various characteristics can be obtained.
[0040]
Further, as in Example 1, the amount of PVB is outside the range of 30 to 200 parts by weight, the aging temperature is outside the range of 150 to 300 ° C, and the heat treatment temperature is outside the range of 600 to 1200 ° C ( Nos. 1 to 108 in Tables 2 to 6) have a bulk density of 0.5 g / cm 3 or more, a three-point bending strength of 300 gf / mm 2 or more, and a specific surface area of 500 m 2 / g or more. (Nos. 109 to 141 in Tables 7 and 8) show that one of the characteristics is low.
[0041]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
[Table 6]
[Table 7]
[Table 8]
【The invention's effect】
As described above, according to the present invention, if necessary, a mesophase-based carbon is added to a mixture of activated carbon powder and / or activated carbon fiber and PVB, an aging treatment is performed in the air, and a heat treatment is performed in a non-oxidizing atmosphere. However, by forming the solid activated carbon by carbonizing the PVB and the mesophase-based carbon, even if the ratio of the activated carbon component is increased, the solid activated carbon can be suitably produced, and the solid activated carbon having a high specific surface area and high strength can be obtained at a high yield. As a result, the mechanical strength of the adsorbent can be improved, and the adsorbing ability can be further improved.
[0049]
In particular, when an electric double layer capacitor is formed by using the solid activated carbon as an electrode, the capacitance can be increased.
[Brief description of the drawings]
FIG. 1 is a schematic view showing a general electric double layer capacitor.
[Explanation of symbols]
1: Electrode 2: electrolyte
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33967796A JP3559408B2 (en) | 1996-12-19 | 1996-12-19 | SOLID ACTIVE CARBON, PROCESS FOR PRODUCING THE SAME, AND ELECTRIC DOUBLE LAYER CAPACITOR USING THE SAME |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33967796A JP3559408B2 (en) | 1996-12-19 | 1996-12-19 | SOLID ACTIVE CARBON, PROCESS FOR PRODUCING THE SAME, AND ELECTRIC DOUBLE LAYER CAPACITOR USING THE SAME |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10182119A JPH10182119A (en) | 1998-07-07 |
| JP3559408B2 true JP3559408B2 (en) | 2004-09-02 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33967796A Expired - Fee Related JP3559408B2 (en) | 1996-12-19 | 1996-12-19 | SOLID ACTIVE CARBON, PROCESS FOR PRODUCING THE SAME, AND ELECTRIC DOUBLE LAYER CAPACITOR USING THE SAME |
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| Country | Link |
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| JP (1) | JP3559408B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3904755B2 (en) * | 1998-09-29 | 2007-04-11 | 京セラ株式会社 | Activated carbon and electric double layer capacitor using the same |
| KR20030093418A (en) * | 2002-06-03 | 2003-12-11 | 이형식 | Carbon x filter |
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| JPH10182119A (en) | 1998-07-07 |
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