JP2002299185A - Method of manufacturing activated carbon cloth, activated carbon cloth and electric double-layer capacitor using the same - Google Patents
Method of manufacturing activated carbon cloth, activated carbon cloth and electric double-layer capacitor using the sameInfo
- Publication number
- JP2002299185A JP2002299185A JP2001105764A JP2001105764A JP2002299185A JP 2002299185 A JP2002299185 A JP 2002299185A JP 2001105764 A JP2001105764 A JP 2001105764A JP 2001105764 A JP2001105764 A JP 2001105764A JP 2002299185 A JP2002299185 A JP 2002299185A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- cloth
- carbon cloth
- cellulosic
- temperature
- 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.)
- Withdrawn
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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、活性炭布の製造方
法、活性炭布及びそれを用いた電気二重層キャパシタに
関する。The present invention relates to a method for producing an activated carbon cloth, an activated carbon cloth, and an electric double layer capacitor using the same.
【０００２】[0002]
【従来の技術】近年、バックアップ電源、補助電源とし
て電気二重層キャパシタが注目を集めており、活性炭の
電気二重層キャパシタの電極としての性能に着目した開
発が広くなされている。活性炭を分極性電極として使用
した電気二重層キャパシタは静電容量に優れるため、エ
レクトロニクス分野の発展と共に、需要も急成長してい
る。また、最近では、従来のメモリーバックアップ電源
等の小型化に加え、モーター等の補助電源に使われるよ
うな大容量製品の開発も行われている。2. Description of the Related Art In recent years, electric double layer capacitors have attracted attention as a backup power supply and an auxiliary power supply, and the development of activated carbon as an electrode of the electric double layer capacitor has been widely performed. An electric double layer capacitor using activated carbon as a polarizable electrode has excellent capacitance, and the demand is rapidly growing with the development of the electronics field. Recently, in addition to miniaturization of conventional memory backup power supplies and the like, large-capacity products used for auxiliary power supplies such as motors have been developed.
【０００３】電気二重層キャパシタの原理は古くから知
られていたが、実際にデバイスとして使用され始めたの
は近年に至ってからである。電気二重層キャパシタの静
電容量は、電気二重層が形成される分極性電極の表面
積、単位面積当たりの電気二重層容量や電極の抵抗等に
よって主に支配されている。実用面では、単位体積当た
りの静電容量を高くし、電気二重層キャパシタの体積を
小さくするために、電極自体の密度を高めることも重要
である。[0003] Although the principle of the electric double layer capacitor has been known for a long time, it has only recently been started to use it as a device. The capacitance of the electric double layer capacitor is mainly controlled by the surface area of the polarizable electrode on which the electric double layer is formed, the electric double layer capacitance per unit area, the resistance of the electrode, and the like. In practical terms, it is also important to increase the density of the electrodes themselves in order to increase the capacitance per unit volume and reduce the volume of the electric double layer capacitor.
【０００４】従来、電気二重層キャパシタ向け活性炭と
しては、（１）樹脂材料、椰子殻、ピッチ及び石炭など
を水蒸気、ガスなどの酸性条件下で賦活した活性炭（大
容量キャパシタ技術と材料、シーエムシー社刊行（１９
９８） 参照）、（２）フェノール繊維布、ピッチ繊維
布を炭化賦活した活性炭繊維布（特開昭６４−８２５１
４号公報）、（３）フェノール樹脂発泡体を炭化、賦活
することにより得られる活性炭成形体（特開平２−２９
７９１５号公報）、（４）セルロース系活性炭素繊維
（特開昭５８−２０６１１６号公報）などが知られてい
る。Conventionally, as activated carbon for electric double layer capacitors, (1) activated carbon obtained by activating resin material, coconut shell, pitch, coal, etc. under acidic conditions such as steam and gas (large capacity capacitor technology and materials, CMC Published by the company (19
98)), (2) Activated carbon fiber cloth obtained by carbonizing phenol fiber cloth and pitch fiber cloth (Japanese Patent Application Laid-Open No. 64-8251).
No. 4) and (3) an activated carbon molded product obtained by carbonizing and activating a phenolic resin foam (JP-A-2-29)
No. 7915) and (4) Cellulosic activated carbon fiber (Japanese Patent Application Laid-Open No. 58-206116).
【０００５】[0005]
【発明が解決しようとする課題】前述したように、キャ
パシタ用の電極としては、高い静電容量且つ低抵抗が要
望されている。しかしながら、（１）の方法で得られた
活性炭を使用した場合、近年の技術革新により高い静電
容量を示すものも得られてきているが、粉末状の活性炭
をテフロン（登録商標）系のバインダーで成型するた
め、必然的に抵抗が高くなる。また、（２）のフェノー
ル繊維布、ピッチ繊維布を炭化賦活した活性炭繊維布で
は、他の汎用の活性炭に比べて高価であること、現在の
炭化・賦活技術では厚み・目付（ｇ／ｍ2）のバラツキ
が比較的大きいことなどが欠点である。As described above, high capacitance and low resistance are required for electrodes for capacitors. However, in the case where the activated carbon obtained by the method (1) is used, one having a high capacitance has been obtained due to recent technical innovation. However, powdered activated carbon is converted to a Teflon (registered trademark) -based binder. Because of the molding, the resistance necessarily increases. Further, phenol fiber cloth (2), the pitch fiber cloth activated carbon fiber cloth carbonized activated, it is expensive compared to other general-purpose activated carbon, Thickness in the current carbonization and activation technology basis weight (g / m 2 The disadvantage is that the variation in ()) is relatively large.
【０００６】さらに、（３）の方法では、比表面積を上
げることが困難であり、そして、（４）の方法では、熱
処理に１５００℃と非常に高温を要し、しかも、水蒸気
等により賦活を試みると、収率が低く、その上、布の収
縮による亀裂、しわが発生し、大面積のものを得ること
ができない。セルロース系活性炭素繊維に関しては、特
開２００１−４０５４８号公報に、炭酸マグネシウムを
５重量％以上含んだ炭酸カルシウムとともに焼成する方
法も開示されているが、この方法でも、昇温速度１０℃
／ｈｒ以下で１週間以上の時間をかけて８００℃以上に
焼成するなど、現実的な速度で生産できない問題点があ
る。In the method (3), it is difficult to increase the specific surface area. In the method (4), the heat treatment requires a very high temperature of 1500 ° C., and the activation is activated by steam or the like. If attempted, the yield is low, and furthermore, cracks and wrinkles are generated due to shrinkage of the cloth, and a large area cannot be obtained. Regarding the cellulosic activated carbon fiber, Japanese Patent Application Laid-Open No. 2001-40548 also discloses a method of firing with calcium carbonate containing 5% by weight or more of magnesium carbonate.
However, there is a problem that the production cannot be performed at a realistic speed, such as firing at 800 ° C. or more at a rate of not more than / hr over one week or more.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、比表面積
及び静電容量に優れ、しかも安価に製造することのでき
る活性炭布を製造する方法について検討し、一旦真空下
で熱処理して得たセルロース系布を賦活処理することに
よって、目的とする活性炭布を得ることができることを
見出し、本発明に至った。すなわち本発明は、真空下、
５００℃以上１４００℃以下の温度にて加熱処理したセ
ルロース系布を賦活処理することを特徴とするセルロー
ス系活性炭布の製造方法である。Means for Solving the Problems The present inventors have studied a method for producing an activated carbon cloth which is excellent in specific surface area and capacitance, and which can be produced at low cost. It has been found that a desired activated carbon cloth can be obtained by activating the cellulose-based cloth thus obtained, and the present invention has been achieved. That is, the present invention, under vacuum,
A method for producing a cellulosic activated carbon cloth, comprising activating a cellulosic cloth heat-treated at a temperature of 500 ° C. or more and 1400 ° C. or less.
【０００８】本発明のもう一つの発明はこの製造方法に
より得られた活性炭布である。また、本発明の別の発明
は、この製造方法により得られた活性炭布を使用した電
気二重層キャパシタ用電極材である。[0008] Another aspect of the present invention is an activated carbon cloth obtained by this production method. Another aspect of the present invention is an electrode material for an electric double layer capacitor using the activated carbon cloth obtained by this manufacturing method.
【０００９】[0009]
【発明の実施の形態】本発明で使用するセルロース系布
としては、木綿、麻等の天然セルロース繊維、ビスコー
スレーヨン、銅アンモニアレーヨン、溶剤紡糸レーヨ
ン、トリアセテート繊維などの人造セルロース繊維から
なる布をあげることができる。なかでも、木綿は入手が
容易で、織りやすく、炭化したときの強度にも優れてい
る点で好ましいセルロース系布である。セルロース系布
には、平織り、綾織り、繻子織り等種々の織り方による
布があるが、強度的な点及び面内の均一性の点で平織り
布が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION As the cellulosic cloth used in the present invention, a cloth made of artificial cellulosic fibers such as cotton, hemp and the like, viscose rayon, cuprammonium rayon, solvent spun rayon, triacetate fiber and the like is used. I can give it. Among them, cotton is a preferred cellulosic cloth because it is easily available, easy to weave, and has excellent strength when carbonized. As the cellulosic cloth, there are cloths of various weaves such as plain weave, twill weave and satin weave, but plain weave cloth is preferable in terms of strength and in-plane uniformity.
【００１０】本発明では、先ずセルロース系布に真空下
加熱処理を行なう。これによって、原料布が炭化、一部
賦活され、炭素繊維にミクロンオーダーのミクロポアが
形成されると共に、引っ張り強度に優れ、摩擦強度の高
い布を得ることができる。In the present invention, first, the cellulose-based cloth is subjected to a heat treatment under vacuum. As a result, the raw material cloth is carbonized and partially activated, micropores on the order of microns are formed in the carbon fibers, and a cloth having excellent tensile strength and high friction strength can be obtained.
【００１１】本発明における真空下とは、大気圧より低
い気圧であり、通常は５００Ｔｏｒｒ以下である。３０
０Ｔｏｒｒ以下、より好ましくは１００Ｔｏｒｒ以下で
実施すると、セルロース系布の燃焼を抑制することがで
き、また、繊維より揮発するタール分の蒸発除去を容易
にすることができるので好ましい。In the present invention, the term "under vacuum" refers to a pressure lower than the atmospheric pressure, and is usually 500 Torr or less. 30
It is preferable to carry out the process at 0 Torr or less, more preferably at 100 Torr or less, because it is possible to suppress the burning of the cellulosic fabric and to facilitate the evaporation and removal of tar components volatilized from the fibers.
【００１２】本発明における加熱温度としては、あまり
低いと、目的とする炭化反応が不十分であり、その結
果、その後の賦活処理に熱的に耐え得る炭化物を得るこ
とが困難であり、一方、あまり高いと、副反応である熱
分解反応の進行度合いが大きくなり、その結果、炭化
物、さらには最終的に得られる活性炭の収率が低くなる
ことがあるので、５００℃以上１４００℃以下、生成す
る炭化繊維の強度を考慮すると、５００℃以上１０００
℃以下で実施するのが好ましい。If the heating temperature in the present invention is too low, the desired carbonization reaction is insufficient, and as a result, it is difficult to obtain a carbide that can thermally withstand the subsequent activation treatment. If the temperature is too high, the degree of progress of the thermal decomposition reaction, which is a side reaction, increases, and as a result, the yield of carbides, and finally the activated carbon finally obtained, may decrease. Considering the strength of the carbonized fiber to be
It is preferably carried out at a temperature of not more than ° C.
【００１３】加熱処理における昇温速度は特に制限され
ないが、急激な温度上昇によって繊維の急激な収縮が起
こる恐れがあること、それに伴う繊維布の歪みが生ずる
ことを考慮し、毎分０．０１℃以上１００℃以下で実施
するのが好ましい。さらに、経済性、操作性を考慮し
て、毎分０．１℃以上５０℃以下の昇温速度で実施する
のが好ましい。最高到達時の保持時間も特に制限される
ものではないが、通常１分以上１０時間以下、好ましく
は５分以上５時間以下で実施するのが好ましい。The rate of temperature rise in the heat treatment is not particularly limited. However, considering that there is a possibility that a sudden rise in temperature may cause sudden shrinkage of the fiber and a resulting distortion of the fiber cloth, the rate of heating may be reduced to 0.01 mm / min. It is preferable to carry out at a temperature of not less than 100 ° C and not more than 100 ° C. Further, in consideration of economy and operability, it is preferable to perform the heating at a rate of 0.1 ° C. or more and 50 ° C. or less per minute. Although the holding time at the time of reaching the maximum is not particularly limited, it is usually performed for 1 minute to 10 hours, preferably 5 minutes to 5 hours.
【００１４】本発明では、以上の加熱処理に続いて賦活
処理を行なう必要がある。賦活処理工程へ移行するに
は、先の真空下加熱工程から、一旦冷却した後、賦活処
理に移行しても、連続的に移行しても構わない。賦活処
理の雰囲気は、酸化性ガス雰囲気とするのが好ましい。
使用する酸化性ガスとしては、水蒸気、二酸化炭素及び
それらの混合ガス、燃焼ガスなどを使用することがで
き、これらの成分比率は特に限定されるものではない。In the present invention, it is necessary to perform an activation treatment subsequent to the above-mentioned heat treatment. In order to shift to the activation treatment step, the cooling step may be performed once after cooling from the previous heating step under vacuum, or may be successively shifted to the activation treatment step. The atmosphere for the activation treatment is preferably an oxidizing gas atmosphere.
As the oxidizing gas to be used, steam, carbon dioxide, a mixed gas thereof, a combustion gas and the like can be used, and the ratio of these components is not particularly limited.
【００１５】賦活温度は特に制限されるものではなく、
これによって、比表面積を制御することができる。通常
は、６００℃以上１５００℃以下、得られるセルロース
系活性炭布の炭素収率、強度を考慮して、８００℃以上
１２００℃以下の範囲で実施するのが好ましい。The activation temperature is not particularly limited.
Thereby, the specific surface area can be controlled. Usually, it is preferably carried out in the range of 800 ° C. to 1200 ° C. in consideration of the carbon yield and strength of the obtained cellulose-based activated carbon cloth.
【００１６】賦活温度に達するまでの昇温速度として
は、特に制限されるものではない。しかし、急激な昇温
は、繊維布の収縮に伴う歪み等を起こすため、通常毎分
０．０１℃から５０℃の範囲、より好ましくは毎分０．
１℃から３０℃の範囲で実施される。The rate of temperature rise up to the activation temperature is not particularly limited. However, a sudden rise in temperature causes distortion or the like due to shrinkage of the fiber cloth, so that it is usually in the range of 0.01 ° C. to 50 ° C. per minute, more preferably 0.1 ° C. per minute.
It is performed in the range of 1 ° C to 30 ° C.
【００１７】賦活時の酸化性ガスの流速（線速度）とし
ては、使用する反応設備によって異なることは言うまで
もないが、通常毎秒０．００１ｍから２００ｍの範囲、
経済性、熱伝達を考慮して、毎秒０．０１ｍから１００
ｍの範囲とするのが好ましい。It goes without saying that the flow rate (linear velocity) of the oxidizing gas at the time of activation differs depending on the reaction equipment used, but it is usually in the range of 0.001 m to 200 m per second.
Considering economy and heat transfer, 0.01m to 100m per second
It is preferred to be within the range of m.
【００１８】賦活温度から降温するときの降温速度も特
に制限されるものではなく、放冷することも、強制的に
冷却することも可能である。バッチ式において、冷却す
る場合には、通常毎分０．０１℃から１００℃の範囲、
より好ましくは、０．１℃から５０℃の範囲で冷却さ
れ、連続の場合もほぼ同様の温度で冷却する。冷却時に
は、賦活ガス雰囲気下でも、窒素、アルゴンなどの不活
性雰囲気下でも行なうことができるが、安全性を考慮し
て、また、得られる活性炭布の酸化を抑制するために、
不活性ガス雰囲気下で実施することが好ましい。The rate of temperature decrease when the temperature is lowered from the activation temperature is not particularly limited, and it is possible to allow cooling or forced cooling. In the batch method, when cooling, usually in the range of 0.01 ° C to 100 ° C per minute,
More preferably, it is cooled in the range of 0.1 ° C. to 50 ° C., and in the case of continuous cooling at substantially the same temperature. At the time of cooling, it can be performed under an activation gas atmosphere or under an inert atmosphere such as nitrogen or argon, but in consideration of safety, and in order to suppress oxidation of the obtained activated carbon cloth,
It is preferable to carry out under an inert gas atmosphere.
【００１９】本発明により得られたセルロース系活性炭
布をキャパシタの電極として使用するには、活性炭布を
そのまま使用すればよいが、活性炭布と集電極を張り合
わせて使用してもよい。In order to use the cellulosic activated carbon cloth obtained according to the present invention as an electrode of a capacitor, the activated carbon cloth may be used as it is, but the activated carbon cloth and the collecting electrode may be bonded together.
【００２０】キャパシタに使用される集電極としては、
キャパシタの溶媒にプロピレンカーボネート等の有機極
性溶媒を使用する場合はアルミ箔が適しており、硫酸等
の水系の溶媒の場合には黒鉛粉末の成形シートを使用す
るのが適している。本発明の活性炭布とアルミ箔等の集
電極を貼り合わせるには、活性炭布の熱ローラープレス
工程において同時に加工することもできるし、熱硬化性
樹脂にグラファイトなどの導電材を練りこんだ導電性ペ
ーストを介して熱接着することも出来る。The collector electrodes used for the capacitors include:
When an organic polar solvent such as propylene carbonate is used as the solvent for the capacitor, an aluminum foil is suitable. When an aqueous solvent such as sulfuric acid is used, a molded sheet of graphite powder is suitable. To bond the activated carbon cloth of the present invention to a collector electrode such as an aluminum foil, the activated carbon cloth can be simultaneously processed in a hot roller pressing step, or a conductive material obtained by kneading a conductive material such as graphite into a thermosetting resin. Heat bonding can also be performed via a paste.
【００２１】本発明で使用される電解液としては、水
系、非水系有機溶媒系のいずれも使用することが出来
る。非水系有機溶媒系電解液における溶媒としては非プ
ロトン性でかつ高誘導電率のものが用いられる。例え
ば、プロピレンカーボネート、γ−ブチロラクトン、ジ
メチルスルホキシド、ジメチルホルムアミド、アセトニ
トリル、エチレンカーボネート、テトラヒドロフラン、
ジメトキシエタン等である。これらの非水系有機溶媒系
は一種又は二種以上を混合して用いることも出来る。As the electrolytic solution used in the present invention, any of an aqueous system and a non-aqueous organic solvent system can be used. As a solvent in the non-aqueous organic solvent-based electrolyte, an aprotic solvent having a high induced electric power is used. For example, propylene carbonate, γ-butyrolactone, dimethyl sulfoxide, dimethylformamide, acetonitrile, ethylene carbonate, tetrahydrofuran,
Dimethoxyethane and the like. These non-aqueous organic solvent systems may be used alone or in combination of two or more.
【００２２】これらの非水系有機溶媒系において、電解
質としては陽イオンと陰イオンの塩が使用される。ここ
で用いられる陰イオンとしては、例えば、過塩素酸イオ
ン、４フッカ化ホウ素イオン、６フッカ化リンイオン、
６フッカ化ヒ素イオン等である。陽イオンとしては、リ
チウムイオン、ナトリウムイオンなどの金属イオン、テ
トラメチルアンモニウム、テトラエチルアンモニウム、
トリメチルエチルアンモニウム、トリエチルメチルアン
モニウム、ジエチルジメチルアンモニウム、Ｎ，Ｎ−ジ
メチルピロリジニウム、Ｎ，Ｎ−ジエチルピロリジニウ
ム、 Ｎ，Ｎ−ジメチルピペリジニウム、 Ｎ，Ｎ−ジエ
チルピペリジニウムなどの第４級アンモニウムなどを使
用することができる。また、本発明において使用される
水系の電解液としては塩化ナトリウム水溶液、水酸化ナ
トリウム水溶液、水酸化カリウム水溶液、塩酸、硫酸水
溶液 等を使用することが出来る。In these non-aqueous organic solvent systems, salts of cations and anions are used as the electrolyte. Examples of the anion used here include a perchlorate ion, a boron tetrafluoride ion, a phosphorus hexafluoride ion,
Arsenic hexafluoride ion and the like. As the cation, lithium ion, metal ion such as sodium ion, tetramethylammonium, tetraethylammonium,
Trimethylethylammonium, triethylmethylammonium, diethyldimethylammonium, N, N-dimethylpyrrolidinium, N, N-diethylpyrrolidinium, N, N-dimethylpiperidinium, N, N-diethylpiperidinium, etc. Quaternary ammonium and the like can be used. Further, as the aqueous electrolyte used in the present invention, an aqueous solution of sodium chloride, an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of hydrochloric acid, an aqueous solution of sulfuric acid and the like can be used.
【００２３】電解液中の電解質の濃度は特に限定しない
が、有機非水系極性溶媒の場合には０．５〜３Ｍ／Ｌ
（モル／リットル）が好ましく、１〜２ Ｍ／Ｌとする
のがより好ましい。水系電解液の場合には電解質の濃度
は２０％〜４０％にするのがよい。The concentration of the electrolyte in the electrolyte is not particularly limited, but in the case of an organic non-aqueous polar solvent, it is 0.5 to 3 M / L.
(Mol / liter), more preferably 1-2 M / L. In the case of an aqueous electrolyte, the concentration of the electrolyte is preferably 20% to 40%.
【００２４】本発明のセルロース系布を電極としたキャ
パシタの概略図を図１に示す。１及び２は集電極、３及
び４は活性炭布からなる分極性電極、５はポリプロピレ
ン不織布などから構成されるセパレーター、６はステン
レスなどの素材で構成される蓋である。なお、本発明に
おいて、静電容量は次の方法により測定した。FIG. 1 is a schematic view of a capacitor using the cellulosic cloth of the present invention as an electrode. Reference numerals 1 and 2 denote collector electrodes, reference numerals 3 and 4 denote polarizable electrodes made of activated carbon cloth, reference numeral 5 denotes a separator composed of a polypropylene nonwoven fabric, and reference numeral 6 denotes a lid composed of a material such as stainless steel. In the present invention, the capacitance was measured by the following method.
【００２５】静電容量の測定：到達電圧２．５Vまで、
電極の単位表面積（ｃｍ2）あたり、３ｍAで低電流充電
し、２．５Ｖで３０分低電圧下補充電する。補充電完了
後、３ｍＡ／ ｃｍ2で放電する。その時１．２Ｖから
１．０Ｖまでの放電傾きから静電容量を求めた。以下、
実施例により本発明を具体的に説明するが、本発明はこ
れに限定されるものではない。Measurement of capacitance: up to 2.5 V
Low current charging is performed at 3 mA per unit surface area (cm 2 ) of the electrode, and supplementary charging is performed at 2.5 V for 30 minutes under low voltage. After completion of the supplementary charge, the battery is discharged at 3 mA / cm 2 . At that time, the capacitance was determined from the discharge gradient from 1.2 V to 1.0 V. Less than,
EXAMPLES The present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
【００２６】[0026]
【実施例】参考例１：真空熱処理による炭化布の調整 原料布として、厚さ０．５ｍｍの市販の平織り木綿布
（糸は２本撚りしたもので、太さは約１５μｍ）を用
い、これを２００ｍｍ角に裁断した後、ステンレス製
（ＳＵＳ３１０Ｓ）の金網に挟んで固定した後、炭化炉
に入れ、炭化炉内を１０Ｔ０ｒｒに減圧した。減圧後、
炉内温度８５０℃まで、毎分３℃で昇温し、８５０℃到
達後、１時間保持した。１時間後、毎分５℃で冷却し、
５０℃まで冷却したところで、窒素を導入して、得られ
た炭化布を取り出した。原料布に対する炭化布の重量収
率は４５重量％であった。Reference Example 1: Preparation of carbonized cloth by vacuum heat treatment As a raw material cloth, a commercially available plain-woven cotton cloth (thickness of about 15 μm with a twist of two yarns) having a thickness of 0.5 mm was used. Was cut into a 200 mm square, and fixed by being sandwiched between stainless steel (SUS310S) wire meshes, and then placed in a carbonization furnace, and the pressure in the carbonization furnace was reduced to 10 T0 rr. After decompression,
The temperature was raised at a rate of 3 ° C. per minute to a furnace temperature of 850 ° C., and after the temperature reached 850 ° C., the temperature was maintained for 1 hour. After 1 hour, cool at 5 ° C per minute,
After cooling to 50 ° C., nitrogen was introduced to take out the obtained carbonized cloth. The weight yield of the carbonized cloth relative to the raw cloth was 45% by weight.
【００２７】実施例１ 参考例１で得られた炭化布１０ｇをＬＰＧ燃焼賦活炉に
入れ、毎分５０℃で昇温し、ＬＰＧ燃焼ガス毎分１ｍの
流速下、９３０℃にて１５分間賦活処理を行なった。賦
活終了後、活性炭布を速やかに窒素気流下に移し、冷却
した。賦活布の炭化布に対する繊維長収縮率は１８％で
あり、収縮斑、皺等は見られなかった。得られた活性炭
布の炭化布からの重量収率、窒素吸着量で測定したＢＥ
Ｔ比表面積を表１に示す。賦活布には収縮斑、皺は認め
られなかった。Example 1 10 g of the carbonized cloth obtained in Reference Example 1 was placed in an LPG combustion activation furnace, heated at 50 ° C./min, and activated at 930 ° C. for 15 minutes at a flow rate of 1 m / min of LPG combustion gas. Processing was performed. After the activation was completed, the activated carbon cloth was quickly moved under a nitrogen stream and cooled. The fiber length shrinkage ratio of the activated cloth to the carbonized cloth was 18%, and no shrinkage spots, wrinkles, etc. were observed. BE obtained by measuring the weight yield of the obtained activated carbon cloth from the carbonized cloth and the nitrogen adsorption amount
Table 1 shows the T specific surface area. No spots or wrinkles were observed on the activated cloth.
【００２８】得られた活性布を、打ち抜き器を用いて直
径２ｃｍの円形に成形した。次いで、１５０℃、減圧下
４時間乾燥してシート状の電極を作製した。これを、露
点−８０℃以下のグローブボックス中で、図１に示すよ
うに、ステンレス蓋に、集電極、分極性電極、ポリプロ
ピレン不織布、分極性電極、及び集電極を積層した後、
１Ｍのテトラエチルアンモニウムテトラフルオロボレー
トを含有するプロピレンカーボネート溶液を分極性電極
に含浸せしめ、ポリプロピレン製の絶縁ガスケットを用
いて、ステンレス上蓋にかしめ封印した。The obtained activated cloth was formed into a circular shape having a diameter of 2 cm using a punching machine. Next, it was dried at 150 ° C. under reduced pressure for 4 hours to produce a sheet-like electrode. In a glove box having a dew point of −80 ° C. or less, as shown in FIG. 1, after stacking a collecting electrode, a polarizable electrode, a polypropylene nonwoven fabric, a polarizable electrode, and a collecting electrode on a stainless steel lid,
A polarizable electrode was impregnated with a propylene carbonate solution containing 1 M tetraethylammonium tetrafluoroborate, and was caulked and sealed on a stainless steel upper lid using an insulating gasket made of polypropylene.
【００２９】日置電機製電気二重層キャパシタ評価装置
を使用して、室温下、２．５Vまでの定電流、充放電サ
イクルテスト１０回を行い、静電容量及び内部抵抗を測
定した。放電カーブより定法にて求めた静電容量の平均
値は、２２Ｆ／ＣＣであった。静電容量及び内部抵抗の
結果を表１に併せて示す。Using a Hioki Electric Double Layer Capacitor Evaluation Apparatus, a constant current up to 2.5 V and 10 charge / discharge cycle tests were performed at room temperature to measure the capacitance and the internal resistance. The average value of the capacitance obtained from the discharge curve by an ordinary method was 22 F / CC. The results of the capacitance and the internal resistance are also shown in Table 1.
【００３０】実施例２ 実施例１において、賦活時間を２０分とした以外は、実
施例１と同様に行った。結果を表１に示す。賦活布には
収縮斑、皺は認められなかった。Example 2 Example 2 was carried out in the same manner as in Example 1, except that the activation time was changed to 20 minutes. Table 1 shows the results. No spots or wrinkles were observed on the activated cloth.
【００３１】実施例３ 実施例１において、賦活時間を３０分とした以外は、実
施例１と同様に行った。結果を表１に示す。賦活布には
収縮斑、皺は認められなかった。Example 3 Example 3 was carried out in the same manner as in Example 1, except that the activation time was changed to 30 minutes. Table 1 shows the results. No spots or wrinkles were observed on the activated cloth.
【００３２】比較例１ 参考例１で使用した市販の平織り綿布１０ｇを、真空下
での加熱処理をすることなく直接ＬＰＧ燃焼賦活炉に入
れ、毎分５０℃で昇温し、ＬＰＧ燃焼ガス毎分１ｍの流
速下、９３０℃にて１５分間賦活処理を行なった。賦活
終了後、活性炭布を速やかに窒素気流下に移し、冷却し
た。賦活布の炭化布に対する重量収率は１０重量％であ
った。また、繊維長収縮率は６０％であり、収縮斑、皺
が激しく、その後のキャパシタ性能評価に供することが
できなかった。Comparative Example 1 10 g of the commercially available plain woven cotton cloth used in Reference Example 1 was directly put into an LPG combustion activation furnace without performing heat treatment under vacuum, and the temperature was raised at 50 ° C. per minute to obtain a LPG combustion gas. The activation treatment was carried out at 930 ° C. for 15 minutes under a flow rate of 1 m. After the activation was completed, the activated carbon cloth was quickly moved under a nitrogen stream and cooled. The weight yield of the activated cloth to the carbonized cloth was 10% by weight. Further, the fiber length shrinkage was 60%, and the shrinkage spots and wrinkles were severe, so that it was not possible to use for subsequent capacitor performance evaluation.
【００３３】参考例２：真空熱処理による炭化布の調整 真空下での熱処理温度を１８００℃とした以外は、参考
例１と同様に炭化布を作製した。原料布に対する炭化布
の重量収率は３０重量％であった。Reference Example 2: Preparation of carbonized cloth by vacuum heat treatment A carbonized cloth was produced in the same manner as in Reference Example 1, except that the heat treatment temperature under vacuum was 1800 ° C. The weight yield of the carbonized cloth relative to the raw cloth was 30% by weight.
【００３４】比較例２ 参考例２で得られた炭化布を使用した以外は実施例１と
同様に炭化布を作製した。結果を表１に示す。賦活布に
は収縮斑、皺は認められなかった。Comparative Example 2 A carbonized cloth was produced in the same manner as in Example 1 except that the carbonized cloth obtained in Reference Example 2 was used. Table 1 shows the results. No spots or wrinkles were observed on the activated cloth.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【発明の効果】本発明により、安価なセルロース系布を
使用して、工業的規模でセルロース系活性炭布を製造す
ることができる。本発明によって得られたセルロース系
活性炭布は、比表面積及び静電容量に優れているので、
電気二重層キャパシタ用分極性電極として有用である。According to the present invention, a cellulose-based activated carbon cloth can be produced on an industrial scale using an inexpensive cellulose-based cloth. Since the cellulose-based activated carbon cloth obtained by the present invention is excellent in specific surface area and capacitance,
It is useful as a polarizable electrode for an electric double layer capacitor.
【図１】本発明の活性炭布をキャパシタの電極に適用し
た一例を示す概略図である。FIG. 1 is a schematic view showing an example in which the activated carbon cloth of the present invention is applied to an electrode of a capacitor.
１ 集電極 ２ 集電極 ３ 分極性電極 ４ 分極性電極 ５ セパレーター ６ 蓋 DESCRIPTION OF SYMBOLS 1 Collector electrode 2 Collector electrode 3 Polarized electrode 4 Polarized electrode 5 Separator 6 Lid
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岩崎 秀治 岡山県倉敷市酒津2045番地の１ 株式会社 クラレ内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hideharu Iwasaki 2045 Sakura, Kurashiki City, Okayama Prefecture 1 Kuraray Co., Ltd.
Claims (9)
温度にて加熱処理したセルロース系布を賦活処理するこ
とを特徴とするセルロース系活性炭布の製造方法。1. A method for producing a cellulosic activated carbon cloth, comprising activating a cellulosic cloth heat-treated at a temperature of 500 ° C. or more and 1400 ° C. or less under vacuum.
０℃以下である請求項１記載のセルロース系活性炭布の
製造方法。2. The activation treatment is performed at a temperature of 600 ° C. or higher and 150
The method for producing a cellulosic activated carbon cloth according to claim 1, wherein the temperature is 0C or lower.
求項１又は請求項２に記載のセルロース系活性炭布の製
造方法。3. The method for producing a cellulosic activated carbon cloth according to claim 1, wherein the degree of vacuum is not more than 500 Torr.
気である請求項１〜３いずれかに記載のセルロース系活
性炭布の製造方法。4. The method for producing a cellulosic activated carbon cloth according to claim 1, wherein the atmosphere of the activation treatment is an atmosphere of an oxidizing gas.
以上２２００ｍ2／ｇ以下である請求項１〜４いずれか
に記載のセルロース系活性炭布の製造方法。5. The activated carbon cloth has a specific surface area of 800 m 2 / g.
The method for producing a cellulose-based activated carbon cloth according to any one or more 2200 m 2 / g or less claims 1-4.
〜５いずれかに記載のセルロース系活性炭布の製造方
法。6. The cellulosic cloth is cotton.
A method for producing a cellulosic activated carbon cloth according to any one of claims 1 to 5.
セルロース系活性炭布の製造方法。7. The method for producing a cellulosic activated carbon cloth according to claim 7, wherein said cotton is a plain woven cloth.
得られた活性炭布。8. An activated carbon cloth obtained by the method according to claim 1.
得られた活性炭布を使用した電気二重層キャパシタ用電
極材。9. An electrode material for an electric double layer capacitor using an activated carbon cloth obtained by the method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001105764A JP2002299185A (en) | 2001-04-04 | 2001-04-04 | Method of manufacturing activated carbon cloth, activated carbon cloth and electric double-layer capacitor using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001105764A JP2002299185A (en) | 2001-04-04 | 2001-04-04 | Method of manufacturing activated carbon cloth, activated carbon cloth and electric double-layer capacitor using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002299185A true JP2002299185A (en) | 2002-10-11 |
Family
ID=18958395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001105764A Withdrawn JP2002299185A (en) | 2001-04-04 | 2001-04-04 | Method of manufacturing activated carbon cloth, activated carbon cloth and electric double-layer capacitor using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002299185A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012114154A (en) * | 2010-11-22 | 2012-06-14 | Institute Of National Colleges Of Technology Japan | Method of manufacturing electrode for electric double layer capacitor |
| JP2013048213A (en) * | 2011-07-26 | 2013-03-07 | Sato Komusho:Kk | Electric double layer capacitor |
| JP2014027031A (en) * | 2012-07-25 | 2014-02-06 | Sato Komusho:Kk | Electric double layer capacitor |
| JP2016018808A (en) * | 2014-07-04 | 2016-02-01 | 株式会社佐藤工務所 | Polarizable electrode for electric double layer capacitor |
-
2001
- 2001-04-04 JP JP2001105764A patent/JP2002299185A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012114154A (en) * | 2010-11-22 | 2012-06-14 | Institute Of National Colleges Of Technology Japan | Method of manufacturing electrode for electric double layer capacitor |
| JP2013048213A (en) * | 2011-07-26 | 2013-03-07 | Sato Komusho:Kk | Electric double layer capacitor |
| JP2014027031A (en) * | 2012-07-25 | 2014-02-06 | Sato Komusho:Kk | Electric double layer capacitor |
| JP2016018808A (en) * | 2014-07-04 | 2016-02-01 | 株式会社佐藤工務所 | Polarizable electrode for electric double layer capacitor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Nitrogen/oxygen co-doped monolithic carbon electrodes derived from melamine foam for high-performance supercapacitors | |
| US7232790B2 (en) | Activated carbon, method for production thereof and use thereof | |
| KR101731494B1 (en) | Nitrogen-containing porous carbon material, method for producing same, and electric double layer capacitor using the nitrogen-containing porous carbon material | |
| EP1142831B1 (en) | Process for producing a carbon material for an electric double layer capacitor electrode, and processes for producing an electric double layer capacitor electrode and an electric double layer capacitor employing it | |
| JP6071261B2 (en) | Porous carbon material, method for producing the same, and electric double layer capacitor using the same | |
| JP5344972B2 (en) | Carbon material for electric double layer capacitor electrode and manufacturing method thereof | |
| Hsiao et al. | Biomass-derived three-dimensional carbon framework for a flexible fibrous supercapacitor and its application as a wearable smart textile | |
| Yan et al. | Salt-assisted pyrolysis of covalent organic frameworks to porous heteroatom-doped carbons for supercapacitive energy storage | |
| KR20110063472A (en) | Carbon material for electric double layer capacitor and process for producing the carbon material | |
| WO2004043859A2 (en) | Active carbon, production method thereof and polarizable electrode | |
| JP4420381B2 (en) | Activated carbon, manufacturing method thereof and polarizable electrode | |
| JPH09320906A (en) | Activated carbon for electric double layer capacitor electrode, its manufacture, and electric double layer capacitor electrode | |
| JP2005129924A (en) | Metal collector for use in electric double layer capacitor, and polarizable electrode as well as electric double layer capacitor using it | |
| JP5145496B2 (en) | Method for producing carbon nanostructure | |
| WO2007037523A1 (en) | Carbon material for electric double layer capacitor and electric double layer capacitor | |
| JP2001040548A (en) | Active carbon fiber, active carbon fiber cloth and its production | |
| Chen et al. | Capacitive properties of carbon nanofibers derived from blends of cellulose acetate and polyacrylonitrile | |
| JP2002299185A (en) | Method of manufacturing activated carbon cloth, activated carbon cloth and electric double-layer capacitor using the same | |
| JP2007269518A (en) | Porous carbon material, method for producing the same, polarizable electrode for electrical double layer capacitor, and electrical double layer capacitor | |
| JP2023030063A (en) | Capacitor electrode, manufacturing method, and capacitor | |
| JPH06267794A (en) | Manufacture of polarizable electrode material | |
| JP2006004997A (en) | Carbon for electric double layer capacitor electrode, its manufacturing method and electric double layer capacitor | |
| JP4916632B2 (en) | Vapor grown carbon fiber and its use | |
| JP4179581B2 (en) | Activated carbon, its production method and its use | |
| US20060000071A1 (en) | Process for fabrication of ultracapacitor electrodes using activated lamp black carbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080221 |
|
| A761 | Written withdrawal of application |
Free format text: JAPANESE INTERMEDIATE CODE: A761 Effective date: 20090303 |