JP2000247621A - Active carbon and its production - Google Patents
Active carbon and its productionInfo
- Publication number
- JP2000247621A JP2000247621A JP11050119A JP5011999A JP2000247621A JP 2000247621 A JP2000247621 A JP 2000247621A JP 11050119 A JP11050119 A JP 11050119A JP 5011999 A JP5011999 A JP 5011999A JP 2000247621 A JP2000247621 A JP 2000247621A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- carbon powder
- active carbon
- reactor
- surface area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 title abstract 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000005011 phenolic resin Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 229920002678 cellulose Polymers 0.000 claims abstract description 6
- 239000001913 cellulose Substances 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 229920001187 thermosetting polymer Polymers 0.000 claims description 11
- 239000006260 foam Substances 0.000 claims description 10
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 9
- 239000007858 starting material Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 19
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 8
- 229920001568 phenolic resin Polymers 0.000 abstract description 8
- 239000012298 atmosphere Substances 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 19
- 238000001994 activation Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 9
- 238000010304 firing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004088 foaming agent Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000004438 BET method Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- FBMGKRKUOZTARV-UHFFFAOYSA-N F.OB(O)O Chemical compound F.OB(O)O FBMGKRKUOZTARV-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 229940099364 dichlorofluoromethane Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940073584 methylene chloride Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
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)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、活性炭、特に電気
二重層コンデンサ等の電池関連に使用される活性炭及び
その製法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to activated carbon, and more particularly to activated carbon used for batteries such as electric double layer capacitors and a method for producing the same.
【０００２】[0002]
【従来の技術】活性炭は、従来古くから吸着用、触媒用
等に使用されているが、近年、エレクトロニクス関係の
製品の小型化、携帯化に伴い、電気二重層を利用したコ
ンデンサ、二次電池等、また昨今の環境問題から浮上し
てきた電気自動車用の燃料電池等、各種電池関連分野に
大量に利用され今後も需要の増大が期待される。電気二
重層コンデンサ（以下キャパシターと略称する。）を例
にとり説明すると、これに使用される分極性電極は単位
体積、単位重量あたりの静電容量を大きくするために、
表面積がある程度大きい必要があること、導電性が良い
こと等から活性炭粉末や活性炭素繊維を使用し薄板状に
し使用されている。しかし、市販の活性炭素繊維をその
まま原料として使用することは、原料的に高価であるた
め、有機繊維を焼成し活性炭素繊維化しバインダー等と
混ぜ抄紙化する、あるいは活性炭粉末を他の樹脂等と組
み合わせて成形し用いるのが一般的になっている。ま
た、使用される電解質の種類により、キャパシターは２
つのタイプに分けられる。一つは、硫酸水溶液を電解質
とするもので、一般的に水系キャパシターもしくは硫酸
系キャパシターと呼ばれている。もう一つのタイプは、
有機系キャパシターと呼ばれるもので、第四アンモニウ
ム塩／プロピレンカーボネート溶液等が電解液に使われ
ている。原料となる活性炭の製造は、一般的には原料を
炭化する工程と、有効表面積を上げるため、それの細孔
を調整するための賦活工程の２工程をかけて製造される
のが普通である。電極用活性炭粉末の原料としては、椰
子殻、大鋸屑、フェノール樹脂、ポリ塩化ビニリデン樹
脂等あるいはこれらの混合物等、様々なものが試みられ
ているが、最終的に電極として大量に使用されるため、
性能特性向上とともに製法、材料コストの面で安価であ
ること、原料が均一であることが重要で、原料、製法の
改良が必要となっている。たとえば安価な椰子殻等の天
然原料については、あらかじめ７００℃程度までの温度
にて焼成、炭化させその後、ロータリーキルン等で７０
０〜９００℃にて数時間賦活処理がなされるが、原料の
ばらつき、不純物等から均一、安定した性能が得られな
い問題がある。ポリ塩化ビニリデン樹脂については、原
料としては高価であり、量産には向いていない。特開平
３―１６４４１６では、熱硬化性樹脂の発泡体を焼成及
び平均粒径１μm 以上に粉砕することにより、賦活する
ことなしに、粒径に比し比表面積２００ｍ2 ／ｇ以上の
比較的比表面積の大きいガラス状カーボン粉末を容易に
得ることができる旨が開示されている。一般にガラス状
カーボンは、熱硬化性樹脂を炭化することにより容易に
得られる。また、通常のガラス状カーボン粉末は、硬質
炭素であり気密性、耐食性、耐薬品性に優れているが、
比表面積が小さく比表面積を上げるため粒を細かく粉砕
するにはかなりの時間、コストがかかり、キャパシター
用には不向きであった。しかしこの発明で得られたガラ
ス状カーボンは、１μm 以上での粒径でも、２００ｍ2
／ｇ以上の比表面積が得られ、従ってかなりの容量特性
が得られ、安定した製造が可能であり、水系キャパシタ
ーでは有効であることがわかった。しかし、有機系キャ
パシターでは、この製品でも、まだ容量不足であった。
この理由は、生成される細孔が小さすぎ、一般的に言わ
れている容量特性に有効なサイズ（１〜３ｎｍ程度）が
少ないこと、また比表面積としてせいぜい５００ｍ2 ／
ｇ程度までしか得られなく、有機系キャパシター用とし
ては、１０００ｍ2 ／ｇ以上の比表面積が更に必要であ
ると考えられた。2. Description of the Related Art Activated carbon has long been used for adsorption and catalysis for a long time. However, in recent years, as electronic products have become smaller and more portable, capacitors and secondary batteries using an electric double layer have been used. In addition, it is used in a variety of battery-related fields, such as fuel cells for electric vehicles, which have emerged from recent environmental problems, and demand is expected to increase in the future. Taking an electric double-layer capacitor (hereinafter abbreviated as a capacitor) as an example, the polarizable electrode used for the purpose is to increase the capacitance per unit volume and unit weight.
Activated carbon powder or activated carbon fiber is used to make a thin plate, because the surface area needs to be large to some extent and the conductivity is good. However, using commercially available activated carbon fiber as a raw material is expensive as a raw material.Therefore, the organic fiber is baked into activated carbon fiber and mixed with a binder or the like to make paper, or activated carbon powder is mixed with another resin or the like. It is common to use them in combination. Also, depending on the type of electrolyte used, the capacitor
Divided into two types. One uses an aqueous solution of sulfuric acid as an electrolyte, and is generally called an aqueous capacitor or a sulfuric acid-based capacitor. Another type is
This is called an organic capacitor, and a quaternary ammonium salt / propylene carbonate solution or the like is used as an electrolyte. The production of activated carbon as a raw material is generally carried out by two steps: a step of carbonizing the raw material, and an activation step for adjusting the pores thereof in order to increase the effective surface area. . Various materials such as coconut shell, sawdust, phenolic resin, polyvinylidene chloride resin and the like or a mixture thereof have been tried as a raw material of the activated carbon powder for an electrode, but since a large amount is finally used as an electrode,
It is important that the production method and material cost are inexpensive and that the raw materials are uniform, as well as the performance characteristics are improved, and it is necessary to improve the raw materials and the production method. For example, natural materials such as inexpensive coconut shells are baked and carbonized at a temperature of up to about 700 ° C.
Although activation treatment is performed at 0 to 900 ° C. for several hours, there is a problem that uniform and stable performance cannot be obtained due to variations in raw materials and impurities. Polyvinylidene chloride resin is expensive as a raw material and is not suitable for mass production. JP-A-3-164416 discloses that a thermosetting resin foam is calcined and pulverized to an average particle diameter of 1 μm or more, thereby activating the foam, and having a specific surface area of 200 m 2 / g or more relative to the particle diameter without activation. It is disclosed that a glassy carbon powder having a large particle size can be easily obtained. Generally, glassy carbon is easily obtained by carbonizing a thermosetting resin. In addition, ordinary glassy carbon powder is hard carbon and has excellent airtightness, corrosion resistance, and chemical resistance.
Since the specific surface area is small and the specific surface area is increased, it takes a considerable time and cost to pulverize the particles finely, and it is not suitable for a capacitor. However, the glassy carbon obtained by the present invention has a particle size of 1 μm or more,
/ G or more was obtained, so that considerable capacity characteristics were obtained, stable production was possible, and it was found to be effective for water-based capacitors. However, the capacity of the organic capacitor was still insufficient even with this product.
The reason for this is that the pores formed are too small, the size (about 1 to 3 nm) effective for the generally known capacity characteristics is small, and the specific surface area is at most 500 m 2 /
g, and it is considered that a specific surface area of 1000 m 2 / g or more is further required for an organic capacitor.
【０００３】[0003]
【発明が解決しようとする課題】本発明によれば、上記
のようなガラス状カーボンの製造過程で、簡易なガス賦
活法を併用することにより、キャパシター用、特に有機
系キャパシターに使用可能な、高性能のガラス状カーボ
ンによる活性炭粉末を安定的に安価に得ることが目的で
ある。通常の活性炭製造における賦活方法としては、水
蒸気、炭酸ガス等のガスと接触反応させる方法や、ＫＯ
Ｈ等の薬品を用いる方法がある。薬品賦活は高性能の活
性炭を得る一つの賦活法であるが、残薬品の除去が必要
なだけでなく、耐食性を要する特殊な装置を必要とする
ため、コスト高となるため、一般的には水蒸気や炭酸ガ
スを用いたガス賦活法により製造されている。水蒸気や
炭酸ガスによる賦活は、通常水蒸気中で７００〜９００
℃、あるいは炭酸ガス中で８５０℃以上での一定温度を
保ち、全体に均一な賦活がなされるよう、ロータリーキ
ルン等で混ぜ、一定時間管理する必要があり、装置的に
も管理的にも面倒なものであった。According to the present invention, by using a simple gas activation method together with the above-mentioned process for producing glassy carbon, it can be used for capacitors, particularly for organic capacitors. It is an object of the present invention to obtain activated carbon powder of high-performance glassy carbon stably at low cost. As the activation method in the ordinary activated carbon production, a method of contacting with a gas such as steam or carbon dioxide gas, or a method of KO
There is a method using a chemical such as H. Chemical activation is an activation method for obtaining high-performance activated carbon, but it is not only necessary to remove residual chemicals but also requires special equipment that requires corrosion resistance, which increases the cost, and is generally used. It is manufactured by a gas activation method using water vapor or carbon dioxide gas. Activation by water vapor or carbon dioxide gas is usually 700 to 900 in water vapor.
It is necessary to maintain a constant temperature of 850 ° C. or more in ℃ or carbon dioxide gas, mix with a rotary kiln, etc., and control for a fixed time so that the whole is uniformly activated. Was something.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、鋭意研究
した結果以下の知見を得た。先の特開平３―１６４４１
６にて得られるような、非酸化性雰囲気下で６００〜１
０００℃の温度域で焼成後1 〜３０μm に粉砕すると比
表面積が２００ｍ2 ／ｇ以上の炭材となる物質、もしく
はその焼成体を原料とし、４〜５０℃／ｈｒで加熱昇温
していく過程で、ある温度域間で水蒸気もしくは炭酸ガ
スに晒し、その後８５０〜１０００℃に焼成後、取り出
し、平均粒径１〜３０μm に粉砕したものは、細孔の多
くが２ｎｍ前後の細孔径からなっており、比表面積１０
００ｍ2 ／ｇ以上の値を示し、有機系キャパシター用の
活性炭として有効である。すなわち、焼成時の昇温過程
の途中に賦活工程を組みこむことにより、１〜３０μm
の粉砕粉でも有機系キャパシターの活性炭として利用で
きる１０００ｍ2 ／ｇ以上の比表面積の活性炭粉末が得
られる。Means for Solving the Problems The present inventors have earnestly studied and obtained the following findings. Japanese Unexamined Patent Publication No. Hei 3-16441
6 to 600 to 1 in a non-oxidizing atmosphere as obtained in
A process of heating and heating at a temperature of 4 to 50 ° C./hr using, as a raw material, a material which becomes a carbonaceous material having a specific surface area of 200 m 2 / g or more when crushed to 1 to 30 μm after firing in a temperature range of 000 ° C. Then, it is exposed to steam or carbon dioxide gas in a certain temperature range, then fired at 850 to 1000 ° C., taken out, and pulverized to an average particle size of 1 to 30 μm. And specific surface area 10
It shows a value of not less than 00 m 2 / g and is effective as activated carbon for organic capacitors. That is, by incorporating the activation step in the middle of the heating process during firing, 1 ~ 30μm
Activated carbon powder having a specific surface area of 1000 m @ 2 / g or more, which can be used as activated carbon of an organic capacitor, can be obtained by using the pulverized powder of the above.
【０００５】[0005]
【発明の実施の形態】さらに詳細に本発明について説明
すれば、本活性炭の原料としては、特開平３―１６４４
１６に示されたような、通常の焼成炭化温度である６０
０〜１０００℃の温度域で焼成炭化後１〜３０μｍに粉
砕するとＢＥＴ法（Ｎ２ガス）による比表面積の測定値
が２００ｍ2 ／ｇ以上の炭材になる物質が好ましい。こ
れは、熱硬化性樹脂に揮発性発泡剤を混合し、発泡させ
硬化させたものが使用できる。本発明の出発原料とし
て、２００ｍ2 ／ｇ以下になる物質では、活性炭の細孔
径のばらつきが大きくなり好ましくなく、本発明による
方法でも必要な比表面積が得られない。このような原料
として好適な物質は、フェノール樹脂、フラン樹脂、塩
素化塩ビ等の熱硬化性樹脂に硬化発泡体を混ぜた各種熱
硬化樹脂発泡体が挙げられるが、価格の点から安価なフ
ェノール樹脂の発泡体が好ましい。揮発性発泡剤は、有
機、無機いずれのものでも良いが、取り扱いの容易性、
発泡効率から沸点が５〜６０℃の範囲にある有機質揮発
性発泡剤が好ましい。例えば、トリクロロモノフルオロ
メタン、ジクロロモノフルオロメタン、メチレンクロリ
ド、トリクロロトリフルオロエタン、アセトン、エーテ
ル、石油エーテル、ペンタン等をあげることが出来る。
発泡剤の使用は、熱硬化性樹脂１００重量部に対し、５
〜５０重量部が適当である。これら原料の樹脂は、熱硬
化性であるので８０〜１００℃程度の温度で硬化する
が、硬化を促進するためフェノールスルホン酸、ベンゼ
ンスルホン酸等の硬化剤をあらかじめ添加してもよい。
本発明者らの検討結果によると、フェノール樹脂とセル
ロースの複合体も同様の作用効果があることが判明し
た。これら原料となる物質は、あらかじめ非酸化性雰囲
気下で焼成してあってもよいが、未焼成の状態でも良
い。製造コストの点からは、あえて焼成後の原料を使う
必要はない。DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail.
The normal calcined carbonization temperature, 60, as shown in FIG.
When calcined and carbonized in a temperature range of 0 to 1000 ° C. and then pulverized to 1 to 30 μm, a substance which becomes a carbonaceous material having a measured specific surface area of 200 m 2 / g or more by the BET method (N2 gas) is preferred. For this, a thermosetting resin mixed with a volatile foaming agent, foamed and cured can be used. If the starting material used in the present invention is a substance having a capacity of 200 m @ 2 / g or less, the variation in the pore diameter of the activated carbon is unfavorable, and the method according to the present invention cannot provide the required specific surface area. Suitable materials as such a raw material include various thermosetting resin foams obtained by mixing a thermosetting resin with a thermosetting resin such as a phenol resin, a furan resin, and chlorinated vinyl chloride. A resin foam is preferred. The volatile foaming agent may be organic or inorganic, but is easy to handle,
Organic volatile foaming agents having a boiling point in the range of 5 to 60 ° C. from the foaming efficiency are preferred. For example, trichloromonofluoromethane, dichloromonofluoromethane, methylene chloride, trichlorotrifluoroethane, acetone, ether, petroleum ether, pentane and the like can be mentioned.
The use of the foaming agent is 5 parts per 100 parts by weight of the thermosetting resin.
~ 50 parts by weight is suitable. Since these resin materials are thermosetting, they are cured at a temperature of about 80 to 100 ° C., but a curing agent such as phenolsulfonic acid or benzenesulfonic acid may be added in advance to accelerate the curing.
According to the examination results of the present inventors, it has been found that a composite of phenol resin and cellulose has the same effect. These raw materials may be fired in advance in a non-oxidizing atmosphere, or may be unfired. From the viewpoint of manufacturing cost, it is not necessary to use raw materials after firing.
【０００６】次にこれら原料となる物質は硬化後、炉中
で、燃焼しない程度に非酸化性雰囲気にて、昇温速度４
〜５０℃／ｈｒで加熱昇温していき、一定温度域で賦活
ガスを流し昇温しながら賦活させる。この一定温度域
は、望ましくは７００〜８３０℃である。これより低温
であると賦活効果が得られない。また、これより高温で
は、反応速度が速すぎて均一な賦活が困難になる。賦活
ガスは、取り扱いの容易さ、経済性から水蒸気あるいは
炭酸ガスが好ましい。ガスは、連続して昇温中、８３０
℃まで流し続ける。その後、水蒸気又は炭酸ガスの流入
を止め、更に昇温を続け８５０〜１０００℃に達した時
点で取り出し、冷却後ミル等にて平均粒径１〜３０μm
に粉砕する。これにより１〜３０μｍの平均粒径でも、
１０００ｍ2 ／ｇ以上の大きな比表面積を持つ電気二重
層コンデンサ（キャパシター）特に有機系キャパシター
の電極に使用できる活性炭粉末としてのガラス状カーボ
ンが得られる。また、上記方法によれば、通常の活性炭
を得る方法としている７００℃近辺での焼成炉での焼
成、およびその後の賦活のための８５０〜９００℃での
ロータリーキルン等での水蒸気、炭酸ガスを流しながら
の再昇温、保持の工程が、焼成炉での昇温工程中に賦活
工程を済ませられ、大幅に工程短縮でき温度管理も昇温
速度の管理のみで楽である。なお、上記条件を外れる
と、所望するような活性炭は得難い。[0006] After these materials are cured, they are heated in a furnace in a non-oxidizing atmosphere to the extent that they do not burn, at a heating rate of 4%.
The temperature is raised by heating at ５０50 ° C./hr, and an activation gas is flowed in a certain temperature range to activate while raising the temperature. This constant temperature range is desirably 700 to 830 ° C. If the temperature is lower than this, the activation effect cannot be obtained. If the temperature is higher than this, the reaction rate is too high, and uniform activation becomes difficult. The activation gas is preferably water vapor or carbon dioxide gas from the viewpoint of ease of handling and economy. The gas was continuously heated at 830
Continue to flow to ° C. Thereafter, the inflow of water vapor or carbon dioxide gas was stopped, the temperature was further increased, and when the temperature reached 850 to 1000 ° C., it was taken out. After cooling, the average particle size was 1 to 30 μm in a mill or the like.
Crushed. Thereby, even with an average particle size of 1 to 30 μm,
Glassy carbon as an activated carbon powder which can be used for an electrode of an electric double layer capacitor (capacitor), particularly an organic capacitor, having a large specific surface area of 1000 m 2 / g or more is obtained. In addition, according to the above-described method, baking is performed in a baking furnace at around 700 ° C., which is a method for obtaining ordinary activated carbon, and steam and carbon dioxide gas are flown in a rotary kiln or the like at 850 to 900 ° C. for subsequent activation. The re-heating and holding process can be completed in the activation process during the heating process in the firing furnace, and the process can be greatly shortened, and the temperature management is easy only by controlling the heating rate. If the above conditions are not satisfied, it is difficult to obtain desired activated carbon.
【０００７】[0007]
【実施例】以下、実施例により本発明を更に詳細に説明
する。原料サンプルＡとしてフェノール樹脂発泡体を使
用した。このフェノール樹脂発泡体は、液状フェノール
樹脂（昭和高分子（株）製ＢＲＬ―１２０Ｚ）、シリコ
ン系界面活性剤（（株）信越化学製Ｆ−３０５）、発泡
剤（フレオン１１３；１，１，２―トリフルオル−１，
２，２―トリクロルエタン）を重量比で１００：２：１
０に配合し高速ミキサーで充分混合した後、予め８０℃
に加熱してある型内に注入し、発泡させて得た。樹脂が
硬化した後に１辺２ｃｍの立方体に切断してサンプルに
供した。原料サンプルＢとしてフェノール樹脂とセルロ
ースの複合体を板状に硬化させたものである昭和電工
（株）製ガラス状カーボン複合板、商品名；ＳＧ−１の
未焼成グリーン成形板を２ｃｍ角に切断してサンプルに
供した。また比較用サンプルＣとしてフェノール発泡体
に使用したフェノール樹脂のみを１００℃で加熱硬化し
た樹脂塊を１辺２ｃｍ角の立方体に切出して比較用のサ
ンプルとした。これら原料サンプルが本発明の材料とし
て好適かどうかを判断するため、８００℃に焼成炭化
後、ボールミルにて各種粒度に粉砕し、窒素ガス吸着法
（ＢＥＴ法）により比表面積を測定し、比表面積を測定
した。その結果を表１に示す。この結果から、原料サン
プルＡ，Ｂは本発明用の材料としての使用ができること
がわかった。The present invention will be described in more detail with reference to the following examples. A phenol resin foam was used as the raw material sample A. This phenolic resin foam is made of a liquid phenolic resin (BRL-120Z, manufactured by Showa Polymer Co., Ltd.), a silicon-based surfactant (F-305, manufactured by Shin-Etsu Chemical Co., Ltd.), and a foaming agent (Freon 113; 1,1,1). 2-trifluoro-1,
2,2-trichloroethane) in a weight ratio of 100: 2: 1
0 and thoroughly mixed with a high-speed mixer.
Into a heated mold and foamed. After the resin was cured, it was cut into a cube having a side of 2 cm and used as a sample. As raw material sample B, a glassy carbon composite plate manufactured by Showa Denko KK, which is obtained by curing a composite of phenolic resin and cellulose into a plate shape; trade name; unfired green molded plate of SG-1 cut into 2 cm square And used for the sample. Further, as a comparative sample C, only a phenol resin used for the phenol foam was heat-cured at 100 ° C., and a resin lump was cut into a 2 cm square cube to obtain a comparative sample. In order to judge whether these raw material samples are suitable as the material of the present invention, calcined at 800 ° C., pulverized to various particle sizes with a ball mill, and measured for specific surface area by nitrogen gas adsorption method (BET method). Was measured. Table 1 shows the results. From these results, it was found that raw material samples A and B can be used as materials for the present invention.
【０００８】各サンプルＡ，Ｂ，Ｃをステンレス容器に
入れ、表２に示した条件で外部から加熱昇温し所定の温
度域でステンレス容器と接続した配管から水蒸気又は炭
酸ガスを導入し、容器内を飽和水蒸気、飽和炭酸ガスと
し、接触反応させ、その後所定の温度で焼き上げた。得
られた活性炭の賦活収率（仕込み量に対する賦活残量
％）、またこの活性炭をボールミルで平均粒径２０μｍ
に粉砕後、窒素ガス吸着法（ＢＥＴ法）により比表面積
を測定した結果を表３に示す。また、粉砕したカーボン
粉末を、テフロン樹脂繊維（三井デュポンフロオロケミ
カル（株）製Ｊ６）とカーボンブラック（電気化学工業
（株）製デンカブラック）と、カーボン粉末：テフロ
ン：カーボンブラック＝８０：１０：１０に配合し、加
圧成型することにより厚さ０．２ｍｍの電極シートと
し、電解液としてテトラエチルメチルアンモニュウム４
フッ化ボレート塩をプロピレンカーボネイト溶媒に３０
％溶かした液を使用し、市販充放電測定装置により、２
ｍＡ／ｃｍ2の電流密度の条件で電気二重層コンデンサ
としての容量性能を測定した。測定結果を表３に示す。
なお、充放電を１０回繰り返し、１０回目の測定値を容
量値とした。Each of the samples A, B, and C is placed in a stainless steel container, heated and heated from the outside under the conditions shown in Table 2, and steam or carbon dioxide gas is introduced from a pipe connected to the stainless steel container in a predetermined temperature range. The inside was made into saturated steam and saturated carbon dioxide gas, and was subjected to a contact reaction, and then baked at a predetermined temperature. The activation yield of the obtained activated carbon (remaining activation% based on the charged amount), and the activated carbon was averaged in a ball mill to an average particle size of 20 μm.
After pulverization, the specific surface area was measured by a nitrogen gas adsorption method (BET method). Further, the pulverized carbon powder was mixed with Teflon resin fiber (J6 manufactured by Mitsui DuPont Fluorochemicals Co., Ltd.) and carbon black (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.), and carbon powder: Teflon: carbon black = 80: 10 : 10 and press-molded to form an electrode sheet having a thickness of 0.2 mm. As an electrolyte, tetraethylmethylammonium 4 was used.
Fluoride borate salt in propylene carbonate solvent 30
% Solution, using a commercially available charge / discharge measurement device
The capacity performance as an electric double layer capacitor was measured under the conditions of a current density of mA / cm 2. Table 3 shows the measurement results.
The charge and discharge were repeated ten times, and the measured value at the tenth time was defined as the capacitance value.
【０００９】[0009]
【表１】 [Table 1]
【表２】 [Table 2]
【表３】 [Table 3]
【００１０】[0010]
【発明の効果】本発明によれば、安価なフェノール樹脂
発泡体、あるいはフェノール樹脂とセルロースの複合体
等を硬化させた後、焼成のための昇温時に、一定温度域
の間に水蒸気あるいは炭酸ガス等の賦活ガスを吹き込む
という簡単な工程により、焼成後１〜３０μｍの比較的
大きな粒径で粉砕した粉末でも、有機系キャパシタ用活
性炭粉末に適する１０００ｍ2 ／ｇ以上の比表面積を持
つガラス状カーボンが得られる。According to the present invention, after curing an inexpensive phenolic resin foam or a composite of phenolic resin and cellulose, etc., when heating for firing, steam or carbonic acid is added during a certain temperature range. By a simple process of blowing an activating gas such as a gas, even if the powder is crushed to a relatively large particle size of 1 to 30 μm after firing, it is suitable for activated carbon powder for organic capacitors and has a specific surface area of 1000 m 2 / g or more. Is obtained.
Claims (8)
００ｍ2 ／ｇ以上であることを特徴とするガラス状カー
ボンからなる活性炭粉末。An average particle size of 1 to 30 μm and a specific surface area of 10
Activated carbon powder comprising glassy carbon having a particle size of at least 00 m 2 / g.
の、もしくはその焼成体を出発原料とすることを特徴と
する請求項１記載の活性炭粉末。2. The activated carbon powder according to claim 1, wherein a cured phenol resin foam or a fired body thereof is used as a starting material.
硬化させたもの、もしくはその焼成体を出発原料とする
ことを特徴とする請求項１記載の活性炭粉末。3. The activated carbon powder according to claim 1, wherein a cured product of a composite of phenol resin and cellulose or a calcined product thereof is used as a starting material.
セルロースの複合体を硬化させ、加熱昇温しながら一定
温度領域で賦活ガスに晒し、その後８５０〜１０００℃
に焼成後、平均粒径１〜３０μm に粉砕することを特徴
とする活性炭粉末の製造法。4. A thermosetting resin foam or a thermosetting resin-cellulose composite is cured and exposed to an activation gas in a constant temperature range while heating and raising the temperature.
And then pulverizing to an average particle size of 1 to 30 μm.
とを特徴とする請求項４記載の活性炭粉末の製造法。5. The method for producing activated carbon powder according to claim 4, wherein the thermosetting resin is a phenol resin.
ことを特徴とする請求項４又は５記載の活性炭粉末の製
造法。6. The method for producing activated carbon powder according to claim 4, wherein the heating rate is 4 to 50 ° C./hr.
とを特徴とする請求項４から６いずれか記載の活性炭粉
末の製造法。7. The method for producing activated carbon powder according to claim 4, wherein the activation gas is steam or carbon dioxide.
０℃であることを特徴とする請求項４から７いずれか記
載の活性炭粉末の製造法。8. A temperature range for exposing to an activation gas is 700 to 83.
The method for producing activated carbon powder according to any one of claims 4 to 7, wherein the temperature is 0 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11050119A JP2000247621A (en) | 1999-02-26 | 1999-02-26 | Active carbon and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11050119A JP2000247621A (en) | 1999-02-26 | 1999-02-26 | Active carbon and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000247621A true JP2000247621A (en) | 2000-09-12 |
Family
ID=12850242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11050119A Pending JP2000247621A (en) | 1999-02-26 | 1999-02-26 | Active carbon and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000247621A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004189586A (en) * | 2002-11-29 | 2004-07-08 | Honda Motor Co Ltd | Activated carbon, polarizable electrode for electric double layer capacitor and electric double layer capacitor using the same |
| KR100447890B1 (en) * | 2001-10-25 | 2004-09-08 | (주)넥센나노텍 | Carbon material for electrode of electric double layered capacitor and method of making the same |
| JP2006131452A (en) * | 2004-11-05 | 2006-05-25 | Tokai Carbon Co Ltd | Method for producing glassy carbon powder |
| EP1757362A4 (en) * | 2004-05-31 | 2007-08-22 | Teikoku Medix Co Ltd | Adsorbent and process for producing the same |
| JP2013040054A (en) * | 2011-08-11 | 2013-02-28 | Lignyte Co Ltd | Carbide and method for producing the carbide |
| CN105895380A (en) * | 2016-04-12 | 2016-08-24 | 齐鲁工业大学 | Three-dimensional reticular polyaniline/phenolic resin-based carbon sphere composite material and preparation method thereof |
| CN111908465A (en) * | 2020-08-04 | 2020-11-10 | 上海欧亚合成材料股份有限公司 | Preparation method of high-specific surface area and high-purity super-capacitor activated carbon |
| CN112086299A (en) * | 2020-09-30 | 2020-12-15 | 华南理工大学 | A kind of supercapacitor flexible thin film electrode material and preparation method thereof |
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1999
- 1999-02-26 JP JP11050119A patent/JP2000247621A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100447890B1 (en) * | 2001-10-25 | 2004-09-08 | (주)넥센나노텍 | Carbon material for electrode of electric double layered capacitor and method of making the same |
| JP2004189586A (en) * | 2002-11-29 | 2004-07-08 | Honda Motor Co Ltd | Activated carbon, polarizable electrode for electric double layer capacitor and electric double layer capacitor using the same |
| EP1757362A4 (en) * | 2004-05-31 | 2007-08-22 | Teikoku Medix Co Ltd | Adsorbent and process for producing the same |
| JP2006131452A (en) * | 2004-11-05 | 2006-05-25 | Tokai Carbon Co Ltd | Method for producing glassy carbon powder |
| JP2013040054A (en) * | 2011-08-11 | 2013-02-28 | Lignyte Co Ltd | Carbide and method for producing the carbide |
| CN105895380A (en) * | 2016-04-12 | 2016-08-24 | 齐鲁工业大学 | Three-dimensional reticular polyaniline/phenolic resin-based carbon sphere composite material and preparation method thereof |
| CN111908465A (en) * | 2020-08-04 | 2020-11-10 | 上海欧亚合成材料股份有限公司 | Preparation method of high-specific surface area and high-purity super-capacitor activated carbon |
| CN112086299A (en) * | 2020-09-30 | 2020-12-15 | 华南理工大学 | A kind of supercapacitor flexible thin film electrode material and preparation method thereof |
| CN112086299B (en) * | 2020-09-30 | 2022-04-22 | 华南理工大学 | Flexible thin film electrode material of super capacitor and preparation method thereof |
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