JPH08115856A - Method for manufacturing activated carbon electrode for electrical double-layer capacitor - Google Patents
Method for manufacturing activated carbon electrode for electrical double-layer capacitorInfo
- Publication number
- JPH08115856A JPH08115856A JP6248186A JP24818694A JPH08115856A JP H08115856 A JPH08115856 A JP H08115856A JP 6248186 A JP6248186 A JP 6248186A JP 24818694 A JP24818694 A JP 24818694A JP H08115856 A JPH08115856 A JP H08115856A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- base material
- activation treatment
- average particle
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- 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)
- Ceramic Products (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電気二重層コンデンサ
ーとして好適に用いられる活性炭電極の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an activated carbon electrode suitable for use as an electric double layer capacitor.
【０００２】[0002]
【従来の技術】電気二重層コンデンサーは、パソコンな
どの電子機器のバックアップ用電源として実用化されて
おり、また自動車の補助バッテリーなどの瞬間大電流供
給用補助電源としても開発が行われている。この電気二
重層コンデンサーの電極は分極性電極と称され、大きな
静電容量を持つことが要求されている。そのために、分
極性電極の材料としては比表面積の大きい導電性の炭素
材料が使用され、特に賦活済みの活性炭が好ましい。賦
活済みの活性炭基材としては、粉末状のものと繊維状の
ものとがある。2. Description of the Related Art Electric double layer capacitors have been put to practical use as a backup power source for electronic devices such as personal computers, and have also been developed as an auxiliary power source for supplying instantaneous large current such as an auxiliary battery for automobiles. The electrode of this electric double layer capacitor is called a polarizable electrode and is required to have a large capacitance. Therefore, a conductive carbon material having a large specific surface area is used as the material of the polarizable electrode, and activated carbon is particularly preferable. The activated carbon base material that has been activated includes powdery ones and fibrous ones.
【０００３】活性炭の製造には、コークス、石炭、ヤシ
ガラ炭などの炭素質のものから、フェノール樹脂等の熱
硬化性樹脂など、様々な熱分解性炭素化合物が原料とし
て用いられる。図７はフェノール樹脂を原料とした活性
炭製造工程の概要である。この図に示す如く、まずフェ
ノール樹脂を硬化した後、乾留して炭素以外の成分を揮
発させる炭化工程を経て、賦活し、必要に応じて、粉
砕、整粒して粉末ないし粒状の活性炭基材を得る。ここ
で、賦活とは、通常、炭酸ガスまたは水蒸気雰囲気中で
の熱処理による活性化処理である。なお、炭素化合物原
料にアクリル繊維などを用いて、繊維形状を保ったま
ま、同様にして、炭化処理などの工程を経て繊維状活性
炭基材を得ることも知られている。In the production of activated carbon, various pyrolyzable carbon compounds such as carbonaceous materials such as coke, coal and coconut husk charcoal to thermosetting resins such as phenol resin are used as raw materials. FIG. 7 is an outline of the activated carbon manufacturing process using phenol resin as a raw material. As shown in this figure, first, after the phenol resin is cured, it is activated by a carbonization step of dry distillation to evaporate components other than carbon, and activated, and if necessary, pulverized and sized to form a powder or granular activated carbon base material. To get Here, activation is usually activation treatment by heat treatment in a carbon dioxide gas or steam atmosphere. It is also known that an acrylic fiber or the like is used as a carbon compound raw material and a fibrous activated carbon base material is similarly obtained through a process such as carbonization while maintaining the fiber shape.
【０００４】従来より、電気二重層コンデンサーの分極
性電極には、前記粉末ないし粒状の活性炭基材を硫酸溶
液と混合してペースト状として用いられているが、活性
炭粒子間の接触抵抗が大きく、大きな電流を流せなかっ
た。また、繊維状活性炭布の場合も、同様に、繊維間の
接触抵抗と単位体積当りの活性炭密度が小さく、大電流
を得ることができなかった。Conventionally, for the polarizable electrode of an electric double layer capacitor, the powdery or granular activated carbon base material is mixed with a sulfuric acid solution and used as a paste, but the contact resistance between the activated carbon particles is large, I couldn't pass a big current. Also in the case of the fibrous activated carbon cloth, similarly, the contact resistance between fibers and the activated carbon density per unit volume were small, and a large current could not be obtained.
【０００５】そこで、図７に示すように、活性炭基材
に、更にバインダーを加えて成形し、加えたバインダー
を同様に炭化して焼結し、板状の成形体とする方法が考
えられる。バインダーには、炭化後、基材と同じ炭素質
となる熱分解性炭素化合物が選択されるが、この場合、
原料と同じフェノール樹脂が好ましい。基材に繊維状活
性炭を用いた場合も、バインダーで繊維間を埋め込み、
同様に炭化して焼結すれば、密度の大きい板状となり、
分極性電極としての使用が期待できる。Therefore, as shown in FIG. 7, a method is conceivable in which a binder is further added to the activated carbon base material to be molded, and the added binder is similarly carbonized and sintered to form a plate-shaped molded body. For the binder, a thermally decomposable carbon compound that becomes carbonaceous after carbonization is selected, but in this case,
The same phenolic resin as the raw material is preferable. Even when fibrous activated carbon is used as the base material, the space between the fibers is embedded with a binder,
Similarly, if carbonized and sintered, it becomes a plate with high density,
It can be expected to be used as a polarizable electrode.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、前記の
ような従来の活性炭基材にバインダーを加えて炭化・焼
結して得た電気二重層コンデンサー用の活性炭分極性電
極は、その重量当りの静電容量が、しばしば基材よりも
低くなるという不都合があった。その原因については、
上記従来の方法においては、加えたバインダーが炭化し
て生成した炭素質成分が、賦活されていないのみなら
ず、該炭素質成分によって基材の活性が何らかの理由で
阻害されるのではないかと推察した。However, an activated carbon polarizable electrode for an electric double layer capacitor obtained by adding a binder to the conventional activated carbon base material and carbonizing / sintering it as described above has a static per unit weight. There is the disadvantage that the capacitance is often lower than that of the substrate. For the cause,
In the above-mentioned conventional method, the carbonaceous component produced by carbonization of the added binder is not only not activated, but it is speculated that the activity of the base material may be hindered by the carbonaceous component for some reason. did.
【０００７】本発明は前記事情に鑑みてなされたもの
で、高い静電容量を実現できる活性炭電極が得られるよ
うにした電気二重層コンデンサー用活性炭電極の製造方
法を提供するものである。The present invention has been made in view of the above circumstances, and provides a method for producing an activated carbon electrode for an electric double layer capacitor, which is capable of obtaining an activated carbon electrode capable of realizing a high electrostatic capacity.
【０００８】[0008]
【課題を解決するための手段】前記課題を解決するため
に、本発明の電気二重層コンデンサー用活性炭電極の製
造方法は、炭素化合物を炭化処理して得た炭化物を活性
化処理を施した後に粉砕して活性炭基材とし、該活性炭
基材にバインダーを加え板状に成形して成形体とし、該
成形体を炭化処理して板状活性炭を製造する方法におい
て、前記活性炭基材の平均粒径が１０μｍ以下であるこ
とを特徴とするものである。また、炭素化合物を炭化処
理して得た炭化物に一次活性化処理を施した後に粉砕し
て平均粒径が１０μｍ以下の活性炭基材とし、該活性炭
基材にバインダーを加え板状に成形して成形体とし、該
成形体を炭化処理した後に再度二次活性化処理を施すこ
とがより望ましい。上記一次および二次活性化処理とし
て、炭酸ガス雰囲気中または水蒸気雰囲気中のいずれか
での熱処理による賦活処理を行なうことができる。ある
いは上記一次および二次活性化処理として、空気中での
酸化処理を行なうとより効果的である。この空気中での
酸化処理は熱処理によって行なうことができる。また二
次活性化処理として空気中での酸化処理を行なった際に
は、付加処理として不活性ガス中での熱処理を行なうの
が好ましい。In order to solve the above-mentioned problems, the method for producing an activated carbon electrode for an electric double layer capacitor of the present invention is a method in which a carbon compound obtained by carbonizing a carbon compound is subjected to an activation treatment. In the method for producing a plate-like activated carbon by crushing to obtain an activated carbon base material, adding a binder to the activated carbon base material to form a plate-shaped product, and carbonizing the formed product, the average particle size of the activated carbon base material. The diameter is 10 μm or less. In addition, a carbide obtained by carbonizing a carbon compound is subjected to a primary activation treatment and then pulverized to obtain an activated carbon base material having an average particle size of 10 μm or less, and a binder is added to the activated carbon base material to form a plate shape. It is more desirable that the formed body is carbonized and then subjected to the secondary activation treatment again. As the primary and secondary activation treatments, activation treatment by heat treatment in either a carbon dioxide gas atmosphere or a steam atmosphere can be performed. Alternatively, it is more effective to perform oxidation treatment in air as the above-mentioned primary and secondary activation treatments. This oxidation treatment in air can be performed by heat treatment. Further, when the oxidation treatment in air is performed as the secondary activation treatment, it is preferable to perform the heat treatment in an inert gas as the additional treatment.
【０００９】[0009]
【作用】本発明者らは、試行錯誤を繰り返しながら鋭意
考究した結果、図７に示した従来の活性炭電極の製造工
程において、活性炭基材の平均粒径が１０μｍ以下であ
ると高い静電容量を実現できる活性炭電極が得られ、１
０μｍを越えると静電容量が著しく低下することを見い
出した。すなわち、本発明の電気二重層コンデンサー用
活性炭電極の製造方法によれば、活性炭基材の平均粒径
を１０μｍ以下とすることによって、その活性炭基材に
バインダーを添加して成形・炭化した場合に、基材の活
性が損なわれず、これに起因する静電容量の低下が抑制
される。また、炭素化合物を炭化処理して得た炭化物を
１次活性化処理を施した後に粉砕して平均粒径が１０μ
ｍ以下の活性炭基材とし、該活性炭基材にバインダーを
加え板状に成形して成形体とし、該成形体を炭化処理し
た後に２次活性化処理を施すと、活性炭基材の粒径によ
る効果と２次活性化処理による効果との相乗効果によ
り、高い静電容量を得ることができる。活性化処理は、
炭酸ガスまたは水蒸気雰囲気中での熱処理によって行な
うことができる。あるいは、活性化処理として空気中で
の酸化処理を行なうと、静電容量のレベルをさらに高め
ることができる。The inventors of the present invention have conducted extensive studies through repeated trial and error, and as a result, in the manufacturing process of the conventional activated carbon electrode shown in FIG. 7, if the average particle size of the activated carbon base material is 10 μm or less, high capacitance is obtained. An activated carbon electrode that can realize
It has been found that when the thickness exceeds 0 μm, the electrostatic capacity significantly decreases. That is, according to the method for producing an activated carbon electrode for an electric double layer capacitor of the present invention, when the average particle diameter of the activated carbon base material is set to 10 μm or less, a binder is added to the activated carbon base material to form and carbonize. The activity of the base material is not impaired, and the decrease in electrostatic capacitance resulting from this is suppressed. Further, the carbide obtained by carbonizing the carbon compound is subjected to primary activation treatment and then pulverized to obtain an average particle diameter of 10 μm.
When the activated carbon base material having a particle size of m or less is added, a binder is added to the activated carbon base material to form a plate, and the formed body is carbonized and then subjected to a secondary activation treatment. A high electrostatic capacitance can be obtained by the synergistic effect of the effect and the effect of the secondary activation treatment. The activation process is
It can be performed by heat treatment in a carbon dioxide gas or steam atmosphere. Alternatively, if the oxidation treatment is performed in air as the activation treatment, the level of capacitance can be further increased.
【００１０】[0010]
【実施例】以下、本発明を詳しく説明する。まず、本発
明の製造方法の第１の実施例として、図７に示す製造工
程において、賦活された炭化物を粉砕して活性炭基材を
得る際に、平均粒径が１０μｍ以下となるように整粒し
て、板状活性炭（活性炭電極）を製造した。本実施例に
おける実験例（実験例１〜６）として、粉砕時間変える
ことによって活性炭基材の粒径を種々に変化させた。ま
た比較のために、比較例１として原料に粉末状のフェノ
ール樹脂を用い、粉砕を行わないで活性炭電極を製造し
た。The present invention will be described in detail below. First, as a first embodiment of the production method of the present invention, in the production process shown in FIG. 7, when activated carbon is crushed to obtain an activated carbon base material, the average particle diameter is adjusted to 10 μm or less. Granules were produced to produce plate-like activated carbon (activated carbon electrode). As experimental examples (Experimental Examples 1 to 6) in this example, the particle size of the activated carbon base material was variously changed by changing the pulverization time. For comparison, as Comparative Example 1, a powdery phenolic resin was used as a raw material, and an activated carbon electrode was manufactured without crushing.
【００１１】（実験例１）ノボラック型フェノール樹脂
を１６０℃で硬化した後、約２ｍｍ角に粉砕した。これ
を窒素ガス中、９００℃で３０分間熱処理して炭化し
た。引続き、炭酸ガス中、９００℃で１．５時間熱処理
して賦活した。次に、振動ボールミルで３０時間粉砕し
て活性炭基材を得た。レーザー散乱光式粒度測定器（マ
イクロトラック）による粒度測定の結果、平均粒径は
０．７μｍであった。この得られた活性炭粉末１００部
に、フェノール樹脂１５部、エタノール８部、およびク
レオソート２０部からなるバインダー４７部を加えて混
練し、圧力５００ｋｇ／ｃｍ2でプレスして、５０×５
０×１ｍｍの板状の成形体とした。(Experimental Example 1) A novolac type phenol resin was cured at 160 ° C. and then pulverized into about 2 mm square. This was heat-treated in nitrogen gas at 900 ° C. for 30 minutes for carbonization. Then, it was activated by heat treatment in carbon dioxide gas at 900 ° C. for 1.5 hours. Next, it was ground for 30 hours with a vibrating ball mill to obtain an activated carbon base material. As a result of particle size measurement by a laser scattered light particle sizer (Microtrac), the average particle size was 0.7 μm. To 100 parts of the obtained activated carbon powder, 47 parts of a binder consisting of 15 parts of phenol resin, 8 parts of ethanol and 20 parts of creosote was added and kneaded, and pressed at a pressure of 500 kg / cm 2 to obtain 50 × 5.
A 0 × 1 mm plate-shaped molded body was prepared.
【００１２】得られた成形体を、窒素ガス中で、昇温速
度１００℃／ｈで９００℃に昇温し、３０分間保持して
炭化処理して板状活性炭（活性炭電極）を得た。炭化処
理後の板状活性炭には、ソリやクラックは認められず、
成形性は良好であった。この板状活性炭から１４ｍｍφ
（厚さ１ｍｍ）の円板を２枚切り出し、真空中で３０ｗ
ｔ％硫酸溶液を含浸させて図２に示す測定用セルを作製
し、静電容量を求めた。図２において、符号１は活性炭
電極、２はガスケット、３は集電極、４はセパレータを
それぞれ示す。静電容量Ｃは一般に、充電後、一定電流
Ｉで放電し、電圧Ｖ1からＶ2まで低下する時間△ｔを測
定し、下式（ｉ）によって求めることができる。 Ｃ＝Ｉ×△ｔ／（Ｖ1−Ｖ2）……（ｉ） ここでは、９００ｍＶで２４時間充電後４ｍＡ／ｃｍ2
で放電し、引続き、２時間充電後４００ｍＡ／ｃｍ2で
放電した。そして、いずれも、Ｖ1＝５４０ｍＶ、Ｖ2＝
３６０ｍＶとして、それぞれ４ｍＡ／ｃｍ2の時５０．
８Ｆ／ｃｍ3、４００ｍＡ／ｃｍ2の時２２．１Ｆ／ｃｍ
3を得た。The obtained molded body was heated to 900 ° C. at a heating rate of 100 ° C./h in nitrogen gas and held for 30 minutes for carbonization treatment to obtain a plate-like activated carbon (activated carbon electrode). No warping or cracks were observed in the plate-like activated carbon after carbonization treatment,
The moldability was good. 14mmφ from this plate-like activated carbon
Cut out 2 (thickness 1mm) discs, 30w in vacuum
A t% sulfuric acid solution was impregnated into the measurement cell shown in FIG. 2 to determine the capacitance. In FIG. 2, reference numeral 1 is an activated carbon electrode, 2 is a gasket, 3 is a collecting electrode, and 4 is a separator. Generally, the electrostatic capacitance C can be obtained by the following equation (i) by measuring the time Δt for discharging from the voltage V 1 to V 2 after discharging with a constant current I after charging. C = I × Δt / (V 1 −V 2 ) ... (i) Here, after charging at 900 mV for 24 hours, 4 mA / cm 2
, And subsequently, after being charged for 2 hours, it was discharged at 400 mA / cm 2 . And in each case, V 1 = 540 mV, V 2 =
When 360 mV and 4 mA / cm 2 respectively, 50.
8F / cm 3, at the time of 400mA / cm 2 22.1F / cm
Got three .
【００１３】（実験例２〜６）振動ボールミルでの粉砕
時間を変えた以外は実験例１と同様にして、種々の平均
粒径の活性炭基材を製造した。得られた活性炭基材に、
実験例１と同じ組成のバインダーを、活性炭基材の平均
粒径に応じて加え、実験例１同様にしてプレス成形した
ところ、いずれも成形性は良好であった。得られた板状
活性炭について、実験例１と同様にして、放電試験を行
い、静電容量を求めた。各実験例における粉砕時間、平
均粒径、およびバインダーの添加量の条件と、得られた
静電容量の結果を実験例１の結果とあわせて表１に示
す。(Experimental Examples 2 to 6) Activated carbon base materials having various average particle diameters were manufactured in the same manner as in Experimental Example 1 except that the grinding time in the vibrating ball mill was changed. On the obtained activated carbon base material,
When a binder having the same composition as in Experimental Example 1 was added according to the average particle size of the activated carbon base material and press-molded in the same manner as in Experimental Example 1, the moldability was good. The obtained plate-like activated carbon was subjected to a discharge test in the same manner as in Experimental Example 1 to determine the capacitance. Table 1 shows the conditions of the crushing time, the average particle size, and the amount of the binder added in each experimental example, and the results of the obtained capacitance together with the result of the experimental example 1.
【００１４】（比較例１）原料として平均粒径約２７μ
ｍの粉末フェノール樹脂を用い、粉砕をしない以外は実
験例１と同様にして、活性炭基材を得、平均粒径を測定
したところ、１９．０μｍであった。バインダーの添加
量を４０．８部とした以外は、実験例１と同様にして板
状活性炭を得、放電試験を行って静電容量を求めた。そ
の結果を表１に示す。(Comparative Example 1) As a raw material, the average particle size is about 27 μm.
An activated carbon base material was obtained in the same manner as in Experimental Example 1 except that the powdered phenolic resin of m was not pulverized, and the average particle size was measured to be 19.0 μm. A plate-like activated carbon was obtained in the same manner as in Experimental Example 1 except that the amount of the binder added was changed to 40.8 parts, and a discharge test was performed to determine the capacitance. Table 1 shows the results.
【００１５】[0015]
【表１】 [Table 1]
【００１６】表１の結果より、活性炭基材の平均粒径と
静電容量との関係をグラフに表したものを図３に示す。
この図から明らかなように、平均粒径１０μｍ以下では
高い静電容量が維持されるが、１０μｍを越えると静電
容量が著しく低下することが認められる。なお、比較例
１のように原料に粉末のフェノール樹脂を用いると粉砕
が不要であるが、平均粒径が１０μｍ以上となり、高い
静電容量が得られない。From the results in Table 1, a graph showing the relationship between the average particle size of the activated carbon base material and the electrostatic capacity is shown in FIG.
As is clear from this figure, when the average particle size is 10 μm or less, a high capacitance is maintained, but when it exceeds 10 μm, the capacitance is remarkably reduced. When powdered phenolic resin is used as the raw material as in Comparative Example 1, pulverization is unnecessary, but the average particle size is 10 μm or more, and high capacitance cannot be obtained.
【００１７】次に、本発明の第２の実施例として、図１
に示すように、活性炭基材を成形し、得られた成形体を
炭化した後に、再度２次活性化処理を施して板状活性炭
を製造し、活性炭基材の粒径と静電容量との関係を調べ
た。尚、本実施例において、１次活性化および２次活性
化として炭酸ガス中での熱処理を行った。また比較例２
として、原料に粉末状のフェノール樹脂を用いた場合に
ついても同様に調べた。Next, as a second embodiment of the present invention, FIG.
As shown in Fig. 1, after the activated carbon base material is molded and the obtained molded body is carbonized, the secondary activation treatment is performed again to produce a plate-shaped activated carbon. I investigated the relationship. In this example, heat treatment in carbon dioxide was performed as the primary activation and the secondary activation. Comparative Example 2
As the above, the same investigation was carried out when a powdered phenolic resin was used as a raw material.
【００１８】（実験例７）活性炭基材を板状に成形し、
炭化する工程までは実験例１と同様にして行い、得られ
た炭化処理品を、再び、炭酸ガス中で、８００℃で１０
時間熱処理して２次賦活した。ただし、バインダーの添
加量は４７．２部とした。実験例１と同様にして静電容
量を求めた。その結果を表２に示す。(Experimental Example 7) An activated carbon substrate was formed into a plate shape,
The steps up to the carbonization step are performed in the same manner as in Experimental Example 1, and the carbonized product obtained is again treated in carbon dioxide gas at 800 ° C. for 10
It was heat-treated for a time to be secondarily activated. However, the amount of binder added was 47.2 parts. The capacitance was determined in the same manner as in Experimental Example 1. The results are shown in Table 2.
【００１９】（実験例８〜１２）振動ボールミルでの粉
砕時間を変えた以外は実験例７と同様にして、種々の平
均粒径の活性炭基材を製造し、粒径に応じた量のバイン
ダーを添加して、プレス成形した。得られた板状活性炭
について、実験例１と同様にして静電容量を求めた。各
実験例における粉砕時間、平均粒径、およびバインダー
の添加量の条件と、得られた静電容量の結果を表２に示
す。(Experimental Examples 8 to 12) Activated carbon base materials having various average particle diameters were produced in the same manner as in Experimental Example 7 except that the crushing time in the vibrating ball mill was changed, and the binder was used in an amount corresponding to the particle diameter. Was added and press-molded. The capacitance of the obtained plate-like activated carbon was determined in the same manner as in Experimental Example 1. Table 2 shows the conditions of the grinding time, the average particle size, the amount of the binder added, and the obtained electrostatic capacity in each experimental example.
【００２０】（比較例２）原料として平均粒径約２７μ
ｍの粉末フェノール樹脂を用い、粉砕をしない以外は実
験例７と同様にして、活性炭基材を得、平均粒径を測定
したところ、１９．０μｍであった。バインダーの添加
量を４０．８部として、実験例７と同様にして板状活性
炭を得、実験例１と同様にして放電試験を行って静電容
量を求めた。その結果を表２に示す。(Comparative Example 2) As a raw material, the average particle size is about 27 μm.
An activated carbon base material was obtained in the same manner as in Experimental Example 7 except that the powdered phenolic resin of m was not pulverized, and the average particle size was measured. As a result, it was 19.0 μm. A plate-like activated carbon was obtained in the same manner as in Experimental Example 7 with the added amount of the binder being 40.8 parts, and a discharge test was performed in the same manner as in Experimental Example 1 to determine the capacitance. The results are shown in Table 2.
【００２１】[0021]
【表２】 [Table 2]
【００２２】表２の結果より、活性炭基材の平均粒径と
静電容量との関係をグラフに表したものを図４に示す。
この図から明らかなように、平均粒径１０μｍ以下では
高い静電容量が維持されるが、１０μｍを越えると静電
容量が著しく低下することが認められる。なお、比較例
２のように原料に粉末のフェノール樹脂を用いると粉砕
が不要であるが、平均粒径が１０μｍ以上となり、高い
静電容量が得られない。From the results shown in Table 2, a graph showing the relationship between the average particle size of the activated carbon base material and the electrostatic capacity is shown in FIG.
As is clear from this figure, when the average particle size is 10 μm or less, a high capacitance is maintained, but when it exceeds 10 μm, the capacitance is remarkably reduced. When powdered phenolic resin is used as the raw material as in Comparative Example 2, pulverization is unnecessary, but the average particle diameter is 10 μm or more, and high capacitance cannot be obtained.
【００２３】次に、本発明の第３の実施例として、図１
に示す工程において、１次活性化処理および２次活性化
処理として水蒸気中の熱処理を行って板状活性炭を製造
し、活性炭基材の粒径と静電容量との関係を調べた。ま
た比較例３として、原料に粉末状のフェノール樹脂を用
いた場合についても同様に調べた。Next, as a third embodiment of the present invention, FIG.
In the step shown in (1), heat treatment in steam was performed as the primary activation treatment and the secondary activation treatment to produce plate-like activated carbon, and the relationship between the particle size of the activated carbon base material and the capacitance was investigated. Further, as Comparative Example 3, the same investigation was carried out in the case where a powdery phenol resin was used as a raw material.
【００２４】（実験例１３）図１に示す工程において、
１次活性化処理として、水蒸気雰囲気中で８００℃、３
時間の熱処理を行って、平均粒径が０．８μｍの活性基
材を得、２次活性化処理として、水蒸気中で８００℃、
１０時間の熱処理を行った以外は実験例７と同様にして
板状活性炭を製造した。ただし、バインダーの添加量は
４６．８部とした。実験例１と同様にして静電容量を求
めた。その結果を表３に示す。Experimental Example 13 In the process shown in FIG.
As a primary activation treatment, 800 ° C in a steam atmosphere, 3
Heat treatment is performed for an hour to obtain an active substrate having an average particle size of 0.8 μm, and the secondary activation treatment is 800 ° C. in steam.
A plate-like activated carbon was produced in the same manner as in Experimental Example 7 except that the heat treatment was performed for 10 hours. However, the addition amount of the binder was 46.8 parts. The capacitance was determined in the same manner as in Experimental Example 1. Table 3 shows the results.
【００２５】（実験例１４〜１８）振動ボールミルでの
粉砕時間を変えた以外は実験例１３と同様にして、種々
の平均粒径の活性炭基材を製造し、粒径に応じた量のバ
インダーを添加して、プレス成形し、板状活性炭を得
た。実験例１と同様にして静電容量を求めた。各実験例
における粉砕時間、平均粒径、およびバインダーの添加
量の条件と、得られた静電容量の結果を表３に示す。(Experimental Examples 14 to 18) Activated carbon base materials having various average particle sizes were produced in the same manner as in Experimental Example 13 except that the crushing time in the vibrating ball mill was changed, and the amount of the binder was adjusted according to the particle size. Was added and press-molded to obtain plate-like activated carbon. The capacitance was determined in the same manner as in Experimental Example 1. Table 3 shows the conditions of the crushing time, the average particle size, and the amount of the binder added in each experimental example, and the obtained electrostatic capacity results.
【００２６】（比較例３）原料として平均粒径約２７μ
ｍの粉末フェノール樹脂を用い、粉砕をしない以外は実
験例１３と同様にして、活性炭基材を得、平均粒径を測
定したところ、１８．５μｍであった。またバインダー
の添加量を４０．２部として、実験例１３と同様にして
板状活性炭を得、実験例１と同様にして放電試験を行っ
て静電容量を求めた。その結果を表３に示す。(Comparative Example 3) As a raw material, the average particle size is about 27 μm.
An activated carbon base material was obtained in the same manner as in Experimental Example 13 except that the powdered phenolic resin of m was not pulverized, and the average particle size was measured to be 18.5 μm. Further, with the addition amount of the binder being 40.2 parts, a plate-like activated carbon was obtained in the same manner as in Experimental Example 13, and a discharge test was performed in the same manner as in Experimental Example 1 to determine the capacitance. Table 3 shows the results.
【００２７】[0027]
【表３】 [Table 3]
【００２８】表３の結果より、活性炭基材の平均粒径と
静電容量との関係をグラフに表したものを図５に示す。
この図から明らかなように、平均粒径１０μｍ以下では
高い静電容量が維持されるが、１０μｍを越えると静電
容量が著しく低下することが認められる。また図４と図
５とを比較すると、１次賦活および２次賦活を炭酸ガス
中で行った場合（図４）の結果と、１次賦活および２次
賦活を水蒸気中で行った場合（図５）の結果との間に大
きな差は認められなかった。なお、比較例２のように原
料に粉末のフェノール樹脂を用いると粉砕が不要である
が、平均粒径が１０μｍ以上となり、高い静電容量が得
られない。From the results shown in Table 3, a graph showing the relationship between the average particle size of the activated carbon base material and the electrostatic capacity is shown in FIG.
As is clear from this figure, when the average particle size is 10 μm or less, a high capacitance is maintained, but when it exceeds 10 μm, the capacitance is remarkably reduced. Further, comparing FIG. 4 and FIG. 5, the results of the case where primary activation and secondary activation are carried out in carbon dioxide gas (FIG. 4) and the case where primary activation and secondary activation are carried out in water vapor (FIG. No significant difference was observed with the result of 5). When powdered phenolic resin is used as the raw material as in Comparative Example 2, pulverization is unnecessary, but the average particle diameter is 10 μm or more, and high capacitance cannot be obtained.
【００２９】次に、本発明の第４の実施例として、図１
に示す工程において、１次活性化処理として空気中での
酸化熱処理を行い、２次活性化処理として空気中での酸
化熱処理を行った後、窒素雰囲気での熱処理を行って板
状活性炭を製造し、活性炭基材の粒径と静電容量との関
係を調べた。また比較例４として、原料に粉末状のフェ
ノール樹脂を用いた場合についても同様に調べた。Next, as a fourth embodiment of the present invention, FIG.
In the process shown in (1), the oxidative heat treatment in air is performed as the primary activation treatment, the oxidative heat treatment in the air is performed as the secondary activation treatment, and then the heat treatment is performed in the nitrogen atmosphere to produce the plate-like activated carbon. Then, the relationship between the particle size of the activated carbon base material and the electrostatic capacity was investigated. Further, as Comparative Example 4, the same investigation was carried out in the case where a powdery phenolic resin was used as a raw material.
【００３０】（実験例１９）図１に示す工程において、
１次活性化処理として、空気中で３５０℃、１時間の酸
化熱処理を行って、平均粒径が０．８μｍの活性基材を
得、２次活性化処理として、空気中で３５０℃、１時間
の酸化熱処理に引続き窒素中９００℃、０．５時間の熱
処理を行った以外は実験例７と同様にして板状活性炭を
製造した。ただし、バインダーの添加量は４７．４部と
した。実験例１と同様にして静電容量を求めた。その結
果を表４に示す。Experimental Example 19 In the process shown in FIG.
As a primary activation treatment, an oxidative heat treatment is performed in air at 350 ° C. for 1 hour to obtain an active base material having an average particle diameter of 0.8 μm. A plate-like activated carbon was produced in the same manner as in Experimental Example 7, except that the heat treatment was carried out at 900 ° C. for 0.5 hours in nitrogen subsequently to the heat treatment for an hour. However, the amount of binder added was 47.4 parts. The capacitance was determined in the same manner as in Experimental Example 1. The results are shown in Table 4.
【００３１】（実験例２０〜２４）振動ボールミルでの
粉砕時間を変えた以外は実験例１９と同様にして、種々
の平均粒径の活性炭基材を製造し、粒径に応じた量のバ
インダーを添加して、プレス成形し、板状活性炭を得
た。実験例１と同様にして静電容量を求めた。各実験例
における粉砕時間、平均粒径、およびバインダーの添加
量の条件と、得られた静電容量の結果を表４に示す。(Experimental Examples 20 to 24) Activated carbon base materials having various average particle sizes were produced in the same manner as in Experimental Example 19 except that the crushing time in the vibrating ball mill was changed, and the binder was used in an amount corresponding to the particle size. Was added and press-molded to obtain plate-like activated carbon. The capacitance was determined in the same manner as in Experimental Example 1. Table 4 shows the conditions of the crushing time, the average particle size, the amount of the binder added, and the obtained electrostatic capacity in each experimental example.
【００３２】（比較例４）原料として平均粒径約２７μ
ｍの粉末フェノール樹脂を用い、粉砕をしない以外は実
験例１９と同様にして、活性炭基材を得、平均粒径を測
定したところ、１８．０μｍであった。またバインダー
の添加量を４１．０部として、実験例１９と同様にして
板状活性炭を得、実験例１と同様にして放電試験を行っ
て静電容量を求めた。その結果を表４に示す。(Comparative Example 4) As a raw material, the average particle size is about 27 μm.
An activated carbon base material was obtained in the same manner as in Experimental Example 19 except that the powdered phenolic resin of m was not pulverized, and the average particle size was measured, and it was 18.0 μm. Further, with the addition amount of the binder being 41.0 parts, a plate-like activated carbon was obtained in the same manner as in Experimental Example 19, and a discharge test was performed in the same manner as in Experimental Example 1 to determine the capacitance. The results are shown in Table 4.
【００３３】[0033]
【表４】 [Table 4]
【００３４】表４の結果より、活性炭基材の平均粒径と
静電容量との関係をグラフに表したものを図６に示す。
この図から明らかなように、平均粒径１０μｍ以下では
高い静電容量が維持されるが、１０μｍを越えると静電
容量が著しく低下することが認められる。また図４また
は図５と図６とを比較すると、１次活性化処理および２
次活性化処理として炭酸ガス中賦活または水蒸気中賦活
を行った場合（図４または図５）よりも、１次活性化処
理および２次活性化処理として空気中での酸化熱処理を
行った場合（図６）の方が、得られる静電容量のレベル
が高いことが認められた。From the results of Table 4, a graph showing the relationship between the average particle size of the activated carbon base material and the electrostatic capacity is shown in FIG.
As is clear from this figure, when the average particle size is 10 μm or less, a high capacitance is maintained, but when it exceeds 10 μm, the capacitance is remarkably reduced. In addition, comparing FIG. 4 or FIG. 5 with FIG.
When the oxidation heat treatment in air is performed as the primary activation treatment and the secondary activation treatment as compared with the case where activation in carbon dioxide gas or water vapor is performed as the secondary activation treatment (FIG. 4 or 5) ( It was confirmed that the obtained capacitance level was higher in FIG. 6).
【００３５】[0035]
【発明の効果】以上説明したように本発明によれば、炭
素化合物を炭化処理して得た炭化物を活性化処理を施し
た後に粉砕して活性炭基材とし、該活性炭基材にバイン
ダーを加え板状に成形して成形体とし、該成形体を炭化
処理して板状活性炭を製造する方法において、活性炭基
材の平均粒径を１０μｍ以下とすることによって、高い
静電容量を実現できる電気二重層コンデンサー用の活性
炭電極を得ることができる。As described above, according to the present invention, a carbonized product obtained by carbonizing a carbon compound is subjected to activation treatment and then crushed to obtain an activated carbon base material, and a binder is added to the activated carbon base material. In a method for producing a plate-shaped activated carbon by forming the plate-shaped into a molded body and carbonizing the molded body, it is possible to realize high capacitance by setting the average particle diameter of the activated carbon base material to 10 μm or less. An activated carbon electrode for a double layer capacitor can be obtained.
【００３６】また、炭素化合物を炭化処理して得た炭化
物を活性化処理を施した後に粉砕して平均粒径が１０μ
ｍ以下の活性炭基材とし、該活性炭基材にバインダーを
加え板状に成形して成形体とし、該成形体を炭化処理し
た後に再度活性化処理を施すと、活性炭基材の粒径によ
る効果と２次活性化処理による効果との相乗効果によ
り、高い静電容量を得ることができる。活性化処理とし
て空気中での酸化処理を行なうと、静電容量のレベルを
さらに高めることができる。The carbide obtained by carbonizing the carbon compound is activated and then pulverized to obtain an average particle diameter of 10 μm.
When an activated carbon base material having a particle size of m or less is added, and a binder is added to the activated carbon base material to form a molded body, and the molded body is carbonized and then activated again, the effect of the particle size of the activated carbon base material is obtained. A high electrostatic capacitance can be obtained by the synergistic effect of the above and the effect of the secondary activation treatment. When the oxidation treatment in air is performed as the activation treatment, the level of capacitance can be further increased.
【図１】 本発明の活性炭電極の製造方法の一例を示す
工程図である。FIG. 1 is a process drawing showing an example of a method for manufacturing an activated carbon electrode of the present invention.
【図２】 本発明の実施例において作製した活性炭電極
の断面図である。FIG. 2 is a cross-sectional view of an activated carbon electrode produced in an example of the present invention.
【図３】 本発明の第１の実施例の結果を示し、活性炭
基材の平均粒径と活性炭電極の静電容量との関係を示す
グラフである。FIG. 3 is a graph showing the results of the first example of the present invention and showing the relationship between the average particle size of the activated carbon base material and the electrostatic capacity of the activated carbon electrode.
【図４】 本発明の第２の実施例の結果を示し、活性炭
基材の平均粒径と活性炭電極の静電容量との関係を示す
グラフである。FIG. 4 is a graph showing the results of the second example of the present invention and showing the relationship between the average particle size of the activated carbon base material and the electrostatic capacitance of the activated carbon electrode.
【図５】 本発明の第３の実施例の結果を示し、活性炭
基材の平均粒径と活性炭電極の静電容量との関係を示す
グラフである。FIG. 5 is a graph showing the results of the third example of the present invention and showing the relationship between the average particle size of the activated carbon base material and the electrostatic capacitance of the activated carbon electrode.
【図６】 本発明の第４の実施例の結果を示し、活性炭
基材の平均粒径と活性炭電極の静電容量との関係を示す
グラフである。FIG. 6 is a graph showing the results of Example 4 of the present invention and showing the relationship between the average particle size of the activated carbon base material and the electrostatic capacitance of the activated carbon electrode.
【図７】 従来の活性炭および活性炭電極の製造工程を
説明する図である。FIG. 7 is a diagram illustrating a conventional manufacturing process of activated carbon and an activated carbon electrode.
１……活性炭電極、２……ガスケット、３……集電極、
４……セパレータ。1 ... Activated carbon electrode, 2 ... Gasket, 3 ... Collection electrode,
4 ... Separator.
フロントページの続き (72)発明者 中村 章寛 山梨県北巨摩郡高根町下黒沢3054−３ 日 本酸素株式会社山梨研究所内 (72)発明者 丸茂 信一 山梨県北巨摩郡高根町下黒沢3054−３ 日 本酸素株式会社山梨研究所内 (72)発明者 宮川 俊哉 山梨県北巨摩郡高根町下黒沢3054−３ 日 本酸素株式会社山梨研究所内Front Page Continuation (72) Inventor Akihiro Nakamura 3054-3 Shimokurosawa Shimokurosawa, Takane-cho, Kitakoma-gun, Yamanashi Prefecture Yamanashi Research Institute (72) Inventor Shinichi Marumo 3054-3 Shimokurosawa, Takane-cho, Kitakoma-gun Yamanashi Nihon Oxygen Yamanashi Laboratory Co., Ltd. (72) Inventor Toshiya Miyagawa 3054-3 Shimokurosawa Shimokurosawa, Takane-cho, Kitakoma-gun, Yamanashi Nihon Oxygen Co., Ltd. Yamanashi Laboratory
Claims (4)
活性化処理を施した後に粉砕して活性炭基材とし、該活
性炭基材にバインダーを加え板状に成形して成形体と
し、該成形体を炭化処理して板状活性炭を製造する方法
において、前記活性炭基材の平均粒径が１０μｍ以下で
あることを特徴とする電気二重層コンデンサー用活性炭
電極の製造方法。1. A carbonized product obtained by carbonizing a carbon compound is subjected to activation treatment and then pulverized to obtain an activated carbon base material, and a binder is added to the activated carbon base material to form a plate-like body, A method for producing a plate-like activated carbon by carbonizing a formed body, wherein the activated carbon base material has an average particle size of 10 μm or less, and a method for producing an activated carbon electrode for an electric double layer capacitor.
活性化処理を施した後に粉砕して平均粒径が１０μｍ以
下の活性炭基材とし、該活性炭基材にバインダーを加え
板状に成形して成形体とし、該成形体を炭化処理した後
に再度活性化処理を施すことを特徴とする電気二重層コ
ンデンサー用活性炭電極の製造方法。2. A carbonized product obtained by carbonizing a carbon compound is subjected to activation treatment and then pulverized to obtain an activated carbon base material having an average particle size of 10 μm or less, and a binder is added to the activated carbon base material to form a plate shape. A method for producing an activated carbon electrode for an electric double layer capacitor, which comprises subjecting the formed body to a carbonization treatment, and then subjecting the formed body to a carbonization treatment and then an activation treatment again.
気中または水蒸気雰囲気中のいずれかでの熱処理による
賦活処理を行なうことを特徴とする請求項２記載の電気
二重層コンデンサー用活性炭電極の製造方法。3. The method for producing an activated carbon electrode for an electric double layer capacitor according to claim 2, wherein the activation treatment is an activation treatment by heat treatment in either a carbon dioxide gas atmosphere or a steam atmosphere. .
処理を行なうことを特徴とする請求項２記載の電気二重
層コンデンサー用活性炭電極の製造方法。4. The method for producing an activated carbon electrode for an electric double layer capacitor according to claim 2, wherein the activation treatment is an oxidation treatment in air.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6248186A JPH08115856A (en) | 1994-10-13 | 1994-10-13 | Method for manufacturing activated carbon electrode for electrical double-layer capacitor |
| US08/523,622 US5603867A (en) | 1994-09-09 | 1995-09-05 | Method of production for active carbon electrode for use as electrical double layer condenser and active carbon electrode obtained thereby |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6248186A JPH08115856A (en) | 1994-10-13 | 1994-10-13 | Method for manufacturing activated carbon electrode for electrical double-layer capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08115856A true JPH08115856A (en) | 1996-05-07 |
Family
ID=17174489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6248186A Withdrawn JPH08115856A (en) | 1994-09-09 | 1994-10-13 | Method for manufacturing activated carbon electrode for electrical double-layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08115856A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008007387A (en) * | 2006-06-30 | 2008-01-17 | Kansai Coke & Chem Co Ltd | Method and apparatus for highly purifying activated carbon |
| CN105776205A (en) * | 2016-03-31 | 2016-07-20 | 神华集团有限责任公司 | Preparation method of coal-based activated carbon for flue gas internal circulation |
-
1994
- 1994-10-13 JP JP6248186A patent/JPH08115856A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008007387A (en) * | 2006-06-30 | 2008-01-17 | Kansai Coke & Chem Co Ltd | Method and apparatus for highly purifying activated carbon |
| CN105776205A (en) * | 2016-03-31 | 2016-07-20 | 神华集团有限责任公司 | Preparation method of coal-based activated carbon for flue gas internal circulation |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20020115 |