JP2011111335A - Nitrogen-containing carbon porous body and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nitrogen-containing carbon porous body having a large specific surface area and a high ratio of nitrogen atoms. <P>SOLUTION: The method for producing such a nitrogen-containing carbon porous body includes a step of heat-treating a nitrogen-containing carbon material at 300-500°C in the presence of an oxygen-containing gas. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a nitrogen-containing carbon porous body and a method for producing the same.

  Conventionally, carbon porous bodies have been used as adsorbents, catalyst carriers, and the like, taking advantage of their high specific surface area. In addition, because of its excellent conductivity and the like, recently it has been used and studied for electronic materials such as capacitors and fuel cells that require a high specific surface area and conductivity.

  A carbon porous body is a porous body having a skeleton formed of carbon atoms. By providing a high specific surface area by gas activation treatment or chemical activation treatment, the performance as an adsorbent, catalyst, capacitor, etc. will be improved. Is being considered. On the other hand, a nitrogen-containing carbon porous body having improved adsorption characteristics by containing nitrogen in the carbon porous body and a method for producing the same have been proposed (for example, Patent Document 1 and Patent Document 2). In addition, it is known that if a carbon material used in the field of electronic devices such as capacitors can contain nitrogen atoms, the capacity per surface area is increased (for example, Patent Document 3 and Patent Document 4). As a method for producing such a nitrogen-containing carbon material, a method of heating at 700 to 900 ° C. in the presence of water vapor or carbon dioxide has been proposed (for example, Patent Document 5).

Japanese Patent Application Laid-Open No. 2004-165857 JP 2006-124250 A Japanese Patent Laid-Open No. 9-27317 JP 2005-239456 A JP 2008-239418 A

  As described above, the nitrogen-containing carbon porous body has a large specific surface area and is an excellent material containing a certain amount of nitrogen atoms. However, the specific surface area of the nitrogen-containing carbon porous body can be further increased and the nitrogen atom content can be increased. Development of manufacturing technology that can be further increased is desired.

  This invention is made | formed in view of the said situation, and makes it a main objective to provide the manufacturing method of a nitrogen containing carbon porous body with a large specific surface area and a high content rate of a nitrogen atom.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have surprisingly found that the nitrogen-containing carbon material is heat-treated at 300 to 500 ° C. in the presence of an oxygen-containing gas. It has been found that a nitrogen-containing carbon porous body having a large surface area and a high nitrogen atom content ratio can be obtained, and has led to the present invention.

That is, the present invention is as follows.
[1]
The manufacturing method of a nitrogen containing carbon porous body including the process of heat-processing a nitrogen containing carbon material at 300-500 degreeC in presence of oxygen containing gas.
[2]
The method for producing a nitrogen-containing carbon porous material according to [1], wherein the nitrogen-containing carbon porous material satisfies the following conditions (1) and (2):
(1) The atomic ratio (N / C) of nitrogen atoms to carbon atoms in the nitrogen-carbon porous body is 0.25 or more.
(2) The specific surface area by BET method is 350 m < ² > / g or more.
[3]
The method for producing a nitrogen-containing carbon porous material according to [1] or [2], wherein the nitrogen-containing carbon material is obtained by carbonizing at least azulmic acid.
[4]
A nitrogen-containing porous carbon material that satisfies the following conditions (1) and (2);
(1) The atomic ratio (N / C) of nitrogen atoms to carbon atoms in the nitrogen-carbon porous body is 0.25 or more.
(2) The specific surface area by BET method is 350 m < ² > / g or more.

  According to the method for producing a nitrogen-containing carbon porous body of the present invention, a nitrogen-containing carbon porous body having a large specific surface area and a high content ratio of nitrogen atoms can be produced.

A graph in which the specific surface area is plotted on the horizontal axis and the N / C value is plotted on the vertical axis for the nitrogen-containing carbon porous body of Production Example 1, Examples 1, 2 and Comparative Examples 1, 3-7. is there.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are exemplifications for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

  The manufacturing method of the nitrogen-containing carbon porous body of this Embodiment includes the process of heat-processing a nitrogen-containing carbon material at 300-500 degreeC in presence of oxygen-containing gas. The nitrogen-containing carbon porous body obtained in this way has not only a large specific surface area but also a high content ratio of nitrogen atoms.

  As a method for increasing the specific surface area of the nitrogen-containing carbon material, heating the nitrogen-containing carbon material at a high temperature of 700 ° C. or higher in the presence of water vapor or carbon dioxide has been conventionally performed. According to this method, although the specific surface area of the nitrogen-containing carbon material increases, on the other hand, many nitrogen atoms escape from the nitrogen-containing carbon material, and as a result, the nitrogen content of the nitrogen-containing carbon material decreases. The inventors have determined. Furthermore, it has been found that when the nitrogen-containing carbon material obtained by such a manufacturing method is used as an electrode material of a capacitor, the capacity does not increase greatly. The reason for this is not clear, but while there is probably an increase in capacity due to an increase in specific surface area, the pseudo capacity expressed by nitrogen atoms decreases due to a decrease in the number of nitrogen atoms, resulting in a large capacity. Did not increase. As a result of intensive studies based on these findings, surprisingly, the nitrogen-containing carbon material is not only large in specific surface area but also contains nitrogen atoms by heat treatment at 300 to 500 ° C. in the presence of an oxygen-containing gas. It has been found that a nitrogen-containing carbon porous body having a high amount can be obtained. Furthermore, it has been found that an electrode material such as a capacitor using the nitrogen-containing porous carbon obtained in the present embodiment has particularly excellent electrical characteristics.

  The nitrogen-containing carbon material used in the present embodiment is a carbon material containing nitrogen. Nitrogen-containing carbon materials include, for example, a method of polymerizing a low-molecular nitrogen-containing organic compound as a raw material and carbonizing the obtained polymer, and chemical vapor deposition (CVD) using a low-molecular nitrogen-containing organic compound as a raw material. ), A method in which a polymer is impregnated or reacted with a low-molecular nitrogen-containing organic compound and then carbonized, a method in which a natural product containing nitrogen is carbonized, and a carbonized product is treated with ammonia. It can be produced by a method of producing by post-treatment such as ammoxidation treatment.

  Specifically, chemical vapor deposition of nitrogen-containing organic compounds such as pyrrole, acetonitrile, 2,3,6,7-tetracyano-1,4,5,8-tetraazanaphthalene, melamine resin, urea resin, A method of carbonizing aniline resin, polyacrylonitrile, azulmic acid, melem polymer, polypyrrole, polyimide, etc., a method of mixing a phenol resin or furan resin with phthalocyanine in a solvent and evaporating the solvent, followed by carbonization It can be produced by a method of carbonizing beans, a method of reacting an ammonia gas and an oxygen-containing gas with a carbon material such as activated carbon, or the like. From the viewpoint of obtaining a nitrogen-containing carbon porous body having a higher nitrogen atom content, a nitrogen-containing carbon material having a higher nitrogen content is preferred. Examples of the nitrogen-containing carbon material having a high nitrogen content include a nitrogen-containing carbon material produced by carbonizing azulmic acid or melem polymer, and more preferably a nitrogen-containing carbon material produced by carbonizing azulmic acid. It is a carbon material. Regarding azulmic acid, Patent Document 5, Angew. Chem. 72, 379-384 (1960), vacuum science, 16, 64-72 (1969), and the like.

  The nitrogen-containing carbon material used in the present embodiment is preferably heat-treated as described above. Thereby, the nitrogen-containing carbon material can be carbonized. Although the temperature of heat processing is not specifically limited, Preferably it is 300-1500 degreeC, More preferably, it is 600-1200 degreeC, More preferably, it is 700-1000 degreeC.

  As an example of the nitrogen-containing carbon material used in the present embodiment, a nitrogen-containing carbon material obtained by carbonizing azulmic acid will be described. The azulmic acid that can be used in the present embodiment is not limited to the following, but is a hydrocyanic acid polymer obtained by polymerizing a raw material mainly containing hydrocyanic acid. Here, as the raw material containing hydrocyanic acid, the abundance ratio of the other polymerizable substance to hydrocyanic acid is preferably 40% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. Particularly preferably, it is 1% by mass or less.

  Azulmic acid can be obtained by polymerizing hydrocyanic acid by various methods. The polymerization method is not particularly limited, and a known method can be used. For example, by heating or leaving a hydrocyanic acid solution or liquefied hydrocyanic acid for a long time, adding a base, irradiating light, emitting high energy, performing various discharges, or electrolyzing a potassium cyanide aqueous solution Can be manufactured.

The base used in the method for polymerizing hydrocyanic acid in the presence of a base is not particularly limited as long as hydrocyanic acid can be polymerized. Examples of the base include sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, organic base, ammonia, aqueous ammonia and the like. Examples of the organic base include primary amine R ¹ NH ₂ , secondary amine R ¹ R ² NH, tertiary amine R ¹ R ² R ³ N, quaternary amine R ¹ R ² R ³ R ⁴ N ^{+ and the} like. Wherein R ^{1 to} R ⁴ are the same or different and each represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, a hexyl group, or a group obtained by combining them. R ¹ to R ⁴ may contain a functional group.). Of these, aliphatic or cycloaliphatic tertiary amines are preferred. For example, trimethylamine, triethylamine, tripropylamine, tributylamine, dicyclohexylmethylamine, tetramethylammonium hydroxide, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), etc. Can be mentioned. Azulmic acid can also be produced by recovering from the purifying process of cyanuric acid by-produced in an ammonic acid oxidizing process such as propylene.

  Next, the process of heat-treating the nitrogen-containing carbon material at 300 to 500 ° C. in the presence of an oxygen-containing gas will be described. The oxygen-containing gas may be a gas containing at least oxygen, and usually air can be used. As the oxygen-containing gas, a gas diluted by adding nitrogen gas, helium gas, argon gas, or neon gas to air may be used, or oxygen gas may be further added to increase the oxygen concentration. The oxygen concentration of the oxygen-containing gas is not particularly limited, but is preferably 5 to 30% from the viewpoint of production efficiency and safety. From the viewpoint of energy saving, it is more preferable to use air as it is.

  The temperature of heat processing is 300-500 degreeC, Preferably it is 320-480 degreeC, More preferably, it is 380-460 degreeC. When the temperature is lower than 300 ° C., the specific surface area of the obtained nitrogen-containing carbon porous body becomes low. When the temperature is higher than 500 ° C., the nitrogen-containing carbon material itself burns. The time for the heat treatment is not particularly limited, and is, for example, 5 minutes to 10 hours, preferably 15 minutes to 3 hours. The pressure of the heat treatment is not particularly limited, and is, for example, 0.01 to 5 MPa, preferably 0.05 to 1 MPa, more preferably 0.08 to 0.3 MPa, and further preferably 0.09 to 0.00. 15 MPa.

  The method for the heat treatment is not particularly limited, and for example, a heating furnace can be used. As the heating furnace, a rotary kiln, tunnel furnace, tubular furnace, fluidized firing furnace, muffle furnace, or the like can be used.

The nitrogen-containing carbon porous body obtained in the production method of the present embodiment can be preferably a nitrogen-containing carbon porous body that satisfies the following conditions (1) and (2).
(1) The atomic ratio (N / C) of nitrogen atoms to carbon atoms in the nitrogen-containing carbon porous body is 0.25 or more.
(2) The specific surface area by BET method is 350 m ² / g or more.

A nitrogen-containing carbon porous body obtained by the manufacturing method of the present embodiment will be described.
<Condition (1)>
The N / C value is preferably 0.25 or more, more preferably 0.27 or more, and further preferably 0.30 or more, from the viewpoint of adsorption capacity and capacitor capacity. Further, the N / C value is preferably 1.00 or less, more preferably 0.80 or less, and further preferably 0.60 or less. The abundance ratio (N / C value) of nitrogen atoms relative to carbon atoms in condition (1) can be measured by the method described in the examples described later.

<Condition (2)>
The specific surface area according to the BET method is 350 m ² / g or more, preferably 400 m ² / g or more. Moreover, 2500 m < ² > / g or less is preferable and 2000 m < ² > / g or less is more preferable. According to this Embodiment, since the specific surface area of a nitrogen-containing carbon porous body can be enlarged in the said range, the more excellent adsorption ability can be exhibited. The specific surface area of the condition (2) can be measured by the method described in Examples described later.

  As a preferred embodiment of the nitrogen-containing carbon porous body, it is preferable to have a layered structure. In the case of a nitrogen-containing carbon porous body having a layered structure, an X-ray diffraction diagram obtained using CuKα rays as an X-ray source has a peak at a diffraction angle (2θ) of 23.5 to 25.5 °. More preferably, it has a peak at a position of 23.7 to 25.0 °, and more preferably has a peak at 23.9 to 24.5 °. Moreover, it is preferable to have a peak in the position of 43.0-46.0 degrees of the diffraction angle (2 (theta)) of a nitrogen-containing carbon porous body, and it is more preferable to have a peak in the position of 44.0-45.5. Furthermore, it is preferable that the peak of 23.5 to 25.5 ° has the highest intensity when the diffraction angle (2θ) is 15 to 50 °.

  Since the nitrogen-containing carbon porous body obtained by the production method of the present embodiment has a large specific surface area and a large nitrogen content, it can be used as an adsorbent and a catalyst carrier. Moreover, since it is excellent in electrical characteristics such as conductivity, it can be used as an electrode for capacitors, an electrode catalyst for fuel cells, and the like.

The nitrogen-containing carbon porous body according to the present embodiment is preferably a nitrogen-containing carbon porous body that satisfies the above conditions (1) and (2).
(1) The atomic ratio (N / C) of nitrogen atoms to carbon atoms in the nitrogen-containing carbon porous body is 0.25 or more.
(2) The specific surface area by BET method is 350 m ² / g or more.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, these are examples, and the present invention is not limited to the following examples.

<Analysis method>
(CHN analysis)
Using a MICRO CORDER JM10 manufactured by J Science Lab Co., Ltd., a sample of 2500 μg was filled in a sample table and subjected to CHN analysis. The sample furnace was set to 950 ° C., the combustion furnace (copper oxide catalyst) was set to 850 ° C., and the reduction furnace (consisting of a silver grain + copper oxide zone, a reduced copper zone, and a copper oxide zone) was set to 550 ° C. The flow rate of oxygen was set to 15 mL / min, and the flow rate of helium was set to 150 mL / min. A heat conduction detector (TCD) was used as a detector. Calibration was performed by the method described in the manual using Antipyrine.

(Measurement method of specific surface area)
The specific surface area was measured by the BET method using AUTOSORB-3-MP manufactured by Yuasa Ionics. Specifically, the sample was vacuum degassed at 300 ° C. for 8 hours and measured. The nitrogen adsorption isotherm was measured at the liquid nitrogen temperature, and the specific surface area was measured.

[Production Example 1]
<Manufacture of nitrogen-containing carbon materials>
An aqueous solution in which 150 g of hydrocyanic acid was dissolved in 350 g of water was prepared, and 120 g of a 25% aqueous ammonia solution was added over 10 minutes while stirring to obtain a mixed aqueous solution. When the obtained mixed aqueous solution was heated to 35 ° C. to initiate polymerization, a blackish brown polymer started to precipitate, and the temperature gradually increased to 45 ° C. After 2 hours from the start of the reaction, a 30% by mass aqueous solution of hydrocyanic acid was added to the reaction solution at a rate of 200 g / h over 4 hours. During the addition, the reaction temperature was controlled to be kept at 50 ° C. When the cooling was stopped after the addition was completed, the temperature of the reaction solution rose to 90 ° C., stayed at 90 ° C. for about 1 hour, and then the temperature gradually dropped. Thereafter, the reaction was carried out for 100 hours. After completion of the reaction, the resulting black precipitate was separated by filtration. The yield at this time was 97% (mass ratio). After washing with water, it was dried in a drier at 120 ° C. for 5 hours to obtain azulmic acid.

  10 g of the obtained azulmic acid was filled in a quartz tube having an inner diameter of 25 mm, and 250 Ncc / min. In a nitrogen stream, the temperature was raised to 800 ° C. over 1 hour, held at 800 ° C. for 1 hour and carbonized to obtain a nitrogen-containing carbon material. Table 1 shows the specific surface area of the obtained nitrogen-containing carbon material and the ratio of the number of nitrogen atoms to carbon atoms (N / C value).

[Example 1]
3 g of the nitrogen-containing carbon material obtained in Production Example 1 was heated to 350 ° C. over 0.5 hours under atmospheric pressure in an air atmosphere, subjected to heat treatment at 350 ° C. for 0.5 hours, and then cooled. Thus, a nitrogen-containing carbon porous body was obtained. Table 1 shows the specific surface area of the obtained nitrogen-containing carbon porous material and the ratio of the number of nitrogen atoms to carbon atoms (N / C value).

[Example 2]
3 g of the nitrogen-containing carbon material obtained in Production Example 1 was heated to 450 ° C. in an air atmosphere at atmospheric pressure over 0.5 hours, subjected to heat treatment at 450 ° C. for 0.5 hours, and then cooled. Thus, a nitrogen-containing carbon porous body was obtained. Table 1 shows the specific surface area of the obtained nitrogen-containing carbon porous material and the ratio of the number of nitrogen atoms to carbon atoms (N / C value).

[Comparative Example 1]
3 g of the nitrogen-containing carbon material obtained in Production Example 1 was heated to 250 ° C. in an air atmosphere at atmospheric pressure over 0.5 hours, subjected to heat treatment at 250 ° C. for 0.5 hours, and then cooled down. Thus, a nitrogen-containing carbon porous body was obtained. Table 1 shows the specific surface area of the obtained nitrogen-containing carbon porous material and the ratio of the number of nitrogen atoms to carbon atoms (N / C value).

[Comparative Example 2]
3 g of the nitrogen-containing carbon material obtained in Production Example 1 was heated to 580 ° C. in an air atmosphere at atmospheric pressure over 0.5 hours, heated at 580 ° C. for 0.5 hours, and then cooled. When trying to obtain a nitrogen-containing carbon porous body, the sample almost burned and was hardly recovered.

[Comparative Example 3]
A quartz tube having an inner diameter of 25 mm was filled with 3 g of the nitrogen-containing carbon material obtained in Production Example 1, and 200 Ncc / min. The temperature was raised to 350 ° C. in a nitrogen stream of 0.5 hours over the course of 0.5 hours, and when the temperature reached 350 ° C., 400 Ncc / min. The mixed gas stream of carbon dioxide and nitrogen (50% by volume of carbon dioxide) was switched to heat treatment for 0.5 hours, and then the temperature was lowered to obtain a nitrogen-containing carbon porous body. Table 1 shows the specific surface area of the obtained nitrogen-containing carbon porous material and the ratio of the number of nitrogen atoms to carbon atoms (N / C value).

[Comparative Example 4]
A quartz tube having an inner diameter of 25 mm was filled with 3 g of the nitrogen-containing carbon material obtained in Production Example 1, and 200 Ncc / min. The temperature was raised to 800 ° C. over 1 hour in a nitrogen stream, and when the temperature reached 800 ° C., 400 Ncc / min. The mixed gas stream of carbon dioxide and nitrogen (50% by volume of carbon dioxide) was switched to heat treatment for 2 hours, and then the temperature was lowered to obtain a nitrogen-containing carbon porous body. Table 1 shows the specific surface area of the obtained nitrogen-containing carbon porous material and the ratio of the number of nitrogen atoms to carbon atoms (N / C value).

[Comparative Example 5]
A quartz tube having an inner diameter of 25 mm was filled with 3 g of the nitrogen-containing carbon material obtained in Production Example 1, and 200 Ncc / min. In a nitrogen stream, the temperature was raised to 900 ° C. over 1 hour, and when the temperature reached 900 ° C., 400 Ncc / min. The mixed gas stream of carbon dioxide and nitrogen (50% by volume of carbon dioxide) was switched to heat treatment for 2 hours, and then the temperature was lowered to obtain a nitrogen-containing carbon porous body. Table 1 shows the specific surface area of the obtained nitrogen-containing carbon porous material and the ratio of the number of nitrogen atoms to carbon atoms (N / C value).

[Comparative Example 6]
3 g of the nitrogen-containing carbon material obtained in Production Example 1 was filled in a quartz tube having an inner diameter of 25 mm, and 300 Ncc / min. The temperature was raised to 350 ° C. in a nitrogen stream of 0.5 hours, and when the temperature reached 350 ° C., switching to a nitrogen gas stream in which pure water was bubbled was performed, followed by heat treatment for 0.5 hours. The temperature was lowered to obtain a nitrogen-containing carbon porous body. The water vapor concentration at this time was 3 vol% calculated from the amount of decrease in pure water. Table 1 shows the specific surface area of the obtained nitrogen-containing carbon porous material and the ratio of the number of nitrogen atoms to carbon atoms (N / C value).

[Comparative Example 7]
3 g of the nitrogen-containing carbon material obtained in Production Example 1 was filled in a quartz tube having an inner diameter of 25 mm, and 300 Ncc / min. In a nitrogen stream, the temperature was raised to 750 ° C. over 1 hour, and when the temperature reached 750 ° C., switching to a nitrogen gas stream in which pure water was bubbled was performed, followed by a heat treatment for 4 hours, and then the temperature was lowered and the nitrogen was lowered. A containing carbon porous body was obtained. The water vapor concentration at this time was 3 vol% calculated from the amount of decrease in pure water. Table 1 shows the specific surface area of the obtained nitrogen-containing carbon porous material and the ratio of the number of nitrogen atoms to carbon atoms (N / C value).

  FIG. 1 plots the specific surface area on the horizontal axis and the N / C value on the vertical axis for the nitrogen-containing carbon material of Production Example 1, the nitrogen-containing carbon porous bodies of Examples 1 and 2 and Comparative Examples 1 and 3-7. It is a graph. From the above, it was confirmed that the nitrogen-containing carbon porous material of each Example had a high specific surface area and a high N / C value. On the other hand, a nitrogen-containing carbon porous body was not obtained in Comparative Example 2, and a nitrogen-containing carbon porous body was obtained in Comparative Examples 1 and 3-7, but it was confirmed that at least one of the specific surface area and the N / C value was low. It was done.

  Next, using the nitrogen-containing carbon material obtained in Production Example 1 and the nitrogen-containing carbon porous body obtained in Example 1 and Comparative Example 7, an electric double layer capacitor was produced, and their performance was evaluated.

<Method for producing electrode for electric double layer capacitor>
A nitrogen-containing carbon porous body (or nitrogen-containing carbon material), polytetrafluoroethylene (manufactured by Daikin Industries, F-201), and acetylene black (manufactured by Denki Kagaku Kogyo, Denka black) Containing carbon material): polytetrafluoroethylene: acetylene black = kneaded at a mass ratio of 85: 5: 10 to prepare pellets, and a platinum mesh was crimped as a current collector to form an electrode. The electrode area was adjusted to 1.13 cm ² .

<Capacity of the nitrogen-containing carbon material of Production Example 1>
Two electrodes produced by the above electrode production method were opposed to each other with a separator (GB-100R, manufactured by Advantech Co., Ltd.), and an aqueous solution of 7M-KOH was filled as an electrolytic solution to constitute an electric double layer capacitor. . When a constant current charge / discharge measurement was performed at ^2.5 mA / cm ² using a constant current measuring device (HJ1001-SM8, manufactured by Hokuto Denko Co., Ltd.) and the capacity per single electrode was measured, it was 110 F / g.

<Capacity 1 of the nitrogen-containing carbon porous material of Example 1>
Two electrodes produced by the above electrode production method were opposed to each other with a separator (GB-100R, manufactured by Advantech Co., Ltd.), and an aqueous solution of 7M-KOH was filled as an electrolytic solution to constitute an electric double layer capacitor. . When a constant current charge / discharge measurement was performed at ^2.5 mA / cm ² using a constant current measuring device (HJ1001-SM8, manufactured by Hokuto Denko Co., Ltd.) and the capacity per single electrode was measured, it was 165 F / g.

<Capacity of the nitrogen-containing porous carbon of Comparative Example 7>
Two electrodes produced by the above electrode production method were opposed to each other with a separator (GB-100R, manufactured by Advantech Co., Ltd.), and an aqueous solution of 7M-KOH was filled as an electrolytic solution to constitute an electric double layer capacitor. . When a constant current charge / discharge measurement was performed at ^2.5 mA / cm ² using a constant current measuring apparatus (HJ1001-SM8, manufactured by Hokuto Denko Co., Ltd.) and the capacity per single electrode was measured, it was 116 F / g.

<Volume 2 of the nitrogen-containing carbon porous material of Example 1>
The two electrodes prepared by the above electrode manufacturing method are opposed to each other with a separator (manufactured by Advantech Co., Ltd., GB-100R) interposed therebetween, filled with an aqueous solution of 2M-H ₂ SO ₄ as an electrolyte, and an electric double layer capacitor is obtained. Made up. When a constant current charge / discharge measurement was performed at ^2.5 mA / cm ² using a constant current measuring device (HJ1001-SM8, manufactured by Hokuto Denko Co., Ltd.), and the capacity per single electrode was measured, it was 200 F / g.

In Example 1, a nitrogen-containing carbon porous body having the same N / C value and a large specific surface area was obtained from the nitrogen-containing carbon material of Production Example 1, and the capacity of the electrode produced therefrom was the nitrogen content of Production Example 1 Significant increase over the capacity of electrodes made from carbon materials. On the other hand, in Comparative Example 7, a nitrogen-containing carbon porous body having a large specific surface area (N / C value was about ½) was obtained from the nitrogen-containing carbon material of Production Example 1. It was confirmed that there was almost no increase in capacity. Furthermore, in Example 1, when 2M-H ₂ SO ₄ was used instead of 7M-KOH, the capacity of the electrode was further improved. It has been found that a nitrogen-containing carbon porous body having a large specific surface area and a high nitrogen atom content ratio is useful.

  The nitrogen-containing carbon porous body obtained by the production method of the present invention has a large specific surface area and a high ratio of nitrogen atoms, and thus is useful for various applications such as adsorbents, catalyst carriers, capacitor electrodes, and fuel cell electrode catalysts. is there.

Claims (4)

  The manufacturing method of a nitrogen containing carbon porous body including the process of heat-processing a nitrogen containing carbon material at 300-500 degreeC in presence of oxygen containing gas. The method for producing a nitrogen-containing carbon porous body according to claim 1, wherein the nitrogen-containing carbon porous body satisfies the following conditions (1) and (2):
(1) The atomic ratio (N / C) of nitrogen atoms to carbon atoms in the nitrogen-carbon porous body is 0.25 or more.
(2) The specific surface area by BET method is 350 m < ² > / g or more.   The said nitrogen-containing carbon material is a manufacturing method of the nitrogen-containing carbon porous body of Claim 1 or 2 obtained by carbonizing an azurmic acid at least. A nitrogen-containing porous carbon material that satisfies the following conditions (1) and (2);
(1) The atomic ratio (N / C) of nitrogen atoms to carbon atoms in the nitrogen-carbon porous body is 0.25 or more.
(2) The specific surface area by BET method is 350 m < ² > / g or more.