JP2017039630A - Porous carbon material and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a porous carbon material usable as a fuel cell catalyst and having high oxygen reduction activity, a manufacturing method therefor and a catalyst and electrode using the same.SOLUTION: A porous carbon material contains nitrogen and at least one metal selected from iron, cobalt, nickel, copper, zinc, lithium, sodium, potassium, magnesium and calcium, and has specific surface area of 450 m/g or more. N/C ratio of all nitrogen atoms to all carbon atoms is 0.020 to 0.200 and metal/N ratio of all metal atoms to all nitrogen atoms is 0.02 to 2.00.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a porous carbon material and a method for producing the same.

  Fuel cells are attracting attention as environmentally friendly power sources with high efficiency. However, fuel cells use platinum and an alloy material containing platinum, which are scarce and have a small amount of resources, and are one of the major obstacles to popularization.

  In particular, the cathode side requires a large amount of platinum to promote the oxygen reduction reaction, and an electrode catalyst that does not use expensive noble metals such as platinum is required. Therefore, the development of platinum alternative catalysts is being actively promoted around the world. However, the power generation performance and durability are still not sufficient and have not been put into practical use.

  In patent document 1, the carbon catalyst containing nitrogen and a metal is described. In order to obtain high oxygen reduction activity, the ratio of nitrogen atoms having different binding energies has been studied.

  Non-Patent Documents 1 to 3 produce a precursor by polymerizing aniline in the presence of a carbon material. The obtained precursor is calcined to form a catalyst layer on the surface of the carbon material. However, the polymer and the calcined material fill the pores of the carbon material, and the specific surface area is often smaller than the raw carbon material. ing.

JP 2009-291706 A

Science, 2011, 332, 443. J. et al. Phys. Chem. 2012, 116, 16001. J. et al. Mater. Chem. A. 2014, 2, 1242.

  An object of the present invention is to provide a porous carbon material having high oxygen reduction activity that can be used as a fuel cell catalyst, a production method thereof, and a catalyst and an electrode using the same.

  The present inventors have found that the specific surface area can be adjusted by changing the metal ratio in the precursor of the porous carbon material and the firing conditions, and further increasing the specific surface area to effectively utilize the interior of the material. It has been found that catalytic activity can be obtained. The present invention has been completed based on these findings.

According to the present invention, the following porous carbon materials and the like are provided.
1. Nitrogen and
Including at least one metal selected from iron, cobalt, nickel, copper, zinc, lithium, sodium, potassium, magnesium and calcium;
A porous carbon material having a specific surface area of 450 m ² / g or more,
Porous carbon in which the N / C ratio of all nitrogen atoms to all carbon atoms is 0.020 to 0.200, and the metal / N ratio of all metal atoms to all nitrogen atoms is 0.02 to 2.00 material.
2. 2. The porous carbon material according to 1, obtained by firing under conditions of 500 ° C. to 1500 ° C. in an inert gas atmosphere.
3. The raw material is selected from (1) a polymer of an aromatic ring compound or nitrogen-containing heterocyclic compound containing a nitrogen-containing group, and (2) iron, cobalt, nickel, copper, zinc, lithium, sodium, potassium, magnesium and calcium. Using a metal compound comprising at least one metal to be prepared,
2. The method for producing a porous carbon material according to 1, wherein the precursor is fired.
4). 4. The production method according to 3, wherein the precursor is further produced by using (3) a carbon raw material as a raw material.
5). 5. The production method according to 4, wherein the mass ratio of the (1) polymer is 50% by mass or more in the total of the (3) carbon raw material and the (1) polymer.
6). The manufacturing method in any one of 3-5 whose aromatic ring compound containing the said nitrogen-containing group is at least 1 sort (s) selected from benzonitrile and its derivative (s), and aniline and its derivative (s).
7). The production method according to any one of 3 to 6, wherein the nitrogen-containing heterocyclic compound is at least one selected from a nitrogen-containing heterocyclic monocyclic compound and a nitrogen-containing condensed heterocyclic compound.
8). The production method according to any one of 3 to 7, wherein the mass ratio of the (2) metal compound is larger than the mass ratio of the (1) polymer.
9. The manufacturing method in any one of 3-8 which bakes the said precursor at 500 to 1500 degreeC in inert gas atmosphere.
10. A catalyst for oxygen reduction or fuel cell comprising the porous carbon material according to 10.1 or 2.
11. An electrode material comprising the porous carbon material described in 2 or 1.
A mixture comprising the porous carbon material according to 12.1 or 2 and a conductive carbon material.
13. A mixture comprising the porous carbon material according to 1 or 2 and an ion conductive material.
14. A molded body obtained from the mixture according to 12 or 13.
15. A fuel cell comprising: a solid electrolyte; and an electrode disposed opposite to the solid electrolyte, the porous carbon material according to 1 or 2 being provided on at least one of the electrodes.
16. A power generator including a solid electrolyte and electrodes arranged to face each other with the solid electrolyte interposed therebetween, and having the porous carbon material according to 1 or 2 on at least one of the electrodes.
17. A power storage device including an electrode material and an electrolyte, wherein the electrode material includes the porous carbon material according to 1 or 2.

  ADVANTAGE OF THE INVENTION According to this invention, the porous carbon material which has high oxygen reduction activity which can be used as a fuel cell catalyst, its manufacturing method, a catalyst using the same, and an electrode can be provided.

It is a schematic diagram of the manufacturing process of the porous carbon material of this invention. It is a figure which shows the relationship between the mass ratio of the metal compound in a precursor, and a specific surface area. It is a schematic block diagram of one Embodiment of the fuel cell of this invention. It is a schematic block diagram of one Embodiment of the electrical storage apparatus of this invention.

The porous carbon material of the present invention contains nitrogen and metal in carbon and has a specific surface area of 450 m ² / g or more. Examples of metals include transition metals such as iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn), and alkalis such as lithium (Li), sodium (Na), and potassium (K). An alkaline earth metal such as metal, magnesium (Mg), calcium (Ca), or the like can be used. Specifically, at least one metal selected from iron, cobalt, nickel, copper, zinc, lithium, sodium, potassium, magnesium and calcium is included.
Since the metal species is preferably a transition metal having an affinity for nitrogen and oxygen, it is preferable to include one or more of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn). .
In particular, iron (Fe) and cobalt (Co) are also included in biological enzymes and are known to catalyze the oxygen reduction reaction, and it is preferable to use one of these.

In order to activate the metal, it is preferable that nitrogen and the metal are coordinated. Therefore, the greater the amount of nitrogen, the better the activity. However, if the amount of nitrogen is too large, the electron conductivity may be hindered.
The elemental ratio (N / C) of the total carbon amount and the total nitrogen amount determined by elemental analysis is usually 0.020 to 0.200, preferably 0.022 to 0.120, more preferably 0.8. It is 025-0.120, More preferably, it is 0.055-0.120.

  It is preferable to effectively utilize the entire catalyst, and in order to evaluate this, it is better to evaluate the amount present on the whole rather than the amount present on the surface. Therefore, it is preferable to evaluate the total amount by elemental analysis rather than XPS (X-ray photoelectron spectroscopy) which is a surface analysis method.

The greater the dispersibility of the metal, the higher the active site density, and the higher the activity as a catalyst. Therefore, it is preferable that the amount of metal is not too much with respect to the amount of nitrogen that is the support site.
The elemental ratio (metal / nitrogen) of the total metal amount and the total nitrogen amount determined by elemental analysis is usually from 0.010 to 2.00, preferably from 0.012 to 1.00, more preferably from 0.02. It is 015 to 0.500, More preferably, it is 0.020 to 0.400.

  The porous carbon material of the present invention may be composed only of atoms derived from raw materials described later. A part of the atoms derived from the raw material may disappear during the production. Inevitable impurities may be included.

In order to effectively utilize the active site, it is preferable that the specific surface area is large. The specific surface area determined by the BET method, is usually 450~1300m ² / g, preferably 500~1300m ² / g, more preferably 550~1300m ² / g, more preferably 650~1300m ² / g.

The oxygen reduction activity value of the porous carbon material was 0.70 Vvs. The voltage of RHE is preferably −0.80 to −3.60 mA / cm ² , more preferably −1.50 to −3.60 mA / cm ² , and more preferably −1.80 to −3. .60 mA / cm ² .

  Since the porous carbon material of the present invention has a large specific surface area and nitrogen and metal are introduced into the material, it has an excellent oxygen reduction activity. Therefore, it can be used as an electrode catalyst for fuel cells. Further, since it is a porous carbon material having conductivity, it can also be used as various electrode materials. Further, the porous carbon material of the present invention can be produced at low cost without using expensive platinum.

Hereinafter, the manufacturing method of the porous carbon material of this invention is demonstrated.
The porous carbon material of the present invention is a precursor using (1) a polymer of an aromatic ring compound or nitrogen-containing heterocyclic compound containing a nitrogen-containing group and (2) a metal compound containing the above metal as a raw material. Can be produced by firing this precursor.

FIG. 1 shows a schematic diagram of the production process of the porous carbon material of the present invention.
FIG. 1A shows a precursor in which a metal compound is attached to a polymer. When this precursor is baked, a porous carbon material having a large surface area and containing a metal is formed as shown in FIG. 1B. . Since the surface area is large, it can be used even inside the catalyst.

  The polymer includes an oligomer, a polymer, or a mixture thereof. The degree of polymerization is not limited, but is usually 10 or more. Polymers are preferred because low molecular weight compounds cause volatilization and sublimation, making firing difficult. A polymer is preferred.

  The metal used as a raw material is as described above, and corresponds to the metal contained in the porous carbon material. As the metal compound, metal chloride, metal nitrate, metal oxide, metal acetate, metal complex compound and the like can be used.

  The aromatic ring compound or nitrogen-containing heterocyclic compound containing a nitrogen-containing group constituting the polymer used as a raw material contains a nitrogen atom in a ring structure such as a 5-membered ring structure or a 6-membered ring structure, or a ring When the structure has a nitrogen-containing group, nitrogen atoms are likely to remain even after calcination, leading to an improvement in catalytic activity. The nitrogen-containing group is preferably in the vicinity of the ring structure.

  Examples of nitrogen-containing groups include amino groups and nitro groups. Examples of the aromatic ring include a benzene ring and a naphthalene ring. Aromatic hydrocarbon rings are preferred. The aromatic ring compound substituted with a nitrogen-containing group is preferably benzonitrile, aniline or a derivative thereof.

  The nitrogen-containing heterocyclic compound is preferably at least one selected from nitrogen-containing heterocyclic monocyclic compounds and nitrogen-containing condensed heterocyclic compounds. It is preferable that other hetero atoms other than nitrogen are not included. For example, from 5-membered ring compound pyrrole and derivatives thereof, diazoles and derivatives thereof, triazoles and derivatives thereof, pyridine and derivatives thereof as 6-membered ring compounds, diazines and derivatives thereof, and triazines and derivatives thereof. At least one selected. Examples include quinoline, phenanthroline and purine.

  As shown in FIG. 2, when the mass ratio of the metal compound in the precursor is increased, the specific surface area is increased. Therefore, it is preferable that the mass ratio of the metal compound is larger than the mass ratio of the polymer. Specifically, the mass of the metal compound is preferably at least twice the mass of the polymer, more preferably at least 5 times, and even more preferably at least 10 times. The upper limit is usually less than double.

  The precursor may be produced using (3) a carbon raw material as a raw material. Examples of the carbon raw material include carbon black, graphite, graphene, and carbon nanotube. The present invention can be produced without using a carbon raw material. The amount of the carbon raw material is, for example, 0 to 80% by mass, preferably 0 to 50% by mass.

  Remaining a large amount of nitrogen leads to high activity. Therefore, it is preferable that the mass ratio of the polymer in the raw material to be carbon of the porous carbon material is 50% by mass or more. 80 mass% or more, 90 mass% or more, or 100 mass%.

  When the precursor is produced, forming a coordination bond between the metal and nitrogen is effective for residual nitrogen, so when mixing the polymer and the metal compound, use a polar solvent such as alcohol or water. It is preferable to mix in a solvent. When irradiated with ultrasonic waves, the polymer is easily dispersed in a polar solvent. After mixing, the precursor is obtained by drying, but may be pulverized using a mortar or the like in order to improve the uniformity of the precursor.

  Firing is preferably performed by firing the precursor at a temperature of 500 ° C. to 1500 ° C. in an inert gas (nitrogen, argon, etc.) atmosphere. A high temperature is preferable for carbonization, but a lower temperature is preferable for leaving nitrogen atoms and coordination metals. Therefore, it is preferably 600 ° C to 1200 ° C, more preferably 650 ° C to 1100 ° C, and further preferably 700 ° C to 1000 ° C. The firing time can be adjusted within a range where the effects of the present invention can be obtained, but is usually 0.5 hours to 10 hours, preferably 1 hour to 5 hours.

  It is preferable to remove unnecessary metal from the fired material. Therefore, it is preferable to wash using an acid such as sulfuric acid. Moreover, after acid cleaning, in order to prevent adsorption | suction of ion, it is preferable to wash | clean with ion-exchange water etc.

  As described above, since the porous carbon material of the present invention has oxygen reduction activity, it can be used as a catalyst. Moreover, since it has electroconductivity, it can be used also as an electrode material.

  The porous carbon material of the present invention can be used for various applications. For example, a fuel cell, a power generation device, a power storage device (battery, electric double layer capacitor, etc.) can be configured.

  When a fuel cell is constructed using the porous carbon material of the present invention, a fuel cell is constructed from a solid electrolyte and two (a pair) of electrode catalysts arranged opposite to each other with the solid electrolyte interposed therebetween. Thus, the porous carbon material of the present invention is used for at least one of the two (pair) electrode catalysts. When the power storage device is configured using the porous carbon material of the present invention, the power storage device is configured to include the electrode material and the electrolyte, and the porous carbon material of the present invention is used as the electrode material.

  Here, FIG. 3 shows a schematic configuration diagram of an embodiment of a fuel cell using the porous carbon material of the present invention. This fuel cell has a pair of electrode catalyst layers 2 and 3 arranged to face each other with the solid polymer electrolyte 1 sandwiched therebetween, and the electrode catalyst layers 2 and 3 are further disposed outside the electrode catalyst layers 2 and 3, respectively. It has the support bodies 4 and 5 for supporting. This is a so-called solid polymer fuel cell (PFEC).

  The left electrode catalyst layer 2 in the figure is an anode electrode catalyst layer (fuel electrode). The electrode catalyst layer 3 on the right side in the figure is a cathode electrode catalyst layer (oxidant electrode). A fuel cell can be constituted by using the porous carbon material of the present invention for either one or both of the pair of electrode catalyst layers 2 and 3.

As the solid polymer electrolyte 1, a fluorine-based cation exchange resin membrane can be used.
Support 4 and 5, to support the anode electrode catalyst layer 2 and cathode catalyst layer 3, and performs supply and discharge of the reaction gas such as fuel gas H ₂ and oxygen-containing gas O _2. The supports 4 and 5 are usually constituted by an outer separator and an inner (electrolyte side) gas diffusion layer. However, depending on the properties of the catalyst, the gas diffusion layer is not required and the support is constituted only by the separator. It becomes possible. For example, by using a catalyst having a large specific surface area and a high gas diffusibility for the electrode catalyst layer, the catalyst layer also functions as a gas diffusion layer, so that the gas diffusion layer can be omitted. .

  According to the configuration of the fuel cell of this embodiment, since the porous carbon material of the present invention having high activity is used for at least one of the anode electrode catalyst layer 2 and the cathode electrode catalyst layer 3, the fuel cell having high performance. Can be realized at a cost sufficiently lower than when a platinum catalyst is used.

  The fuel cell of the above-described embodiment is a polymer electrolyte fuel cell (PFEC). The porous carbon material of the present invention can be applied not only to a polymer electrolyte fuel cell (PFEC) but also to other types of fuel cells as long as it can use a carbon catalyst. It is.

Next, FIG. 4 shows a schematic configuration diagram of an electric double layer capacitor as an embodiment of a power storage device using the porous carbon material of the present invention.
In this electric double layer capacitor, the first electrode 21 and the second electrode 22 which are polarizable electrodes are opposed to each other through the separator 23, and are accommodated in the outer lid 24a and the outer case 24b.
The first electrode 21 and the second electrode 22 are connected to the exterior lid 24a and the exterior case 24b via current collectors 25, respectively.
The separator 23 is impregnated with an electrolytic solution. The interior is sealed by caulking the exterior lid 24a and the exterior case 24b while being electrically insulated via the gasket 26.

  In the electric double layer capacitor of the present embodiment, the porous carbon material of the present invention can be applied to the first electrode 21 and / or the second electrode 22. And the electric double layer capacitor by which the porous carbon material was applied to the electrode material can be comprised.

  The porous carbon material of the present invention is electrochemically inactive with respect to the electrolytic solution and has appropriate electrical conductivity. For this reason, the electrostatic capacitance per unit volume of an electrode can be improved by applying as an electrode of a capacitor.

  Further, like the electric double layer capacitor of the above-described embodiment, the porous carbon material of the present invention is used as an electrode material composed of a carbon material, such as a negative electrode material of a lithium ion secondary battery. be able to.

  In addition, the porous carbon material may be used alone or in combination with other substances. For example, a mixture of a porous carbon material and a conductive carbon material is used for fuel cell electrodes, capacitors, and the like. A mixture of a porous carbon material and an ion conductive material is used for a fuel cell electrode or the like. You may form and use the molded object of various forms from these mixtures as needed.

Example 1
(1) Production of porous carbon material Ketjen Black EC300J (manufactured by Lion), polyaniline (manufactured by Aldrich, Mw: 65000) and iron chloride hexahydrate in methanol at a 1: 1: 1 ratio in methanol Mixed. This methanol solution was irradiated with ultrasonic waves for 30 minutes and dried under reduced pressure using an evaporator to obtain a precursor. The obtained precursor was heated from room temperature to 700 ° C. in a nitrogen atmosphere over 70 minutes, and kept as it was for 4 hours. After maintaining at 700 ° C., the calcined precursor was placed in 0.5 M sulfuric acid and stirred at 80 ° C. for 1 hour to remove excess metal. After filtration, it was washed with distilled water and vacuum dried at 120 ° C. to obtain a porous carbon material.

The characteristics of the obtained porous carbon material were measured by the following method. The results are shown in Table 1.
(Elemental analysis)
Carbon, hydrogen, and nitrogen content were measured using a fully automatic elemental analyzer (vario EL cube) manufactured by Elemental.
The iron content was measured using an ICP emission spectrophotometer manufactured by Agilent Technologies after the ashing treatment.

(Specific surface area measurement)
After pretreatment by vacuum evacuation under heating at 150 ° C. for 3 hours, an adsorption isotherm was determined by a nitrogen adsorption method, BET specific surface area analysis was performed, and a specific surface area value was calculated.

(Oxygen reduction activity)
500 μl of isopropanol, 450 μl of distilled water, 50 μl of 5 wt% Nafion solution and 6 mg of porous carbon material were mixed and sonicated for 1 hour to prepare a slurry solution. 80 μl of the prepared slurry solution was taken, applied on a carbon electrode (10 mmφ), and dried at 50 ° C.
A cyclic voltammogram was measured using a carbon electrode as a working electrode, a platinum wire as a counter electrode, and a reversible hydrogen electrode as a reference electrode. The electrolytic solution was a 0.1M perchloric acid solution, which was measured after oxygen bubbling for 30 minutes. The sweep speed was 10 mV / s. The current value at 0.70 V was defined as oxygen reduction activity.

Example 2
In Example 1, except that the method for firing the precursor was changed, that is, the temperature was raised from room temperature to 800 ° C. over 80 minutes in a nitrogen atmosphere, and kept for 4 hours in the same manner as in Example 1. A porous carbon material was obtained and evaluated. The results are shown in Table 1.

Example 3
In Example 1, a porous carbon material was obtained and evaluated in the same manner as in Example 1 except that the triazine polymer 1 having the following formula was used instead of polyaniline. The results are shown in Table 1.

Example 4
In Example 1, a porous carbon material was obtained and evaluated in the same manner as in Example 1 except that the triazine polymer 2 having the following formula was used instead of polyaniline. The results are shown in Table 1.

Example 5
In Example 1, a porous carbon material was obtained and evaluated in the same manner as in Example 1 except that the mass ratio of ketjen black, polyaniline, and iron chloride hexahydrate was changed to 1: 1: 3. The results are shown in Table 1.

Example 6
In Example 1, porous material was used in the same manner as in Example 1 except that polyaniline and iron chloride hexahydrate were used in a mass ratio of 1: 6 without using ketjen black as a precursor raw material. A carbonaceous material was obtained and evaluated. The results are shown in Table 1.

Example 7
In Example 6, a porous carbon material was obtained and evaluated in the same manner as in Example 6 except that the mass ratio of polyaniline to iron chloride hexahydrate was 1: 4. The results are shown in Table 1.

Example 8
In Example 6, a porous carbon material was obtained and evaluated in the same manner as in Example 6 except that the mass ratio of polyaniline to iron chloride hexahydrate was 1:12. The results are shown in Table 1.

Example 9
In Example 8, except that the method for firing the precursor was changed, that is, the temperature was raised from room temperature to 800 ° C. over 80 minutes in a nitrogen atmosphere, and kept for 4 hours in the same manner as in Example 8, A porous carbon material was obtained and evaluated. The results are shown in Table 1.

Example 10
In Example 8, except that the method for firing the precursor was changed, that is, the temperature was raised from room temperature to 1000 ° C. in a nitrogen atmosphere over 100 minutes, and the state was maintained for 2 hours in the same manner as in Example 8, A porous carbon material was obtained and evaluated. The results are shown in Table 1.

Example 11
In Example 6, except that the method for firing the precursor was changed, that is, the temperature was raised from room temperature to 900 ° C. over 90 minutes in a nitrogen atmosphere, and the state was maintained for 2 hours in the same manner as in Example 6, A porous carbon material was obtained and evaluated. The results are shown in Table 1.

Comparative Example 1
In Example 1, porous material was used in the same manner as in Example 1 except that ketjen black and iron chloride hexahydrate were used at a mass ratio of 1: 6 without using polyaniline as a precursor raw material. A carbonaceous material was obtained and evaluated. The results are shown in Table 1.

Comparative Example 2
In Example 1, a porous carbon material was obtained and evaluated in the same manner as in Example 1 except that the mass ratio of Ketjen Black, polyaniline, and iron chloride hexahydrate was changed to 1: 1: 0.75. did. The results are shown in Table 1.

Comparative Example 3
In Example 6, except that the precursor firing method was changed, that is, the temperature was raised from room temperature to 900 ° C. over 90 minutes in a nitrogen atmosphere, and the state was maintained for 4 hours in the same manner as in Example 6, A porous carbon material was obtained and evaluated. The results are shown in Table 1.

Comparative Example 4
In Example 6, except that the method for firing the precursor was changed, that is, the temperature was raised from room temperature to 600 ° C. over 60 minutes in a nitrogen atmosphere, and was kept as it was for 4 hours. A porous carbon material was obtained and evaluated. The results are shown in Table 1.

  FIG. 2 shows the relationship between the mass ratio of iron chloride hexahydrate and the specific surface area in the total mass of the precursor.

  The porous carbon material of the present invention has an excellent oxygen reduction activity, and can be used as a catalyst for oxygen reduction or a fuel cell. It can also be used as an electrode material in fuel cells, power generation equipment, power storage devices, and the like.

  DESCRIPTION OF SYMBOLS 1 Solid polymer electrolyte, 2 Anode electrode catalyst layer (fuel electrode), 3 Cathode electrode catalyst layer (oxidant electrode), 4, 5 Support body, 21 1st electrode, 22 2nd electrode, 23 Separator, 24a Exterior Lid, 24b Exterior case, 25 Current collector, 26 Gasket

Claims (17)

Nitrogen and
Including at least one metal selected from iron, cobalt, nickel, copper, zinc, lithium, sodium, potassium, magnesium and calcium;
A porous carbon material having a specific surface area of 450 m ² / g or more,
Porous carbon in which the N / C ratio of all nitrogen atoms to all carbon atoms is 0.020 to 0.200, and the metal / N ratio of all metal atoms to all nitrogen atoms is 0.02 to 2.00 material.   The porous carbon material according to claim 1, which is obtained by firing under conditions of 500 ° C. to 1500 ° C. in an inert gas atmosphere. The raw material is selected from (1) a polymer of an aromatic ring compound or nitrogen-containing heterocyclic compound containing a nitrogen-containing group, and (2) iron, cobalt, nickel, copper, zinc, lithium, sodium, potassium, magnesium and calcium. Using a metal compound comprising at least one metal to be prepared,
The method for producing a porous carbon material according to claim 1, wherein the precursor is fired.   The manufacturing method according to claim 3, wherein the precursor is further produced by using (3) a carbon raw material as a raw material.   The manufacturing method according to claim 4, wherein the mass ratio of the (1) polymer is 50% by mass or more in the total of the (3) carbon raw material and the (1) polymer.   The method according to any one of claims 3 to 5, wherein the aromatic ring compound containing a nitrogen-containing group is at least one selected from benzonitrile and derivatives thereof, and aniline and derivatives thereof.   The production method according to claim 3, wherein the nitrogen-containing heterocyclic compound is at least one selected from a nitrogen-containing heterocyclic monocyclic compound and a nitrogen-containing condensed heterocyclic compound.   The production method according to claim 3, wherein the mass ratio of the (2) metal compound is greater than the mass ratio of the (1) polymer.   The manufacturing method according to claim 3, wherein the precursor is fired at 500 ° C. to 1500 ° C. in an inert gas atmosphere.   An oxygen reduction or fuel cell catalyst comprising the porous carbon material according to claim 1 or 2.   An electrode material comprising the porous carbon material according to claim 1.   A mixture comprising the porous carbon material according to claim 1 or 2 and a conductive carbon material.   A mixture comprising the porous carbon material according to claim 1 or 2 and an ion conductive material.   The molded object obtained from the mixture of Claim 12 or 13.   A fuel cell comprising: a solid electrolyte; and an electrode disposed opposite to the solid electrolyte, wherein the porous carbon material according to claim 1 or 2 is provided on at least one of the electrodes.   3. A power generator including a solid electrolyte and an electrode disposed opposite to the solid electrolyte, and having the porous carbon material according to claim 1 at least one of the electrodes.   A power storage device comprising an electrode material and an electrolyte, wherein the electrode material comprises the porous carbon material according to claim 1.

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