Porous carbon and method of manufacturing same

Abstract

A porous carbon that has an extremely high specific surface area while being crystalline, and a method of manufacturing the porous carbon are provided. A porous carbon has mesopores 4 and a carbonaceous wall 3 constituting an outer wall of the mesopores 4, wherein the carbonaceous wall 3 has a portion forming a layered structure. The porous carbon is fabricated by mixing a polyamic acid resin 1 as a carbon precursor with magnesium oxide 2 as template particles; heat-treating the mixture in a nitrogen atmosphere at 1000° C. for 1 hour to cause the polyamic acid resin to undergo heat decomposition; washing the resultant sample with a sulfuric acid solution at a concentration of 1 mol/L to dissolve MgO away; and heat-treating the noncrystalline porous carbon in a nitrogen atmosphere at 2500° C.

Claims

1. A porous carbon comprising: mesopores, a carbonaceous wall constituting an outer wall of the mesopores, the carbonaceous wall forming a mesh three-dimensional network structure, and micropores, wherein the micropores are each formed in a position facing the mesopores in the carbonaceous wall, wherein the carbonaceous wall has a portion forming a layered structure, and wherein the porous carbon consists of carbon.

2. The porous carbon according to claim 1, wherein the specific surface area is 200 m.sup.2/g or more.

3. The porous carbon according to claim 1, wherein the mesopores are open pores, and the hollow portions are connected to each other.

4. The porous carbon according to claim 1, wherein the capacity of the mesopores is 0.2 ml/g or more.

5. The porous carbon according to claim 1, wherein the bulk density is from 0.1 g/cc to 1.0 g/cc.

6. The porous carbon according to claim 1, wherein the thickness of the portion forming a layered structure is from 1 nm to 100 nm.

7. A porous carbon comprising: mesopores, a carbonaceous wall constituting an outer wall of the mesopores, the carbonaceous wall forming a mesh three-dimensional network structure, and micropores, wherein the micropores are each formed in a position facing the mesopores in the carbonaceous wall, wherein a peak is present at a Bragg angle 2θ of 26.45° in an X-ray diffraction spectrum to a CuKα ray (wavelength 1.541 angstroms) of the carbonaceous wall, and wherein the porous carbon consists of carbon.

8. The porous carbon according to claim 7, wherein the specific surface area is 200 m.sup.2/g or more.

9. The porous carbon according to claim 7, wherein the mesopores are open pores, and the hollow portions are connected to each other.

10. The porous carbon according to claim 7, wherein the capacity of the mesopores is 0.2 ml/g or more.

11. The porous carbon according to claim 7, wherein the bulk density is from 0.1 g/cc to 1.0 g/cc.

12. The porous carbon according to claim 7, wherein the carbonaceous wall has a portion forming a layered structure.

13. The porous carbon according to claim 7, wherein the specific resistance is 1.0×10.sup.2Ω.Math.cm or less.

14. A method of manufacturing a porous carbon consisting of carbon, the porous carbon having a three-dimensional network structure, wherein a noncrystalline carbonaceous carbonized body having mesopores is manufactured by the steps of: mixing a flowable material containing an organic resin with template particles comprising at least one alkaline-earth metal compound selected from the group consisting of an oxide, a hydroxide, a carbonate and an organic acid salt of an alkaline-earth metal, to prepare a mixture; carbonizing the mixture in a non-oxidizing atmosphere to prepare a carbonized substance; and removing the template particles in the carbonized substance to obtain the noncrystalline carbonaceous carbonized body having mesopores, wherein the carbon yield of the flowable material is from 40% to 85%, the noncrystalline carbonaceous carbonized body having mesopores is subjected to a crystallization treatment to heat a target in a non-oxidizing atmosphere or a reduced-pressure atmosphere at a temperature equal to or higher than a temperature at which the noncrystalline carbonaceous carbonized body having mesopores is crystallized, thereby obtaining the porous carbon comprising: the mesopores; a carbonaceous wall constituting an outer wall of the mesopores, the carbonaceous wall forming the three-dimensional network structure, the carbonaceous wall having a portion forming a layered structure; and micropores each formed in a position facing the mesopores in the carbonaceous wall.

15. The method of manufacturing a porous carbon according to claim 14, the diameters of the template particles are substantially the same as each other.

16. The method of manufacturing a porous carbon according to claim 14, wherein the flowable material shows flowability at a temperature of 200° C. or lower.

17. The method of manufacturing a porous carbon according to claim 14, wherein the flowable material is at least one selected from the group consisting of a polyimide containing at least one nitrogen or fluorine atom in its unit structure, a phenolic resin and a pitch.

18. The method of manufacturing a porous carbon according to claim 14, wherein in the step of removing the template particles, the remaining ratio of the template particles after the removing is restricted to 0.5% or less.

19. The porous carbon according to claim 1, wherein the capacity of the micropores is 0.12 ml/g or more.

20. The porous carbon according to claim 7, wherein the capacity of the micropores is 0.12 ml/g or more.

21. The method of manufacturing a porous carbon according to claim 14, wherein the crystallization treatment is conducted at a temperature of 2000° C. or lower.

22. The porous carbon according to claim 12, wherein the thickness of the portion forming a layered structure is from 1 nm to 100 nm.

23. A porous carbon comprising: mesopores, a carbonaceous wall constituting an outer wall of the mesopores, the carbonaceous wall forming a mesh three-dimensional network structure, and micropores, wherein the micropores are each formed in a position facing the mesopores in the carbonaceous wall, wherein the carbonaceous wall has a portion being graphitized, wherein the porous carbon consists of carbon, and wherein the capacity of the micropores is 0.12 ml/g or more.

24. The porous carbon according to claim 23, wherein the specific surface area is 200 m.sup.2/g or more.

25. The porous carbon according to claim 23, wherein the mesopores are open pores, and the hollow portions are connected to each other.

26. The porous carbon according to claim 23, wherein the capacity of the mesopores is 0.2 ml/g or more.

27. The porous carbon according to claim 23, wherein the bulk density is from 0.1 g/cc to 1.0 g/cc.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 illustrates a manufacturing process of the present invention, wherein FIG. 1(a) shows a state in which a polyamic acid resin and magnesium oxide are mixed: FIG. 1(b) shows a mixture that has been heat-treated; and FIG. 1(c) shows porous carbon.

(2) FIG. 2 is a STEM (scanning transmission electron microscope) photograph of a present invention carbon A1.

(3) FIG. 3 is a STEM photograph of a present invention carbon A2.

(4) FIG. 4 is a STEM photograph of a present invention carbon A4.

(5) FIG. 5 is a graph showing the relationship of the relative pressure and the amount of N.sub.2 adsorbed for the present invention carbons A1 to A4.

(6) FIG. 6 is a graph showing the relationship between pore diameters and their proportions in the present invention carbon A1.

(7) FIG. 7 is a graph showing the relationship between pore diameters and their proportions in the present invention carbon A2.

(8) FIG. 8 is a graph showing the relationship between pore diameters and their proportions in the present invention carbon A4.

(9) FIG. 9 shows X-ray diffraction charts of the present invention carbons A1 and A4.

BEST MODE FOR CARRYING OUT THE INVENTION

(10) Herein below, embodiments of the present invention will be described. A porous carbon of the present invention is obtained in the following manner: an organic resin is wet- or dry-mixed with an oxide (template particles) in a solution or powder state, the mixture is carbonized in a non-oxidizing atmosphere or a reduced-pressure atmosphere at a temperature of, for example, 500° C. or higher, and then washed to remove the oxide, thereby fabricating a noncrystalline porous carbon (carbonaceous carbonized body). Thereafter, the noncrystalline porous carbon is heat-treated in a non-oxidizing atmosphere or a reduced-pressure atmosphere at a temperature equal to or higher than a temperature at which the noncrystalline porous carbon is crystallized (e.g., 2000° C.).

(11) Preferably, the noncrystalline porous carbon has a multiplicity of mesopores having substantially the same particle diameter as each other, wherein micropores are formed at positions facing the mesopores in a carbonaceous wall formed between the mesopores. In the heat treatment of the noncrystalline porous carbon, a state in which a multiplicity of mesopores exist is maintained, and moreover, at least a part of the carbon portion (carbonaceous wall) forms a layered structure. Therefore, by this heat treatment, a porous carbon having developed crystallinity is obtained.

(12) As the organic resin, a polyimide containing at least one nitrogen atom or fluorine atom in its unit structure, or a resin having a carbonization yield of from 40% by weight to 85% by weight, for example a phenol resin or a pitch, is suitably used.

(13) Here, the polyimide containing at least one nitrogen or fluorine atom in its unit structure can be obtained by polycondensation of an acid component and a diamine component. However, in this case, it is necessary that either one of or both of the acid component and the diamine component contain at least one nitrogen atom or fluorine atom.

(14) Specifically, a polyamic acid, which is the precursor of the polyimide, is deposited, and the solvent is removed by heating, to obtain a polyamic acid film. Next, the obtained polyamic acid film is subjected to heat imidization at 200° C. or higher, so that the polyimide can be manufactured.

(15) Examples of the diamine include: aromatic diamines including 2,2-Bis(4-aminophenyl)hexafluoropropane, 2,2′-Bis(trifluoromethyl)-benzidine, and 4,4′-diaminooctafluorobiphenyl, and 3,3′-difluoro-4,4′-diaminodiphenylmethane, 3,3′-difluoro-4,4′-diaminodiphenylether, 3,3′-di(trifluoromethyl)-4,4′-diaminodiphenylether, 3,3′-difluoro-4,4′-diaminodiphenylpropane, 3,3′-difluoro-4,4′-diaminodiphenylhexafluoropropane, 3,3′-difluoro-4,4′-diaminobenzophenone, 3,3′,5,5′-tetrafluoro-4,4′-diaminodiphenylmethane, 3,3′,5,5′-tetra(trifluoromethyl)-4,4′-diaminodiphenylmethane, 3,3′,5,5′-tetrafluoro-4,4′-diaminodiphenylpropane, 3,3′,5,5′-tetra(trifluoromethyl)-4,4′-diaminodiphenylpropane, 3,3′,5,5′-tetrafluoro-4,4′-diaminodiphenylhexafluoropropane, 1,3-diamino-5-(perfluorononenyloxy)benzene, 1,3-diamino-4-methyl-5-(perfluorononenyloxy)benzene, 1,3-diamino-4-methoxy-5-(perfluorononenyloxy)benzene, 1,3-diamino-2,4,6-trifluoro-5-(perfluorononenyloxy)benzene, 1,3-diamino-4-chloro-5-(perfluorononenyloxy)benzene, 1,3-diamino-4-pbromo-5-(perfluorononenyloxy)benzene, 1,2-diamino-4-(perfluorononenyloxy)benzene, 1,2-diamino-4-methyl-5-(perfluorononenyloxy)benzene, 1,2-diamino-4-methoxy-5-(perfluorononenyloxy)benzene, 1,2-diamino-3,4,6-trifluoro-5-(perfluorononenyloxy)benzene, 1,2-diamino-4-chloro-5-(perfluorononenyloxy)benzene, 1,2-diamino-4-bromo-5-(perfluorononenyloxy)benzene, 1,4-diamino-3-(perfluorononenyloxy)benzene, 1,4-diamino-2-methyl-5-(perfluorononenyloxy)benzene, 1,4-diamino-2-methoxy-5-(perfluorononenyloxy)benzene, 1,4-diamino-2,3,6-trifluoro-5-(perfluorononenyloxy)benzene, 1,4-diamino-2-chloro-5-(perfluorononenyloxy)benzene, 1,4-diamino-2-pbromo-5-(perfluorononenyloxy)benzene, 1,3-diamino-5-(perfluorohexenyloxy)benzene, 1,3-diamino-4-methyl-5-(perfluorohexenyloxy)benzene, 1,3-diamino-4-methoxy-5-(perfluorohexenyloxy)benzene, 1,3-diamino-2,4,6-trifluoro-5-(perfluorohexenyloxy)benzene, 1,3-diamino-4-chloro-5-(perfluorohexenyloxy)benzene, 1,3-diamino-4-bromo-5-(perfluorohexenyloxy)benzene, 1,2-diamino-4-(perfluorohexenyloxy)benzene, 1,2-diamino-4-methyl-5-(perfluorohexenyloxy)benzene, 1,2-diamino-4-methoxy-5-(perfluorohexenyloxy)benzene, 1,2-diamino-3,4,6-trifluoro-5-(perfluorohexenyloxy)benzene, 1,2-diamino-4-chloro-5-(perfluorohexenyloxy)benzene, 1,2-diamino-4-bromo-5-(perfluorohexenyloxy)benzene, 1,4-diamino-3-(perfluorohexenyloxy)benzene, 1,4-diamino-2-methyl-5-(perfluorohexenyloxy)benzene, 1,4-diamino-2-methoxy-5-(perfluorohexenyloxy)benzene, 1,4-diamino-2,3,6-trifluoro-5-(perfluorohexenyloxy)benzene, 1,4-diamino-2-chloro-5-(perfluorohexenyloxy)benzene, 1,4-diamino-2-bromo-5-(perfluorohexenyloxy)benzene; and p-phenylenediamine (PPD) and dioxydianiline, which do not contain fluorine atoms. It is also possible that two or more of the foregoing aromatic diamines may be used in combination as the diamine component.

(16) Examples of the acid component include: 4,4-(hexafluoroisoproylidene)diphthalic anhydride (6FDA), which contains fluorine atoms; and 3,4,3′,4′-biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA), which contain no fluorine atom.

(17) Examples of the organic solvent used as the solvent for the polyimide precursor include N-methyl-2-pyrrolidone and dimethylformamide.

(18) The technique for imidization may follow either heat imidization or chemical imidization as indicated by known methods [for example, see “Shin Kobunshi Jikkengaku, 3, Kobunshi no Gosei Hanno (2)” (Experimental Polymer Science, New Edition, 3, Synthesis and reaction of polymer [2]), edited by Society of Polymer Science, Japan, Kyoritsu Shuppan, Tokyo, Mar. 28, 1996, p. 158]. The present invention is not limited to this method of imidization.

(19) Furthermore, it is possible to use a resin having a carbon yield of 40% or higher, such as petroleum-based tar pitch and an acrylic resin, other than the polyimide.

(20) Examples of the source material used as the above-mentioned oxide include metal organic acids the state of which changes into magnesium oxide during the thermal decomposition process by a heat treatment (including magnesium citrate, magnesium oxalate, calcium citrate, and calcium oxalate) in addition to alkaline-earth metal oxides (magnesium oxide and calcium oxide).

(21) As the cleaning solution for removing the oxide, it is preferable to use a dilute acid of 2 mol/L or lower of a common inorganic acid, such as hydrochloric acid, sulfuric acid, nitric acid, citric acid, acetic acid, and formic acid. It is also possible to use hot water of 80° C. or higher.

(22) Preferably, carbonization of the aforementioned mixture is performed in a non-oxidizing atmosphere or a reduced-pressure atmosphere at a temperature of from 500° C. to 1500° C. The reason is as follows. Because the resin having a high carbon yield is a polymer, the carbonization is insufficient and the do not develop sufficiently at a temperature of lower than 500° C. On the other hand, at a temperature of 1500° C. or higher, the shrinkage is great and the oxide is carbonized and made into a large size; therefore, the pore size becomes small and the specific surface area becomes small. The non-oxidizing atmosphere is an argon atmosphere, a nitrogen atmosphere or the like, and the reduced-pressure atmosphere is an atmosphere at 133 Pa (1 torr) or less.

(23) When the aforementioned noncrystalline porous carbon is heat-treated, it is necessary to perform the heat treatment in a non-oxidizing atmosphere or a reduced-pressure atmosphere. In this case, the non-oxidizing atmosphere is the argon atmosphere, the nitrogen atmosphere or the like as described above, and the reduced-pressure atmosphere is the atmosphere at 133 Pa (1 torr) or less as described above. Further, the heat treatment temperature is not limited as long as it is equal to or higher than a temperature at which a noncrystalline carbon is crystallized, but the heat treatment temperature is preferably 800° C. or higher, more desirably 2000° C. or higher for forming a layered structure (crystallization) smoothly and in a short time. However, if the temperature is excessively high, a waste of energy occurs, and therefore the heat treatment temperature is preferably 2500° C. or lower.

EXAMPLES

Example 1

(24) First, as illustrated in FIG. 1(a), a polyamic acid resin 1 (imide-based resin) as a carbon precursor and magnesium oxide 2 (MgO, average crystallite size 5 nm) as template particles were mixed at a weight ratio of 90:10. Next, as illustrated in FIG. 1(b), the mixture was heat-treated in a nitrogen atmosphere at 1000° C. for 1 hour, to allow the polyamic acid resin to undergo heat decomposition, so that a carbonized substance including a carbonaceous wall 3 was obtained. Then, as illustrated in FIG. 1(c), the resulting carbonized substance was washed with a sulfuric acid solution added at a concentration of 1 mol/L, to dissolve MgO away completely, whereby porous carbon 5 having a multiplicity of pores 4 was obtained. Lastly, the noncrystalline porous carbon was heat-treated in a nitrogen atmosphere at 2500° C. for 1 hour to obtain a porous carbon.

(25) The porous carbon fabricated in this manner is hereinafter referred to as a present invention carbon A1.

(26) FIG. 2 shows a STEM (scanning transmission electron microscope) photograph of the present invention carbon A1. As clearly seen from FIG. 2, at least a part of the carbon portion of the present invention carbon A1 forms a layered shape, and accordingly it is observed that crystallinity of at least a part of the carbon portion is developed. That is, it is observed that in the present invention carbon A1, crystallinity of at least a part of the carbonaceous wall 3 is developed. The interlayer distance between adjacent layers is about 0.33 nm, and therefore in the case of a structure of 11 layers, the thickness of the carbon layer forming a layered shape is 3.3 nm (0.33 nm×[11−1]). It was observed that the present invention carbon A1 formed a three-dimensional network structure (spongy carbon form), and the mesopores were open pores, so that the hollow portions were connected to each other.

Example 2

(27) A porous carbon was fabricated in the same manner as described in Example 1 above, except that the temperature for heat-treating a noncrystalline porous carbon was 2000° C.

(28) The porous carbon fabricated in this manner is hereinafter referred to as a present invention carbon A2.

(29) FIG. 3 shows a STEM photograph of the present invention carbon A2. As clearly seen from FIG. 3, at least a part of the carbon portion of the present invention carbon A2 forms a layered shape, and accordingly it is observed that crystallinity of at least a part of the carbon portion is developed. It was also observed that the present invention carbon A2 formed a three-dimensional network structure (spongy carbon form), and the mesopores were open pores, so that the hollow portions were connected to each other.

Example 3

(30) A porous carbon was fabricated in the same manner as described in Example 1 above, except that the temperature for heat-treating a noncrystalline porous carbon was 1400° C.

(31) The porous carbon fabricated in this manner is hereinafter referred to as a present invention carbon A3.

Example 4

(32) A porous carbon was fabricated in the same manner as described in Example 1 above, except that the temperature for heat-treating a noncrystalline porous carbon was 900° C.

(33) The porous carbon fabricated in this manner is hereinafter referred to as a present invention carbon A4.

(34) FIG. 4 shows a STEM (scanning transmission electron microscope) photograph of the present invention carbon A4. As clearly seen from FIG. 4, at least a part of the carbon portion of the present invention carbon A4 forms a layered shape, and accordingly it is observed that crystallinity of at least a part of the carbon portion is developed. It was also observed that the present invention carbon A4 formed a three-dimensional network structure (spongy carbon form), and the mesopores were open pores, so that the hollow portions were connected to each other.

Comparative Example 1

(35) A porous carbon was fabricated in the same manner as described in Example 1 above, except that as a carbon material before heat treatment, an activated carbon (reagent manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of the noncrystalline porous carbon, and the activated carbon was heat-treated at 2000° C.

(36) The porous carbon fabricated in this manner is hereinafter referred to as a present invention carbon Z1.

Comparative Example 2

(37) A porous carbon was fabricated in the same manner as described in Example 1 above, except that as a carbon material before heat treatment, an activated carbon (reagent manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of the noncrystalline porous carbon, and the activated carbon was heat-treated at 1400° C.

(38) The porous carbon fabricated in this manner is hereinafter referred to as a present invention carbon Z2.

Comparative Example 3

(39) A porous carbon was fabricated in the same manner as described in Example 1 above, except that as a carbon material before heat treatment, an activated carbon (reagent manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of the noncrystalline porous carbon, and the activated carbon was not heat-treated.

(40) The porous carbon fabricated in this manner is hereinafter referred to as a present invention carbon Z3.

Experiment 1

(41) The relationship between the pressure and the amount of N.sub.2 adsorbed (adsorption isotherm) was studied for the present invention carbons A1 to A4. The results are shown in FIG. 5.

(42) In this experiment, measurements were made by a nitrogen adsorption method using a specific-surface area measuring device (Bellsorp 18, BEL Japan, Inc.). About 0.1 g of the sample was taken in a cell, degassed in a sample pretreatment section of the device at 300° C. for about 5 hours, and then measured.

(43) As clearly seen from FIG. 5, when the relative pressure is in the range of from 0 to 0.1, it is observed that the present invention carbons A3 and A4 adsorb large amounts of N.sub.2 gas, while the present invention carbon A2 adsorbs a small amount of N.sub.2 gas as compared to the present invention carbons A3 and A4, and the present invention carbon A1 adsorbs little N.sub.2 gas. On the other hand, when the relative pressure is in the range exceeding 0.1, it is observed that the present invention carbons A1 and A2 adsorb small amounts of N.sub.2 gas as compared to the present invention carbons A3 and A4, but sufficiently adsorb N.sub.2 gas. The experiment 2 described below was conducted for examining the reason why these experiment results were obtained.

Experiment 2

(44) For the present invention carbons A1 to A4 and comparative carbons Z1 to Z3, the BET specific surface area, the mesopore capacity and the micropore capacity were determined. The results are shown in Table 1. The BET specific surface area was calculated from the results of the adsorption isotherm using the BET method. The mesopore capacity was examined by the BJH (Berret-Joyner-Halenda) method. Further, the micropore capacity was examined by the HK (Horbath-Kawazoe) method.

(45) TABLE-US-00001 TABLE 1 BET Type of carbon material Heat treatment temperature Specific surface area Mesopore capacity Micropore capacity Type of carbon before heat treatment (° C.) (m.sup.2/g) (ml/g) (ml/g) Present invention carbon A1 Porous carbon 2500 340 0.55 0.12 Present invention carbon A2 2000 1450 1.00 0.50 Present invention carbon A3 1400 1700 1.42 0.62 Present invention carbon A4 900 1640 1.59 0.59 Comparative carbon Z1 Activated carbon 2000 12 0 0.02 Comparative carbon Z2 1400 300 0.01 or less 0.10 Comparative carbon Z3 None 1600 0.02 0.56

(46) As clearly seen from Table 1, for the present invention carbons A3 and A4 formed by heat-treating a porous carbon, which is used as a carbon material before heat treatment, at 900° C. or 1400° C., the capacities of mesopores having a high gas adsorbing ability when the relative pressure is high and micropores disposed at positions facing the mesopores and having a gas adsorbing ability when the relative pressure is low are both high. Therefore, for the present invention carbons A3 and A4, the gas adsorbing ability is enhanced regardless of whether the relative pressure is high or low.

(47) On the other hand, for the present invention carbon A2 formed by heat-treating a porous carbon, which is used as a carbon material before heat treatment, at 2000° C., the capacities of mesopores and micropores are slightly low as compared to the present invention carbons A3 and A4, so that the gas adsorbing ability is slightly reduced regardless of whether the relative pressure is high or low. For the present invention carbon A1 formed by heat-treating a porous carbon, which is used as a carbon material before heat treatment, at 2500° C., the capacities of mesopores and micropores are low as compared to the present invention carbon A2 as well as the present invention carbons A3 and A4, and particularly the capacity of micropores is significantly low. Thus, the gas absorbing ability is reduced regardless of whether the relative pressure is high or low, and particularly the capacity of micropores is significantly low, and therefore the gas absorbing ability when the relative pressure is low is particularly reduced.

(48) Further, when the comparative carbons Z1 and Z2 are compared to the comparative carbon Z3, it is observed that micropores are significantly decreased due to the heat treatment. In contrast, when the present invention carbons A2, A3 and A4 are compared to one another, it is observed that by having mesopores, a decrease in micropores is suppressed even if the heat treatment temperature is elevated. However, for the present invention carbon A1 in which the heat treatment temperature is elevated to 2500° C., a decrease in micropores is observed.

(49) It is considered that the results of Experiment 1 were obtained from the reason described above.

(50) As described above, the present invention carbons A1 and A2 have a low gas absorbing ability as compared to the present invention carbons A3 and A4, but it is considered that the gas adsorbing ability is remarkably high as compared to a case where an activated carbon, which is used as a carbon material before heat treatment, is heat-treated. The reason for this is as follows. It is considered that for the comparative carbon Z1 formed by heat-treating an activated carbon, which is used as a carbon material before heat treatment, at 2000° C., the capacities of mesopores and micropores are extremely low, so that the gas adsorbing ability is significantly reduced.

(51) Thus, it is considered that the present invention carbons A1 and A2 can sufficiently exhibit an advantage of the carbon, such as a gas adsorbing ability, because a porous state is maintained by having mesopores, although at least a part of the carbon is crystallized.

(52) For the present invention carbon A2, the capacities of mesopores and micropores are slightly low, and therefore the BET specific surface area is also slightly small, as compared to the present invention carbons A3 and A4. For the present invention carbon A1, the capacities of mesopores and micropores are further low, and therefore the BET specific surface area is also further small. However, the present invention carbons A1 and A2 have a remarkably large BET specific surface area as compared to the comparative carbon Z1 in which the capacities of mesopores and micropores are extremely low.

(53) In addition, for enhancing the gas adsorbing ability or the like, the mesopore capacity is desired to be high, but is not limited to the gas adsorbing ability of the present invention carbon A1, i.e. 0.55 ml/g or more. It suffices that the gas adsorbing ability is 0.2 ml/g or more. It is considered that such a low mesopore capacity is obtained when the porous carbon is heat-treated at a temperature of higher than 2500° C.

Experiment 3

(54) The bulk densities of the present invention carbons A1, A2 and A4 were examined. The results are shown in Table 2.

(55) TABLE-US-00002 TABLE 2 Type of carbon Heat treatment Bulk material before temperature density Type of carbon heat treatment (° C.) (g/cc) Present invention carbon A1 Porous carbon 2500 0.27 Present invention carbon A2 2000 0.15 Present invention carbon A4 900 0.14

(56) As clearly seen from Table 2, it is observed that the present invention carbons A1 and A2 have a high bulk density as compared to the present invention carbon A4, and particularly the bulk density of the present invention carbon A1 is high. This is considered to be due to the fact that as described above, for the present invention carbons A1 and A2, the capacities of mesopores and micropores (capacity of the carbon portion) are low as compared to the present invention carbon A4, and particularly for the present invention carbon A1, the capacities of mesopores and micropores are very low.

Experiment 4

(57) The pore size distribution (mesopore size distribution) in the present invention carbons A1, A2 and A4 was examined using the BJH method. The results are shown in FIGS. 6 to 8 (FIG. 6 shows the present invention carbon A1, FIG. 7 shows the present invention carbon A2, and FIG. 8 shows the present invention carbon A4).

(58) As clearly seen from FIGS. 6 to 8, the peak of the mesopore size in the present invention carbons A1. A2 and A4 is from 3 nm to 5 nm, and therefore the peak of the mesopore size is not changed by a difference in heat treatment temperature.

Experiment 5

(59) The specific resistance in the present invention carbons A1 to A4 and the comparative carbons Z1 to Z3 was examined. The results are shown in Table 3. The experiment was conducted as follows. Each carbon and polytetrafluoroethylene (Teflon (registered trademark) 6J) manufactured by Du Pont) as a binder were physically mixed at a weight ratio of 80:20, acetone as a solvent was added to the mixture, and the mixture was processed into a sheet. For drying off the solvent, the sheet was dried at 120° C. for 5 hours to fabricate a sheet of 100 mm×100 mm×1 mm. The specific resistance of the sheet was measured using a four-terminal method.

(60) TABLE-US-00003 TABLE 3 Heat Type of carbon treatment Specific material before temperature resistance Type of carbon heat treatment (° C.) (Ω .Math. cm) Present invention carbon A1 Porous carbon 2500 2.0 Present invention carbon A2 2000 3.1 × 10.sup.1 Present invention carbon A3 1400 1.0 × 10.sup.5 Present invention carbon A4 900 3.5 × 10.sup.5 Comparative carbon Z1 Activated 2000 8.0 × 10.sup.2 Comparative carbon Z2 carbon 1400 3.8 × 10.sup.4 Comparative carbon Z3 None 2.4 × 10.sup.5

(61) As clearly seen from Table 3, when the case is considered where a porous carbon is used as a carbon material before heat treatment, the present invention carbons A1 and A2, the heat treatment temperature of which is 2000° C. or higher, have a specific resistance of from 2.0 Ω.Math.cm to 3.1×10.sup.1Ω.Math.cm, whereas the present invention carbons A3 and A4, the heat treatment temperature of which is lower than 2000° C., have a specific resistance of from 1.0×10.sup.5Ω.Math.cm to 3.5×10.sup.5Ω.Math.cm. Therefore, it is observed that the present invention carbons A1 and A2 have a remarkably low specific resistance as compared to the present invention carbons A3 and A4.

(62) On the other hand, when the case is considered where an activated carbon is used as a carbon material before heat treatment, the comparative carbon Z1, the heat treatment temperature of which is 2000° C. or higher, has a specific resistance of 8.0×10.sup.2Ω.Math.cm whereas the comparative carbons Z2 and Z3, the heat treatment temperature of which is lower than 2000° C., have a specific resistance of from 3.8×10.sup.4 cm to 2.4×10.sup.5Ω.Math.cm. Therefore, the comparative carbon Z1 has a low specific resistance as compared the comparative carbons Z2 and Z3. However, it is observed that the comparative carbon Z1 has a high specific resistance when compared to the present invention carbons A1 and A2. The reason for this is not clear, but this is considered to be due to the fact that in the present invention carbons A1 and A2, there exist sufficient mesopores, so that a layered structure grows, whereas in the comparative carbon Z1, there exist little mesopores, so that a layered structure hardly grows.

(63) A lower specific resistance is more preferable, but it is not necessary that the specific resistance be 3.1×10.sup.1Ω.Math.cm or less, and use can be made in various fields as long as the specific resistance is 1.0×10.sup.2Ω.Math.cm or less.

Experiment 6

(64) X-ray diffraction (ray source CuKα) was performed for the present invention carbons A1 and A4. The results are shown in FIG. 9.

(65) As clearly seen from FIG. 9, the peak of graphite (002 plane) is evidently observed at a Bragg angle (2θ±0.2°) of 26.45° in the present invention carbon A1, whereas the peak of graphite (002 plane) is not much observed at a Bragg angle of 26.45° in the present invention carbon A4. Therefore, it is observed that carbon is graphitized in the present invention carbon A1, but carbon is not much graphitized in the present invention carbon A4.

(66) When the microcrystal size was determined from the half-width of the peak in the X-ray diffraction result using a Scherrer's equation, the diameter of the microcrystal was about 30 nm.

INDUSTRIAL APPLICABILITY

(67) The present invention is applicable to, for example, a gas adsorbent material, a negative electrode material of a nonaqueous electrolyte battery, and an electrode material of a capacitor.

DESCRIPTION OF REFERENCE NUMERALS

(68) 1—Polyamic acid resin (Imide-based resin) 2—Magnesium oxide 3—Carbonaceous wall 4—Mesopore 5—Porous carbon