Carbon material for catalyst carrier of polymer electrolyte fuel cell, and method of producing the same

Abstract

The present invention is a carbon material for a catalyst carrier of a polymer electrolyte fuel cell, which has a three-dimensional dendritic structure, and simultaneously satisfies the following (A), (B), and (C). (A) By a laser Raman spectroscopic analysis with a wavelength of 532 nm, a standard deviation δ(R) of an intensity ratio (R value) of an intensity of a D-band (near 1360 cm.sup.−1) to an intensity of a G-band (near 1580 cm.sup.−1) measured with a beam diameter of 1 μm at 50 measurement points is from 0.01 to 0.07. (B) A BET specific surface area S.sub.BET is from 400 to 1520 m.sup.2/g. (C) A nitrogen gas adsorption amount V.sub.N:0.4-0.8 during a relative pressure (p/p.sub.0) from 0.4 to 0.8 is from 100 to 300 cc(STP)/g. A method of producing such a carbon material for a catalyst carrier is also included.

Claims

1. A carbon material for a catalyst carrier of a polymer electrolyte fuel cell, which is a porous carbon material with a three-dimensionally branched three-dimensional dendritic structure, and simultaneously satisfying the following (A), (B), and (C): (A) by a Raman spectroscopic analysis in which a laser beam with a wavelength of 532 nm is used as excitation light, a circular beam diameter for irradiating a sample is 1 μm, and 50 arbitrary measurement points are measured with respect to the same sample, an obtained standard deviation δ(R) of a relative intensity ratio I.sub.D/I.sub.G (R value) of an intensity of a D-band (in a range of 1310 cm.sup.−1 to 1410 cm.sup.−1) to an intensity of a G-band (in a range of 1530 cm.sup.−1 to 1630 cm.sup.−1) is from 0.01 to 0.07, (B) a BET specific surface area S.sub.BET obtained by a BET analysis of a nitrogen gas adsorption isotherm is from 400 to 1520 m.sup.2/g, and (C) a nitrogen gas adsorption amount V.sub.N:0.4-0.8 adsorbed during a relative pressure (p/p.sub.0) from 0.4 to 0.8 in the nitrogen gas adsorption isotherm is from 100 to 300 cc(STP)/g.

2. The carbon material for a catalyst carrier of a polymer electrolyte fuel cell according to claim 1, wherein a standard deviation δ(ΔG) of a full width at half maximum ΔG of the G-band (in a range of 1530 cm.sup.−1 to 1630 cm.sup.−1) in the Raman spectroscopic analysis of (A) above is from 0.10 to 1.30.

3. The carbon material for a catalyst carrier of a polymer electrolyte fuel cell according to claim 1, wherein an average value R.sub.ave of measured R values in the Raman spectroscopic analysis of (A) above is from 1.3 to 1.85.

4. The carbon material for a catalyst carrier of a polymer electrolyte fuel cell according to claim 2, wherein an average value ΔG.sub.ave of measured ΔG values in the Raman spectroscopic analysis of (A) above is from 45 to 75 cm′.

5. A method of producing a carbon material for a catalyst carrier of a polymer electrolyte fuel cell comprising: producing an acetylide by blowing an acetylene gas into a reaction solution comprising an aqueous ammonia solution of silver nitrate to synthesize silver acetylide, a first heat treatment of heat-treating the silver acetylide at a temperature of from 40 to 80° C. to prepare a silver particle-encapsulated intermediate, a second heat treatment of causing a self-decomposing and explosive reaction of the silver particle-encapsulated intermediate at a temperature of from 120 to 200° C. to yield a decomposition product, an oxidation treatment of heat-treating the decomposition product in an oxygen-containing atmosphere with an oxygen content of from 1 to 25% by volume at from 80 to 150° C. for from 10 min to 100 min to obtain the decomposition product which has been subjected to an oxidation treatment and freed from nonaromatic carbon by combustion of an oxygen-containing gas, washing to remove silver from the decomposition product after the oxidation treatment to yield a carbon material intermediate, and a third heat treatment of heat-treating the carbon material intermediate in a vacuum or an inert gas atmosphere at a temperature of from 1600 to 2300° C. to yield a carbon material for a catalyst carrier.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a graph chart having plotted the R values and ΔG values measured at 50 measurement points for the carbon material for a catalyst carrier of Experimental Example 5 on an R value vs. ΔG value graph.

(2) FIG. 2 is a graph chart having plotted the R values and ΔG values measured at 50 measurement points for the carbon material for a catalyst carrier of Experimental Example 19 on an R value vs. ΔG value graph.

(3) FIG. 3 is a graph chart having plotted the R values and ΔG values measured at 50 measurement points for the carbon material for a catalyst carrier of Experimental Example 22 on an R value vs. ΔG value graph.

(4) FIG. 4 is a graph chart having plotted the R values and ΔG values measured at 50 measurement points for the carbon material for a catalyst carrier of Experimental Example 8 on an R value vs. ΔG value graph.

(5) FIG. 5 is a graph chart having plotted the R values and ΔG values measured at 50 measurement points for the carbon material for a catalyst carrier of Experimental Example 13 on an R value vs. ΔG value graph.

(6) FIG. 6 is a graph chart showing the Raman spectrum obtained by a Raman spectroscopic analysis on the porous carbon material of Experimental Example 5.

(7) FIG. 7 is a graph chart showing the Raman spectrum obtained by a Raman spectroscopic analysis on the porous carbon material of Experimental Example 29.

(8) FIG. 8 is a graph chart showing the Raman spectrum obtained by a Raman spectroscopic analysis on the porous carbon material of Experimental Example 33.

(9) FIG. 9 is a photograph showing the measurement method of measuring a branch diameter, when a carbon material for a catalyst carrier of the present disclosure was observed with SEM.

(10) FIG. 10 is an explanatory diagram showing the method of measuring a branch diameter of a carbon material for a catalyst carrier of the present disclosure.

DESCRIPTION OF EMBODIMENTS

(11) An example of a preferred Embodiment with respect to a carbon material for a catalyst carrier of a polymer electrolyte fuel cell and a producing method therefor of the present disclosure will be described in detail below.

(12) A carbon material for a catalyst carrier of a polymer electrolyte fuel cell of the present disclosure is a porous carbon material which has a three-dimensionally branched three-dimensional dendritic structure, and satisfies the following (A), (B), and (C) at the same time:

(13) (A) By a Raman spectroscopic analysis in which a laser beam with a wavelength of 532 nm is used as excitation light, the circular beam diameter for irradiating a sample is 1 μm, and optional 50 measurement points are measured with respect to the same sample, the obtained standard deviation δ(R) of an intensity ratio I.sub.D/I.sub.G (R value) of the intensity of D-band (near 1360 cm.sup.−1) to the intensity of G-band (near 1580 cm.sup.−1) is from 0.01 to 0.07,
(B) a BET specific surface area S.sub.BET obtained by a BET analysis of a nitrogen gas adsorption isotherm is from 400 to 1520 m.sup.2/g, and
(C) the nitrogen gas adsorption amount V.sub.N:0.4-0.8 adsorbed during the relative pressure (p/p.sub.0) from 0.4 to 0.8 in the nitrogen gas adsorption isotherm is from 100 to 300 cc(STP)/g.

(14) In this regard, the unit of a nitrogen gas adsorption amount is cc(STP)/g, the unit of a BET specific surface area S.sub.BET is m.sup.2/g, and the unit of the average value ΔG.sub.ave of ΔG values is cm.sup.−1.

(15) A carbon material for a catalyst carrier of the present disclosure may be a porous carbon material with a three-dimensionally branched three-dimensional dendritic structure. The porous carbon material with a three-dimensionally branched three-dimensional dendritic structure is preferably including dendritic carbon nanostructures. Specifically, the dendritic carbon nanostructure is yielded from a silver acetylide having a three-dimensional dendritic structure as an intermediate. With respect to the carbon material for a catalyst carrier, the BET specific surface area S.sub.BET is from 400 m.sup.2/g to 1,520 m.sup.2/g, preferably from 400 m.sup.2/g to 1,500 m.sup.2/g, and more preferably from 500 m.sup.2/g to 1,400 m.sup.2/g. When the BET specific surface area S.sub.BET is less than 400 m.sup.2/g, there is a risk that it becomes difficult to support catalyst metal fine particles at a high density in the pores. Meanwhile, when it is allowed to exceed 1,520 m.sup.2/g, the durability tends to be lowered as the crystallinity decreases substantially.

(16) In this regard, a dendritic carbon nanostructure is a dendritic carbon structure having a branch diameter of 10 nm or more and several 100s nanometers or less (for example, 500 nm or less, and preferably 200 nm or less). The branch diameter is measured as in Examples described below using a scanning electron microscope (SEM; SU-9000 manufactured by Hitachi High-Technologies Corporation), and SEM images at 5 visual fields (size 2.5 μm×2 μm) were observed at 100000-fold magnification. Branch diameters were measured at 20 positions in each visual field, and the average value of total 100 measurements is regarded as the branch diameter. The branch diameter is determined as the thickness of a branch of interest measured at the center between the adjacent two branch points (the middle part of the branched branch) (refer to FIG. 9, D in FIG. 9 stands for a branch diameter at one position). Referring to FIG. 10, the method of measuring a branch diameter will be described. In FIG. 10, one branch of interest is shown. For this branch of interest, the branch point BP 1 and the branch point BP 2 are specified. Next the specified branch point BP 1 and branch point BP 2 are connected with a line segment, and the thickness (width) of the branch is measured on the perpendicular bisector BC of the line segment connecting the branch point BP 1 and the branch point BP 2. The measured thickness of the branch is a branch diameter D at one position.

(17) In the present disclosure, with respect to a carbon material for a catalyst carrier optional 50 measurement points are measured with respect to the same sample by a Raman spectroscopic analysis in which a laser beam with a wavelength of 532 nm is used as excitation light, and the circular beam diameter for irradiating a sample is 1 μm. The obtained standard deviation δ(R) of the intensity ratio I.sub.D/I.sub.G (R value) of the intensity of D-band (near 1360 cm.sup.−1) to the intensity of G-band (near 1580 cm.sup.−1) is 0.01 to 0.07 (preferably from 0.01 to 0.06). The lower limit of 0.01 of the standard deviation δ(R) of the R values is a standard deviation inevitable in view of measurement error or the like, and is substantially the minimum standard deviation value. In the present disclosure, there is no particular restriction on the lower limit of the standard deviation δ(R) of the R values. Conversely, when the standard deviation δ(R) of the R values exceeds 0.07, the content of a graphitized product increases. In addition, the particle size of the graphitized product also becomes relatively large. As a result, in a catalyst layer using such a carbon material as the catalyst carrier, a large number of aggregates appear in the layer, and therefore the high current characteristics may deteriorate. The reason why 50 measurement points was selected as the number of measurement points in a Raman spectroscopic analysis was because the number of measurement points was judged as an adequate number for detecting a graphitized material based on the result of the statistical processing of the “dispersion of Raman measurement values” in a Raman spectroscopic analysis.

(18) Further, in a carbon material for a catalyst carrier of the present disclosure, in order to improve the high current characteristics, the dispersion [standard deviation δ(ΔG)] of the full width at half maximum ΔG of the intensity of G-band (near 1580 cm.sup.−1) in the Raman spectroscopic analysis corresponding to the size of the hexagonal carbon layer plane is preferably small. That is, when particles are observed in the size order of 1 μm, it is desirable that the crystallinity of the particles is within a certain range at that size. When the standard deviation δ(ΔG) is large, it means that a graphitized material in the order of 1 μm is contained. When a graphitized material in the order of 1 μm is contained, the pores in a catalyst layer may be eventually collapsed, and as a consequence the high current characteristics may be deteriorated. Therefore, the standard deviation δ(ΔG) of the full width at half maximum ΔG of the intensity of G-band (near 1580 cm.sup.−1) is preferably from 0.10 to 1.30, and more preferably from 0.10 to 1.20. Further, the average value R.sub.ave of the R values is preferably from 1.3 to 1.85. It is more preferably from 1.3 to 1.8. Further, from the viewpoints of improvement of the crystallinity and improvement of the durability, the average value ΔG.sub.ave of the measured ΔG values is preferably from 45 cm.sup.−1 to 75 cm.sup.−1, more preferably from 55 cm.sup.−1 to 65 cm.sup.−1.

(19) For the standard deviation δ(ΔG), the substantial minimum value is 0.10, but in the present disclosure, there is no particular restriction on the lower limit of the standard deviation δ(ΔG). On the contrary, when the standard deviation δ(ΔG) of the full width at half maximum ΔG exceeds 1.30, the pores in the catalyst layer collapse for the above-mentioned reason, so that the high current characteristics may be deteriorated.

(20) When the average value R.sub.ave is less than 1.3, the crystallinity becomes too high and the ruggedness of the pore walls decreases, and the adsorbability of the catalyst metal fine particles to the pore walls may decrease. On the contrary, when it exceeds 1.85, the crystallinity is too low, and the durability may decrease. Meanwhile, the ΔG value is also an index representing crystallinity similarly to the R value. Therefore, when the average value ΔG.sub.ave is less than 45 cm.sup.−1, the crystallinity becomes too high and the ruggedness of the pore walls decreases, and the adsorbability of the catalyst metal fine particles to the pore walls may decrease. On the contrary, when ΔG.sub.ave exceeds 75 cm.sup.−1, the crystallinity is too low and the durability may decrease.

(21) From the viewpoint of the gas diffusibility inside micropores to be formed in the catalyst layer, a carbon material for a catalyst carrier of the present disclosure preferably exhibit a nitrogen gas adsorption amount V.sub.N:0.4-0.8 adsorbed during the relative pressure (p/p.sub.0) from 0.4 to 0.8 in the nitrogen gas adsorption isotherm is 100 cc(STP)/g or more and 300 cc(STP)/g or less, (and more preferably 120 cc(STP)/g or more and 250 cc(STP)/g or less). When the nitrogen gas adsorption amount V.sub.N:0.4-0.8 is less than 100 cc(STP)/g, the pore volume of meso-size pores supporting catalyst metal fine particles becomes small, and there arises a risk that the gas diffusibility in micropores to be formed in a catalyst layer also decreases to increase the reaction resistance. On the contrary, when it exceeds 300 cc(STP)/g, the carbon wall forming the pores becomes too thin, and the mechanical strength of the material may be impaired to cause material destruction at an electrode producing step.

(22) In the method of producing the carbon material for a catalyst carrier of the present disclosure, nonaromatic carbon in a decomposition product obtained by inducing a self-decomposing and explosive reaction of silver acetylide is removed to the extent possible. For this purpose, in addition to the production method heretofore generally adopted, an oxidation treatment step is applied in which a decomposition product is heat-treated in an oxygen-containing atmosphere 80° C. or more and 150° C. or less (preferably 85° C. or more and 145° C. or less) before silver is removed from the decomposition product, so as to remove nonaromatic carbon from the decomposition product to the extent possible. Further, from the viewpoint of removing as selectively as possible nonaromatic carbon which is easily combustible compared to aromatic carbon, the oxygen content in the oxygen-containing atmosphere is preferably from 1% by volume to 25% by volume (preferably from 2% by volume to 23% by volume). Further, the treatment time of the oxidation treatment is from 10 min to 100 min (preferably from 10 min to 90 min). When the treatment temperature during the oxidation treatment is lower than 80° C., oxidation of nonaromatic carbon may become incomplete and a graphitized product may be formed. On the contrary, when the temperature exceeds 150° C., there is a possibility that aromatic carbon which should remain is lost by combustion. Regarding the oxygen content in the oxygen-containing atmosphere, when it is less than 1% by volume, oxidation of nonaromatic carbon may become incomplete, and a graphitized product may be formed. On the contrary, when it exceeds 30% by volume, aromatic carbon which should remain may be lost by combustion. Furthermore, when it is attempted to shorten the treatment time below 10 min, exposure to a stronger oxidizing condition becomes necessary, and not only nonaromatic carbon but also aromatic carbon may be oxidized and consumed. On the contrary, if it exceeds 100 min, the productivity may decrease and the production cost may be increased.

(23) A porous carbon material with a three-dimensionally branched three-dimensional dendritic structure (specifically, carbon material for a catalyst carrier including dendritic carbon nanostructures with a three-dimensional dendritic structure) of the present disclosure, may be prepared through a method similar to the conventional method using a decomposition product of silver acetylide, which is obtained in the oxidation treatment step in the above and from which nonaromatic carbon has been removed to the extent possible.

(24) That is, a carbon material for a catalyst carrier of the present disclosure may be obtained by a producing method having the following steps.

(25) An (acetylide producing step) where an acetylene gas is blown into a reaction solution incliding an ammoniac aqueous solution of silver nitrate to synthesize silver acetylide;

(26) a (first heat treatment step) where the obtained silver acetylide is heat-treated at a temperature of from 40 to 80° C. to prepare a silver particle-encapsulated intermediate;

(27) a (second heat treatment step) where the silver particle-encapsulated intermediate is made to undergo a self-decomposing and explosive reaction at a temperature of from 120 to 200° C., and the decomposition product is recovered;

(28) an (oxidation treatment step) where the recovered decomposition product is heat-treated in an oxygen-containing atmosphere with an oxygen content of from 1 to 25% by volume at from 80 to 150° C. for from 10 min to 100 min to remove nonaromatic carbon by a heat treatment due to combustion of an oxygen-containing gas;

(29) a (washing step) where the carbon material intermediate is recovered by removing silver from the decomposition product after the oxidation treatment;

(30) and

(31) a (third heat treatment step) where the recovered carbon material Intermediate is heat-treated in a vacuum or an inert gas atmosphere at a temperature of from 1600 to 2300° C.

(32) What is essentially important in the present disclosure is removal of the nonaromatic carbon contained in the decomposition product of silver acetylide after the second heat treatment step by combustion with oxygen. By a treatment with an acidic aqueous solution for removing silver used in the conventional washing treatment (for example, washing treatment with hot concentrated sulfuric acid, hot concentrated nitric acid, etc.), silver can be removed, but nonaromatic carbon contained in the decomposition product of silver acetylide cannot be removed. As a result, graphitic carbon is contained in the porous carbon finally obtained after the third heat treatment step. Meanwhile, when the decomposition product of silver acetylide undergoes an oxidation treatment in the exemplified oxygen-containing atmosphere, a carbon material for a catalyst carrier of the present disclosure from which only the nonaromatic carbon has been selectively removed may be obtained.

(33) The carbon material for a catalyst carrier of the present disclosure produced as above is a porous carbon material having a three-dimensionally branched three-dimensional dendritic structure (specifically, a porous carbon material composed of dendritic carbon nanostructures with a three-dimensional dendritic structure) suitable as a catalyst carrier. Further, it is not only equivalent or superior to the conventional porous carbon materials of this type in terms of the BET specific surface area, and the durability, but also it is freed from a highly crystalline graphitized material having a relatively large aggregated structure to the extent possible. Consequently, in a catalyst layer prepared using a porous carbon material of the present disclosure as the catalyst carrier, a reactive gas may be diffused without resistance. Further, micropores suitable for discharging water generated in the catalyst layer (generated water) without delay are formed. As a result, the high current (heavy-load) characteristics of a polymer electrolyte fuel cell may be remarkably improved (in other words, the output voltage at the time of high current may be significantly increased).

EXAMPLES

(34) A carbon material for a catalyst carrier and a production method therefor of the present disclosure will be specifically described below based on Experimental Examples.

(35) The measurements of the BET specific surface area S.sub.BET, nitrogen gas adsorption amount V.sub.N:0.4-0.8, standard deviation δ(R) of the R values, average value R.sub.ave of the R values, standard deviation δ(ΔG) of ΔG values, and average value ΔG.sub.ave of the ΔG values of carbon materials for a catalyst carrier prepared in the following Experimental Examples were respectively conducted as follows.

(36) [Measurement of BET Specific Surface Area, and Nitrogen Gas Adsorption Amount V.sub.N:0.4-0.8].

(37) Approximately 30 mg of the carbon material for a catalyst carrier produced or prepared in each of the Experimental Examples was weighed and dried in a vacuum at 120° C. for 2 hours. Thereafter, nitrogen gas adsorption isotherm was measured using an automatic specific surface area measuring device (BELSORP-MAX, manufactured by MicrotracBEL Corp.) using a nitrogen gas as an adsorbate. The BET specific surface area was calculated by carrying out a BET analysis in the p/p.sub.0 range of from 0.05 to 0.15 of an adsorption isotherm.

(38) Also, the difference between the adsorption amount cc(STP)/g when the p/p.sub.0 of the adsorption isotherm was 0.8, and the adsorption amount cc(STP)/g when the p/p.sub.0 was 0.4 was calculated, and used as the value of V.sub.N:0.4-0.8.

(39) [Measurement of Standard Deviation δ(R) and Average Value R.sub.ave of R Values, and Standard Deviation δ(ΔG) and Average Value ΔG.sub.ave of ΔG Values in Raman Spectroscopic Analysis]

(40) Approximately 3 mg of samples of the carbon material for a catalyst carrier produced or prepared in each of the Experimental Examples was weighed out. The sample was mounted on a laser Raman spectrophotometer (model NRS-3100 manufactured by Jasco Corporation), and a measurement was carried out under measurement conditions: excitation laser: 532 nm, laser power: 10 mW (sample irradiation power: 1.1 mW), microscope arrangement: backscattering, slit: 100 μm×100 μm, objective lens: 100×, spot diameter: 1 μm, exposure time: 30 sec, observation wavenumber: from 2000 to 300 cm.sup.−1, and cumulative number: 6. From each of the obtained 6 spectra, the intensity (peak height) and the full width at half maximum ΔG of the G-band (near 1580 cm.sup.−1) were determined. Further, the intensity (peak height) of the D-band (near 1360 cm.sup.−1), and the R value (relative intensity ratio I.sub.D/I.sub.G) were determined. In this regard, with respect to the same set sample, optional 50 measurement points were measured changing laser irradiation positions. With respect to the data obtained from the 50 measurement points, the standard deviations were calculated to find the standard deviation δ(R) of R values, and the standard deviation δ(ΔG) of ΔG values, as well as the average value R.sub.ave of R values and the average value ΔG.sub.ave of ΔG values.

Experimental Examples 1 to 26

(41) (1) Silver Acetylide Producing Step

(42) Ammonia was added to an aqueous solution of silver nitrate adjusted to a concentration of 5% by mass such that ammonia becomes 8 times as much as silver nitrate in terms of molar ratio to prepare an ammoniac aqueous solution of silver nitrate. Then, firstly a nitrogen gas was blown therein for 40 to 60 min. Thereby, the dissolved oxygen was replaced with the inert gas to eliminate the risk of explosive decomposition of the silver acetylide produced in the silver acetylide producing step.

(43) Next, an acetylene gas was blown into the ammoniac aqueous solution of silver nitrate prepared in this way at room temperature for about 10 min. When the acetylene gas began to emit as bubbles from the reaction solution, the acetylene gas blow was discontinued. When silver nitrate and acetylene in the reaction solution were allowed to react further, a white precipitate of silver acetylide was formed.

(44) The formed precipitate of silver acetylide was recovered by filtration through a membrane filter. The recovered precipitate was redispersed in methanol and filtrated again, and the collected precipitate was transferred into a petri dish,

(45) (2) First Heat Treatment Step

(46) Approximately 0.5 g of silver acetylide yielded in the above silver acetylide producing step of each Experimental Example in a state impregnated with methanol was placed as it was in a stainless steel cylindrical container with a diameter of 5 cm. This was then placed in a vacuum electric heating furnace and dried in a vacuum at 60° C. for about from 15 to 30 min to prepare a silver particle-encapsulated intermediate derived from silver acetylide of each of Experimental Example.

(47) (3) Second Heat Treatment Step

(48) Next, the 60° C. silver particle-encapsulated intermediate obtained in the first heat treatment step immediately after the vacuum drying was directly, without taking out from the vacuum electric heating furnace, heated to a temperature of 200° C. In the course of the heating, a self-decomposing and explosive reaction of silver acetylide was induced to prepare a carbon material intermediate including a composite of silver and carbon.

(49) In the course of this self-decomposing and explosive reaction, silver nano-sized particles (silver nanoparticles) are formed. At the same time, a carbon layer with a hexagonal layer plane is formed surrounding such a silver nanoparticle to form skeleton with a three-dimensional dendritic structure. Furthermore, the produced silver nanoparticles are made porous by explosion energy and erupted outward through pores in the carbon layer to form silver aggregates (silver particles).

(50) (4) Oxidation Treatment Step

(51) The decomposition product composing of a composite of silver and carbon obtained in the second heat treatment step was placed in an oxidation treatment container. Then, an oxygen-mixed nitrogen gas obtained by adding an oxygen gas in a nitrogen gas to the oxygen content shown in Table 1 was circulated through the oxidation treatment container. While circulating the oxygen mixed nitrogen gas through the oxidation treatment container, the temperature was raised at an elevation rate of 10° C./min up to the temperature shown in Table 1. The system was held at the temperature shown in Table 1 for the treatment time shown in Table 1 for performing the oxidation treatment of the decomposition product.

(52) (5) Washing Treatment Step

(53) For the decomposition product after the oxidation treatment composed of a composite of silver and carbon obtained in the oxidation treatment step, a dissolution treatment (washing treatment) on silver was carried out at 60° C. with concentrated nitric acid having a concentration of 30% by mass. By this way, silver particles and other unstable carbon compounds present on the surface of the carbon material intermediate were removed to obtain a cleaned carbon material intermediate.

(54) In Experimental Examples 21, 22, and 23, the washing time in the washing treatment step was set respectively at 3 hours, 5 hours, and 10 hours for the same material obtained in the oxidation treatment step, while the heat treatment temperature in the third heat treatment step was 2000° C.

(55) (6) Third Heat Treatment Step

(56) The carbon material intermediate cleaned in the washing treatment step was heat-treated in an inert gas atmosphere at the heating temperature set forth in Table 1 for 2 hours to yield a carbon material for a catalyst carrier of each of Experimental Examples. The heat treatment temperature in the third heat treatment step was a temperature heretofore generally adopted for the control of crystallinity. Further, it was examined what influence the heat treatment temperature during the third heat treatment would exert on the physical properties and the battery characteristics of a porous carbon material originated from the decomposition product after the oxidation treatment obtained in each Experimental Example.

(57) With respect to the carbon material for a catalyst carrier prepared as above in each of Experimental Examples 1 to 26, the BET specific surface area S.sub.BET, nitrogen gas adsorption amount V.sub.N:0.4-0.8, standard deviation δ(R) of R values, average value R.sub.ave of R values, standard deviation δ(ΔG) of ΔG values, and average value ΔG.sub.ave of ΔG values were measured.

(58) The results are shown in Table 2.

(59) Further, with respect to each of carbon materials for a catalyst carrier obtained in Experimental Examples 5, 19, and 22, as well as Experimental Examples 8 and 13, the R values and the ΔG values measured at 50 measurement points were plotted on a graph of R value vs. ΔG value with the X axis for R values and the Y axis for ΔG values to obtain a dispersed relationship between these values. The results are shown in FIGS. 1 to 5.

Experimental Examples 27 to 34

(60) In addition, commercially available carbon materials were also examined in Experimental Examples 27 to 34.

(61) As porous carbon materials, a porous carbon material A (KETJENBLACK EC300, produced by Lion Specialty Chemicals Co., Ltd.) (Experimental Example 27), and a porous carbon material B (KETJENBLACK EC600JD, produced by Lion Specialty Chemicals Co., Ltd.) (Experimental Examples 28 to 31), each having a dendritic structure with well-developed pores, and a large specific surface area; were used; as a typical porous carbon material not having a dendritic structure, a porous carbon material C (CNOVEL-MH, produced by Toyo Carbon Co., Ltd.) (Experimental Example 32) was used; and as carbon materials having a well-developed dendritic structure, but not having a porous structure, a carbon material D (acetylene black (AB), produced by Denka Co., Ltd.) (Experimental Example 33), and a carbon material E (conductive grade #4300, produced by Tokai Carbon Co., Ltd.) (Experimental Example 34), were used. With respect to the porous carbon material B, four types were prepared based on the temperature at the third heat treatment, namely the porous carbon material B-1 treated at 1400° C., the porous carbon material B-2 treated at 1700° C., the porous carbon material B-3 treated at 2000° C., and the porous carbon material B-4 treated at 2100° C.

(62) Also with respect to the porous carbon material of each of the Experimental Examples 27 to 34, the BET specific surface area S.sub.BET, nitrogen gas adsorption amount V.sub.N:0.4-0.8, standard deviation δ(R) of R values, average value R.sub.ave of R values, standard deviation δ(ΔG) of ΔG values, and average value ΔG.sub.ave of ΔG values were measured.

(63) The results are shown in Table 2.

(64) Further, an example of the Raman spectra obtained in Raman spectroscopic analysis with respect to a porous carbon material obtained in each of Experimental Example 5, Experimental Example 29, and Experimental Example 33 is shown in one of FIGS. 6 to 8. In this regard, in FIG. 6 the assignment of peaks of D-band and G-band is shown.

(65) <<Preparation of Catalyst, Production of Catalyst Layer, Preparation of MEA, Assembly of Fuel Cell, and Evaluation of Battery Performance>>

(66) Next, using each of the thus produced or prepared carbon materials for a catalyst carrier, catalysts for a polymer electrolyte fuel cell, on which a catalyst metal was supported, were prepared as described below. Further, using an obtained catalyst, an ink solution for a catalyst layer was prepared. Next, using the ink solution for a catalyst layer, a catalyst layer was formed. Further, using the formed catalyst layer a membrane electrode assembly (MEA) was produced, and the produced MEA was fitted into a fuel cell, and a power generation test was performed using a fuel cell measuring device. Preparation of each component and cell evaluation by a power generation test will be described in detail below.

(67) (1) Preparation of Catalyst for Polymer Electrolyte Fuel Cell (Carbon Material Supporting Platinum)

(68) Each of carbon materials for a catalyst carrier prepared as above, or commercially available carbon materials, was dispersed in distilled water. Formaldehyde was added to the dispersion, the dispersion was placed in a water bath set at 40° C., and when the temperature of the dispersion reached the water bath temperature of 40° C., an aqueous nitric acid solution of a dinitrodiamine Pt complex was slowly poured into the dispersion with stirring. Then, stirring was continued for about 2 hours, the dispersion was filtrated, and the obtained solid was washed. The solid obtained in this way was dried in a vacuum at 90° C., then pulverized in a mortar. Next, the solid was heat-treated at 200° C. in an argon atmosphere containing 5% by volume of hydrogen for 1 hour to yield a carbon material supporting platinum catalyst particles.

(69) The supported platinum amount of the carbon material supporting platinum was regulated to 40% by mass with respect to the total mass of the carbon material for a catalyst carrier and the platinum particles, which was confirmed by a measurement based on inductively coupled plasma-atomic emission spectrometry (ICP-AES).

(70) (2) Preparation of Catalyst Layer

(71) The carbon material supporting platinum (Pt catalyst) prepared as above was used. Further, Nafion (registered tradename) (produced by DuPont Co., Ltd., persulfonic acid-based ion exchange resin) was used as an electrolyte resin. The Pt catalyst and the Nafion were mixed in an Ar atmosphere, such that the mass of the Nafion solid component is 1.0 times as much as the mass of the carbon material supporting platinum catalyst particles, and 0.5 times as much as non-porous carbon. After stirring gently, the Pt catalyst was crushed by ultrasonic waves. The total solid concentration of the Pt catalyst and the electrolyte resin was adjusted to 1.0% by mass of by adding ethanol, thereby completing a catalyst layer ink solution in which the Pt catalyst and the electrolyte resin were mixed.

(72) A catalyst layer ink solution for spray coating having a platinum concentration of 0.5% by mass was prepared by adding further ethanol to each catalyst layer ink solution having a solid concentration of 1.0% by mass, which was prepared as above. The catalyst layer ink solution for spray coating was sprayed on a Teflon (registered tradename) sheet after adjustment of spraying conditions such that the mass of platinum per unit area of catalyst layer (hereinafter referred to as “platinum basis weight”) become 0.2 mg/cm.sup.2. Then, a drying treatment was carried out in argon at 120° C. for 60 min to complete a catalyst layer.

(73) (3) Preparation of MEA

(74) An MEA (membrane electrode assembly) was produced by the following method using the catalyst layer prepared as above.

(75) A square electrolyte membrane of 6 cm on a side was cut out from a Nafion membrane (NR 211 produced by DuPont Co., Ltd.). Each of the anode or cathode catalyst layer coated on a Teflon (registered tradename) sheet was cut out with a cutter knife into a square of 2.5 cm on a side.

(76) Between the anode catalyst layer and the cathode catalyst layer cut out as above, the electrolyte membrane was inserted such that the two catalyst layers sandwich the central part of the electrolyte membrane. Then, the electrolyte membrane was inserted tightly in contact with the catalyst layers without misalignment between the electrolyte membrane and the catalyst layers, and the laminate was pressed at 120° C. under a pressure of 100 kg/cm.sup.2 for 10 min. After cooling down to room temperature, only the Teflon (registered tradename) sheets were peeled off carefully from the respective catalyst layers of the anode and the cathode to compete an assembly of the catalyst layers and the electrolyte membrane, in which the respective catalyst layers of the anode and the cathode are fixed to the electrolyte membrane.

(77) Next, as a gas diffusion layer, a pair of square carbon paper sheets of 2.5 cm on a side were cut out from carbon paper (35 BC produced by SGL Carbon Co., Ltd.). The assembly of the catalyst layers and the electrolyte membrane was inserted between the carbon paper sheets, such that the respective catalyst layers of the anode and the cathode were placed without misalignment, then the laminate was pressed at 120° C. under a pressure of 50 kg/cm.sup.2 for 10 min, to compete an MEA.

(78) The basis weights of the catalyst metal component, the carbon material, and the electrolyte material in each of the produced MEA were calculated based on the mass of a catalyst layer fixed to the Nafion membrane (electrolyte membrane) found from the difference between the mass of the Teflon (registered tradename) sheet with the catalyst layer before pressing and the mass of the peeled Teflon (registered tradename) sheet after pressing, and the mass ratio of the components in the catalyst layer.

(79) (4) Evaluation of Performance of Fuel Cell

(80) [Evaluation of High Current Characteristics]

(81) An MEA produced using the carbon material for a catalyst carrier produced or prepared in each Experimental Example was fitted into a cell, which was then set on a fuel cell measuring apparatus, and the performance of the fuel cell was evaluated by the following procedure.

(82) With respect to the reactive gases, on the cathode side air was supplied, and on the anode side pure hydrogen was supplied at a back pressure of 0.04 MPa by regulating the pressure with a back pressure regulating valve placed downstream of the cell so that the respective utilization rates became 40% and 70%. Meanwhile, the cell temperature was set at 80° C., and the supplied reactive gases on both the cathode and anode sides were bubbled through distilled water kept at 60° C. in a humidifier, and the power generation in a low humidification state was evaluated.

(83) Under such conditions, and supplying the reactive gasses to the cell, the load was gradually increased, and an inter-terminal voltage of the cell at a current density of 1000 mA/cm.sup.2 was recorded as the output voltage, and the power generation performance of the fuel cell was evaluated. The power generation performance was rated according to following criteria by which A and B were acceptable ranks, and C was a rejected rank. The results are shown in Table 1.

(84) (Acceptable Ranks)

(85) A: The output voltage at 1000 mA/cm.sup.2 is not less than 0.65 V.

(86) B: The output voltage at 1000 mA/cm.sup.2 is not less than 0.60 V and less than 0.65 V.

(87) (Rejected Rank)

(88) C: The output voltage is inferior to B.

(89) [Evaluation of Durability]

(90) In the cell, the anode was kept as it was (pure hydrogen with a gas utilization rate of 40% was supplied after bubbling humidification through distilled water kept at 60° C. in a humidifier). On the other hand, an argon gas under the same humidification condition as above (bubbling through distilled water kept at 60° C. in a humidifier) was fed to the cathode. While maintaining these conditions, a cycle in which an operation of holding the cell voltage at 1.0 V for 4 sec, and then an operation of holding the cell voltage at 1.3 V for 4 sec were performed in series (repetitive operation of rectangular pulse-like voltage profile), was repeated 400 times as a repetitive operation of the rectangular pulse-like voltage variation. Thereafter the durability test was performed by examining the battery performance in the same manner as the evaluation of the high current characteristics described above. The durability was rated according to following criteria by which A and B were acceptable ranks, and C was a rejected rank. The results are shown in Table 1.

(91) (Acceptable Ranks)

(92) A: The decay rate of the output voltage at 1000 mA/cm.sup.2 is not more than 10%.

(93) B: The decay rate of the output voltage at 1000 mA/cm.sup.2 is more than 10% and less than 15%.

(94) (Rejected Rank)

(95) C: Inferior to the acceptable rank B. Namely, the decay rate of the output voltage is not less than 15%.

(96) TABLE-US-00001 TABLE 1 Oxidation treatment step Oxygen Temperature content Treatment of 3rd heat Experiment Temperature (% by time treatment symbol (° C.) volume) (min) (° C.) Remarks Experimental M1 — — — 2000 N Example 1 Experimental M2 60 20 30 2000 N Example 2 Experimental M3 70 20 30 2000 N Example 3 Experimental M4 80 20 30 2000 G Example 4 Experimental M5 100 20 30 2000 G Example 5 Experimental M6 120 20 30 2000 G Example 6 Experimental M7 140 20 30 2000 G Example 7 Experimental M8 160 20 30 2000 N Example 8 Experimental M9 100 20 5 2000 N Example 9 Experimental M10 100 20 10 2000 G Example 10 Experimental M11 100 20 60 2000 G Example 11 Experimental M12 100 20 100 2000 G Example 12 Experimental M13 100 20 120 2000 N Example 13 Experimental M14 140 2 80 2000 G Example 14 Experimental M15 140 2 100 2000 G Example 15 Experimental M16 140 2 120 2000 N Example 16 Experimental M17 70 30 5 2000 N Example 17 Experimental M18 80 30 5 2000 N Example 18 Experimental M19 110 5 80 2000 G Example 19 Experimental M20 110 5 100 2000 G Example 20 Experimental M21 100 15 25 2000 G Example 21 Experimental M22 100 15 25 2000 G Example 22 Experimental M23 100 15 25 2000 G Example 23 Experimental M24 100 15 25 1600 G Example 24 Experimental M25 100 15 25 1800 G Example 25 Experimental M26 100 15 25 2200 G Example 26 Experimental Porous carbon material A 1800 N Example 27 Experimental Porous carbon material B-1 1400 N Example 28 Experimental Porous carbon material B-2 1700 N Example 29 Experimental Porous carbon material B-3 2000 N Example 30 Experimental Porous carbon material B-4 2100 N Example 31 Experimental Porous carbon material C 1800 N Example 32 Experimental Carbon material D — N Example 33 Experimental Carbon material E — N Example 34

(97) TABLE-US-00002 TABLE 2 Power generation performance Carbon material for a catalyst carrier Power generation Experiment S.sub.BET ΔV.sub.N: 0.4-0.8 δ(R) δ(ΔG) R.sub.ave ΔG.sub.ave characteristics at symbol (m.sup.2/g) cc(STP)/g (cm.sup.−1) (cm.sup.−1) (cm.sup.−1) (cm.sup.−1) 1000 mA/cm.sup.2 Durability Remarks Experimental M1 1090 105 0.14 1.82 1.6 57 C B N Example 1 Experimental M2 1130 110 0.14 1.61 1.65 58 C B N Example 2 Experimental M3 1140 115 0.14 1.63 1.7 60 C B N Example 3 Experimental M4 1150 145 0.07 1.28 1.75 61 A B G Example 4 Experimental M5 1160 135 0.06 0.97 1.69 60 A B G Example 5 Experimental M6 1010 130 0.04 0.93 1.6 57 A B G Example 6 Experimental M7 970 125 0.04 0.91 1.55 55 A B G Example 7 Experimental M8 890 90 0.09 1.89 1.66 56 C B N Example 8 Experimental M9 1080 105 0.11 2.02 1.61 57 C B N Example 9 Experimental M10 1100 125 0.07 1.08 1.6 60 B B G Example 10 Experimental M11 1150 135 0.06 1.11 1.65 61 A B G Example 11 Experimental M12 1160 125 0.06 1.37 1.65 60 B B G Example 12 Experimental M13 1170 90 0.09 2.4 1.5 57 C B N Example 13 Experimental M14 1120 150 0.05 1.12 1.65 61 A B G Example 14 Experimental M15 1020 155 0.06 1.14 1.85 67 A B G Example 15 Experimental M16 940 95 0.17 1.37 1.85 72 C B N Example 16 Experimental M17 980 95 0.17 1.48 1.45 64 C B N Example 17 Experimental M18 960 95 0.16 1.47 1.5 62 C B N Example 18 Experimental M19 1120 130 0.05 1 1.66 59 A B G Example 19 Experimental M20 1170 135 0.05 0.79 1.65 58 A B G Example 20 Experimental M21 1180 185 0.04 0.8 1.65 62 A A G Example 21 Experimental M22 1190 195 0.04 0.64 1.7 61 A A G Example 22 Experimental M23 1210 205 0.02 0.62 1.45 62 A A G Example 23 Experimental M24 1520 295 0.02 0.21 1.35 74 A B G Example 24 Experimental M25 1320 245 0.03 0.42 1.7 66 A B G Example 25 Experimental M26 910 145 0.05 0.79 1.6 53 A A G Example 26 Experimental Porous carbon 525 105 0.12 1.42 0.95 39 C B N Example 27 material A Experimental Porous carbon 1200 382 0.11 1.43 1.62 66 B C N Example 28 material B-1 Experimental Porous carbon 580 215 0.11 1.43 0.78 40 B C N Example 29 material B-2 Experimental Porous carbon 360 126 0.11 1.42 0.75 39 C C N Example 30 material B-3 Experimental Porous carbon 290 107 0.11 1.43 0.72 38 C C N Example 31 material B-4 Experimental Porous carbon 1280 280 0.16 1.54 1.06 56 C C N Example 32 material C Experimental Carbon 68 310 0.13 0.39 1.04 68 C A N Example 33 material D Experimental Carbon 35 12 0.12 0.62 0.97 125 C A N Example 34 material E

(98) The entire contents of the disclosures by Japanese Patent Application No. 2017-070829 are incorporated herein by reference.

(99) All the Document, patent application, and technical standards cited herein are also herein incorporated to the same extent as provided for specifically and severally with respect to an individual Document, patent application, and technical standard to the effect that the same should be so incorporated by reference.