Carbon support, metal-supported catalyst, electrode and battery

Abstract

Provided are a carbon support, a metal-supported catalyst, an electrode, and a battery which achieve durability and catalytic activity of the metal-supported catalyst. The present invention relates to a carbon support for supporting catalyst metal particles, having a BET specific surface area of 300 m2 / g or more and a true density of 2.1 g / cm3 or more, and having a carbon structure exhibiting one or more of the following characteristics (i) and (ii) in a Raman spectrum obtained by Raman spectroscopy, the ratio of the intensity of the D band having a peak top near the Raman shift of 1,580 cm <-1 > to the intensity of the G band having a peak top near the Raman shift of 1,580 cm <-1 > is 1.6 or more; and (ii) the ratio of the intensity of the 2D band having a peak top near the Raman shift of 2,700 cm <-1 > to the intensity of the G band having a peak top near the Raman shift of 1,580 cm <-1 > is 0.3 or more.

Description

Technical Field

[0001] The present invention relates to carbon supports, metal-supported catalysts, electrodes and batteries. Background Art

[0002] In Patent Document 1, a carbon support is described which is obtained by subjecting carbon black or activated carbon to a heat treatment at 1,800° C. to 2,500° C. and which has an average lattice spacing d between

[002] planes of 002 The crystallite size Lc is 0.337nm to 0.348nm. (002) The nanostructured carbon fiber is 3nm to 18nm, and the specific surface area is 70m 2 / g to 800m 2 / g, and the electrode catalyst includes platinum or platinum alloy supported on a carbon support.

[0003] In Patent Document 2, graphitized carbon black obtained by subjecting a mixture containing carbon black and a graphitization-promoting substance to heat treatment at 2,000° C. to 2,500° C., and a catalyst for a phosphoric acid fuel cell obtained by supporting platinum on the graphitized carbon black are described. Reference List Patent Literature

[0004] [Patent Document 1] JP 2000-268828A [Patent Document 2] JP 2000-273351A Summary of the Invention Technical issues

[0005] The inventors of the present invention have observed the following problem: when a carbon material subjected to graphitization treatment is used as a carbon support for a metal-supported catalyst, the initial catalytic activity of the metal-supported catalyst decreases, although the durability of the metal-supported catalyst (e.g., corrosion resistance and / or resistance to load fluctuation) is improved.

[0006] The present invention has been made in view of the above problems, and one of the objects of the present invention is to provide a carbon support, a metal-supported catalyst, an electrode, and a battery that achieve the durability and catalytic activity of a metal-supported catalyst. Solutions to the Problem

[0007] [1] In order to solve the above problems, according to one embodiment of the present invention, a carbon support for supporting catalyst metal particles is provided, wherein the BET specific surface area of ​​the carbon support is 300 m 2 / g or more; the true density of the carbon carrier is 2.1g / cm 3Or above; and the carbon support comprises a carbon structure, the carbon structure exhibiting one or more selected from the following characteristics (i) and (ii) in a Raman spectrum obtained by Raman spectroscopy: (i) at 1,340 cm -1 The intensity of the D band with a peak near the top of the Raman shift is relatively close to that at 1,580 cm -1 The ratio of the intensity of the G band having the peak top near the Raman shift of 1,700 cm to 1,700 cm is 1.6 or more; and (ii) the intensity of the G band having the peak top near the Raman shift of 1,700 cm to 1,700 cm is 1.6 or more; -1 The intensity of the 2D band with a peak near the top of the Raman shift is relative to that at 1,580 cm -1 The ratio of the intensity of the G band having the peak top near the Raman shift is 0.3 or more. According to the present invention, a carbon support is provided that achieves durability and catalytic activity of a metal-supported catalyst.

[0008] [2] The carbon support according to the above item [1] may include the carbon structure exhibiting the feature (i). [3] The carbon support according to the above item [1] or [2] may include the carbon structure exhibiting the feature (ii).

[0009] [4] The carbon support according to any one of the above items [1] to [3] has an oxygen content of 1.0 wt% or more. [5] The carbon support according to any one of the above items [1] to [4] may include the carbon structure that exhibits an oxygen content of 1.0 wt% or more at 1,580 cm in a Raman spectrum obtained by Raman spectroscopy. -1 The half-maximum width of the G band near the peak top is 37 cm -1 [6] The carbon support according to any one of items [1] to [5] above, which may include the carbon structure showing a Raman spectrum at 1,340 cm -1 The half-maximum width of the D band near the peak top is 38 cm -1 [7] The carbon support according to any one of items [1] to [6] above, which may include the carbon structure showing a Raman spectrum at 2,700 cm-1 in a Raman spectrum obtained by Raman spectroscopy. -1 The half-maximum width of the 2D band with a peak top near the Raman shift is 57 cm -1 or below.

[0010] [8] The carbon support according to any one of items [1] to [7], which may have a volume of 0.50 cm2 of pores having a pore diameter of 5 nm or more and 70 nm or less. 3 / g or less. [9] The carbon support according to any one of the above items [1] to [8] may have a diameter of 0.20 cm 3

[10] The carbon support according to any one of items [1] to [9] above may have a ratio of the volume of pores having a pore diameter of less than 5 nm to the volume of pores having a pore diameter of 5 nm or more and 70 nm or less of 4.0 or more.

[11] The carbon support according to any one of items [1] to

[10] above may have a pore mode diameter of 7.0 nm or less.

[0011]

[12] The carbon support according to any one of items [1] to

[11] , which may include a carbon structure showing a nitrogen adsorption isotherm of 40 cm-1 at a temperature of 77 K obtained by a nitrogen adsorption method. 3 The difference is obtained by subtracting the nitrogen adsorption amount from the nitrogen desorption amount at a relative pressure (P / P0) of 0.5 (-), wherein the relative pressure (P / P0) is the ratio of the adsorption equilibrium pressure (P) to the saturated vapor pressure (P0).

[13] The carbon support according to any one of the above items [1] to

[12] may include a carbon structure that exhibits a 20 cm-2 adsorption rate in a nitrogen adsorption isotherm obtained at a temperature of 77 K by a nitrogen adsorption method. 3 / g or less, wherein the difference is obtained by subtracting the nitrogen adsorption amount from the nitrogen desorption amount at a relative pressure (P / P0) of 0.8(-), wherein the relative pressure (P / P0) is the ratio of the adsorption equilibrium pressure (P) to the saturated vapor pressure (P0).

[0012]

[14] To address the above problems, according to one embodiment of the present invention, a metal-supported catalyst is provided, comprising: a carbon support according to any one of [1] to

[13] above; and catalytic metal particles supported on the carbon support. According to the present invention, a metal-supported catalyst having durability and catalytic activity is provided.

[0013]

[15] In order to solve the above problems, according to one embodiment of the present invention, an electrode is provided, which includes the metal-supported catalyst of the above item

[14] . According to the present invention, an electrode having durability and catalytic activity is provided.

[0014]

[16] In order to solve the above problems, according to one embodiment of the present invention, a battery is provided, comprising the electrode of the above item

[15] . According to the present invention, a battery having durability and catalytic activity is provided. Advantageous Effects of the Invention

[0015] The present invention provides a carbon support that allows a metal-supported catalyst to have durability and catalytic activity, a metal-supported catalyst, an electrode, and a battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 Shown is a Raman spectrum obtained for the carbon support of Example 1 in Examples according to an embodiment of the present invention. Figure 2 A nitrogen adsorption isotherm obtained for the carbon support according to Example 11 of this embodiment is shown. Figure 3A The pore size distributions obtained for the carbon supports of Example C1 and Example C3 in Examples according to this embodiment are shown. Figure 3B The pore size distributions obtained for the carbon supports of Example C5, Example C7, and Example 2 according to embodiments of this embodiment are shown. Figure 4A Examples of evaluation results of characteristics of the carbon supports in Examples according to this embodiment are shown. Figure 4B Another example of the evaluation results of the characteristics of the carbon support in Examples according to this embodiment is shown. Figure 4C Shown are evaluation results of the performance of the metal-supported catalysts in Examples according to this embodiment. DETAILED DESCRIPTION

[0017] An embodiment of the present invention will be described below. However, the present invention is not limited to the examples described in this embodiment.

[0018] The carbon support according to an embodiment of the present invention (hereinafter referred to as "the support of the present invention") is a porous carbon material mainly composed of carbon. The carbon content of the support of the present invention is not particularly limited as long as the effects of the present invention are achieved. However, for example, the carbon content may be 70% by weight or more, preferably 75% by weight or more, more preferably 80% by weight or more, and particularly preferably 85% by weight or more.

[0019] In addition, for example, the carbon content of the support of the present invention may be 100% by weight or less, 95% by weight or less, or 90% by weight or less. The carbon content of the support of the present invention can be specified by freely combining any of the above lower limits with any of the above upper limits. The carbon content of the carbon support is obtained by elemental analysis (specifically, combustion method).

[0020] The true density of the carrier of the present invention is not particularly limited as long as the effects of the present invention are achieved. However, for example, the true density may be 1.8 g / cm 3 or more, and preferably 1.9 g / cm 3 or more, more preferably 2.0 g / cm 3 or more, still more preferably 2.1 g / cm 3or more, still more preferably 2.2 g / cm 3 or more, and particularly preferably 2.3 g / cm 3 or above.

[0021] Furthermore, for example, the true density of the carrier of the present invention may be 2.6 g / cm 3 Or less, can be 2.5g / cm 3 Or below, can be 2.4g / cm 3 Or below, can be 2.3g / cm 3 Or below, can be 2.2g / cm 3 or less, or can be 2.1g / cm 3 The true density of the carrier of the present invention can be specified by freely combining any one of the above lower limits with any one of the above upper limits. The true density of the carbon carrier is obtained by the constant volume expansion method.

[0022] In this article, the true density measured using the constant volume expansion method for porous carbon materials with closed pores is generally lower than that measured for solid carbon materials. Furthermore, for example, when a porous carbon material undergoes graphitization, some of its pores are closed, increasing the volume of the closed pores. As a result, the true density of the carbon material after graphitization becomes lower than the value measured before graphitization. As described above, the true density of a carbon material reflects the volume of the closed pores in the carbon material.

[0023] On the other hand, when porous carbon material is used as the carbon support of loaded catalyst metal particles, the closed pore in the carbon material is the useless space that can not load catalyst metal particles.Therefore, the relatively large true density of the carrier of the present invention (it reflects the fact that the volume of closed pore is little) means that the carrier of the present invention has the porous structure that is suitable for being used as the carbon support of loaded catalyst metal particles.Specifically, for example, when the carrier of the present invention is the carbon material that undergoes oxidation treatment after graphitization treatment, the hole that it has been closed once by graphitization treatment is opened again by oxidation treatment.Therefore, the true density of the carrier of the present invention is greater than the true density of the carbon material before oxidation treatment.The increase by the true density of oxidation treatment helps to improve the catalytic activity of the metal-loaded catalyst comprising the catalyst metal particles loaded on the carrier of the present invention, because the increase of true density has increased the surface and space that can be used for loaded catalyst metal particles in the carrier of the present invention.

[0024] The carrier of the present invention preferably includes a carbon structure that exhibits a Raman spectrum at 1,580 cm -1 (Specifically, for example, at 1,550 cm -1 or above and 1,610cm -1The half-width at half maximum of the G band having a peak top near the Raman shift (in the range of 0.04 or below) (hereinafter referred to as the "half-width at half-maximum of the broad-band G band") is 37 cm -1 or below.

[0025] In this case, the Raman G half-peak half-width of the carrier of the present invention is more preferably 36 cm -1 or less, still more preferably 35 cm -1 Or less. In addition, the Raman G half maximum half width of the carrier of the present invention is more preferably 34cm -1 or less, still more preferably 33 cm -1 or less, still more preferably 32 cm -1 or less, still more preferably 31 cm -1 or less, still more preferably 30 cm -1 or less, still more preferably 29 cm -1 or less, particularly preferably 28 cm -1 or below.

[0026] Furthermore, for example, the Raman G half-width at half maximum of the carrier of the present invention may be 10 cm -1 or above, can be 15cm -1 or above, can be 18cm -1 or above, can be 20cm -1 or above, can be 22cm -1 or above, can be 24cm -1 or above, can be 26cm -1 or above, can be 27cm -1 or above, or can be 28cm -1 The Raman G half maximum full width of the carrier of the present invention can be specified by freely combining any one of the above lower limits and any one of the above upper limits.

[0027] As used herein, in the Raman spectrum of a carbon material, the G band is a component derived from the carbon atoms that form graphene. Furthermore, the half-width at half maximum of the G band indicates the extent of graphene development. That is, as graphene develops within a carbon structure, the Raman G half-width at half maximum of the carbon structure decreases. In this regard, as graphene develops, the stability of the carbon structure improves. Therefore, a carbon structure exhibiting a Raman G half-width at half maximum equal to or less than the aforementioned upper limit helps improve the durability of a metal-supported catalyst comprising catalyst metal particles supported on a support of the present invention.

[0028] On the other hand, a carbon structure exhibiting an excessively small Raman G half-width at half maximum has a poor ability to support catalyst metal particles because its graphene is overdeveloped. In contrast, a carbon structure exhibiting a moderately large Raman G half-width at half maximum has an excellent ability to support catalyst metal particles because its graphene is not overdeveloped and thus moderately contains strain and / or heteroatoms.

[0029] Furthermore, with the development of graphene, the hydrophilicity of carbon structures has decreased. Therefore, for example, when metal-supported catalysts are applied to fuel cells, carbon structures that exhibit an excessively small Raman G half-width at half maximum have poor ability to retain produced water. In contrast, carbon structures that exhibit a moderately large Raman G half-width at half maximum have excellent ability to retain produced water because they have moderate hydrophilicity.

[0030] Therefore, a carbon structure exhibiting a Raman G half-peak half width equal to or greater than the above lower limit value helps to improve the durability and / or catalytic activity of the metal-supported catalyst comprising the catalyst metal particles supported on the carrier of the present invention (for example, power generation performance (including power generation performance under low humidity conditions) when the metal-supported catalyst is applied to a battery).

[0031] The carrier of the present invention preferably includes a carbon structure that exhibits a Raman spectrum at 1,340 cm -1 (Specifically, for example, at 1,320 cm -1 or above and 1,360cm -1 The half-width at half maximum of the D band having a peak top near the Raman shift (in the range of 0.04 or less) (hereinafter referred to as "Raman D half-width at half maximum") is 38 cm -1 or below.

[0032] In this case, the Raman D half-maximum half-width of the carrier of the present invention is more preferably 36 cm -1 or less, still more preferably 34 cm -1 Or less. In addition, the Raman D half maximum half width of the carrier of the present invention is more preferably 32cm -1 or less, still more preferably 30 cm -1 or less, still more preferably 29cm -1 or less, still more preferably 28cm -1 or less, still more preferably 27 cm -1 or less, still more preferably 26 cm -1 or less, still more preferably 25 cm -1 or less, still more preferably 24 cm -1 or less, particularly preferably 23cm -1 or below.

[0033] Furthermore, for example, the Raman D half-width at half maximum of the carrier of the present invention may be 10 cm -1 or above, can be 15cm -1 or above, can be 18cm -1 or above, can be 20cm -1 or above, can be 21cm -1 or above, can be 22cm -1 or above, or can be 23cm -1 In addition, for example, the Raman D half maximum half width of the carrier of the present invention can be 24 cm -1 or above, can be 25cm -1 or above, can be 26cm -1 or above, can be 27cm -1 or above, can be 28cm -1 or above, or can be 29cm -1 The Raman D half maximum full width of the carrier of the present invention can be specified by freely combining any one of the above lower limits and any one of the above upper limits.

[0034] In this article, according to reference (A. Sadezky et al., Carbon 43 (2005) 1731-1742), in the Raman spectrum of carbon materials, the D band is a component derived from carbon atoms adjacent to the disordered lattice, such as the edge or defect of a graphene layer. In addition, the half-width at half maximum of the D band represents the crystallinity of the carbon around the edge or defect. That is, as the crystallinity of the carbon around the edge or defect in the carbon structure becomes higher, the Raman D half-width at half maximum of the carbon structure decreases. In addition, as the crystallinity of the carbon becomes higher, the stability of the carbon structure is improved. Therefore, a carbon structure exhibiting a Raman D half-width at half maximum equal to or less than the above-mentioned upper limit value contributes to improving the durability of the metal-supported catalyst including the catalyst metal particles supported on the carrier of the present invention.

[0035] On the other hand, a carbon structure exhibiting an excessively small Raman D half-width at half maximum has poor ability to support catalyst metal particles because the crystallinity of carbon around edges or defects is too high. In contrast, a carbon structure exhibiting a moderately large Raman D half-width at half maximum has excellent ability to support catalyst metal particles because the crystallinity of carbon around edges or defects is not excessively high.

[0036] Furthermore, as the crystallinity of carbon increases, the hydrophilicity of the carbon structure decreases. Therefore, for example, when a metal-supported catalyst is applied to a fuel cell, a carbon structure exhibiting an excessively small Raman D half-width at half maximum has a poor ability to retain produced water. In contrast, a carbon structure exhibiting a moderately large Raman D half-width at half maximum has an excellent ability to retain produced water because the structure has moderate hydrophilicity.

[0037] Therefore, a carbon structure exhibiting a Raman D half-width at half maximum equal to or greater than the above lower limit value helps to improve the durability and / or catalytic activity of the metal-supported catalyst comprising catalyst metal particles supported on the carrier of the present invention (for example, power generation performance (including power generation performance under low humidity conditions) when the metal-supported catalyst is applied to a battery).

[0038] The carrier of the present invention preferably includes a carbon structure that exhibits a wavelength at 2,700 cm-1 in its Raman spectrum obtained by Raman spectroscopy. -1 Near (specifically, for example, at 2,670 cm -1 or above and 2,730cm -1 The half-width at half maximum of the 2D band with a peak top (hereinafter referred to as the "broad half-width at half maximum" of 2D) is 57 cm -1 or below.

[0039] In this case, the Raman 2D half-width at half maximum of the carrier of the present invention is more preferably 55 cm -1 or less, still more preferably 54 cm -1 or less, still more preferably 53 cm -1 In addition, the Raman 2D half-width at half maximum of the carrier of the present invention is more preferably 52 cm -1 or less, still more preferably 51 cm -1 or less, still more preferably 50 cm -1 or less, still more preferably 49 cm -1 or less, still more preferably 48 cm -1 or less, still more preferably 47 cm -1 or less, still more preferably 46 cm -1 or less, still more preferably 45 cm -1 or less, still more preferably 44 cm -1 or less, still more preferably 43 cm -1 or less, still more preferably 42 cm -1 or less, still more preferably 41 cm -1 or less, still more preferably 40 cm -1 or less, and particularly preferably 39 cm -1 or below.

[0040] Furthermore, for example, the Raman 2D half-width at half maximum of the carrier of the present invention may be 10 cm -1 or above, can be 15cm -1 or above, can be 20cm -1 or above, can be 25cm-1 or above, can be 30cm -1 or above, or can be 32cm -1 In addition, the Raman 2D half-maximum half-width of the carrier of the present invention can be 34cm -1 or above, can be 36cm -1 or above, can be 38cm -1 or above, can be 40cm -1 or above, can be 42cm -1 or above, can be 44cm -1 or above, can be 46cm -1 or above, can be 48cm -1 or above, or can be 50cm -1 The Raman 2D half-width at half maximum of the carrier of the present invention can be specified by freely combining any one of the above lower limits and any one of the above upper limits.

[0041] In this article, in the Raman spectrum of a carbon material, the 2D band is a component derived from the carbon atoms that form the graphene layer. In addition, the half-width at half maximum of the 2D band represents the uniformity of the graphene layer. That is, as the graphene layer in the carbon structure becomes more uniform, the Raman 2D half-width at half maximum of the carbon structure decreases. In addition, as the graphene layer becomes more uniform, the stability of the carbon structure is improved. Therefore, a carbon structure that exhibits a Raman 2D half-width at half maximum equal to or less than the above upper limit value helps improve the durability of a metal-supported catalyst including catalyst metal particles supported on a carrier of the present invention.

[0042] On the other hand, a carbon structure exhibiting an excessively small Raman 2D half-width at half maximum has a poor ability to support catalyst metal particles because the uniformity of its graphene layer is too high. In contrast, a carbon structure exhibiting a moderately large Raman 2D half-width at half maximum has an excellent ability to support catalyst metal particles because its graphene layer has moderate defects or strain.

[0043] Furthermore, as the graphene layer becomes more uniform, the hydrophilicity of the carbon structure decreases. Therefore, for example, when a metal-supported catalyst is applied to a fuel cell, a carbon structure exhibiting an excessively small Raman 2D half-width at half maximum has a poor ability to retain produced water. In contrast, a carbon structure exhibiting a moderately large Raman 2D half-width at half maximum has an excellent ability to retain produced water because it has moderate hydrophilicity.

[0044] Therefore, a carbon structure exhibiting a Raman 2D half-width at half maximum equal to or greater than the above lower limit value helps to improve the durability and / or catalytic activity of a metal-supported catalyst comprising catalyst metal particles supported on a carrier of the present invention (for example, power generation performance (including power generation performance under low humidification conditions) when the metal-supported catalyst is applied to a battery).

[0045] The carrier of the present invention preferably includes a carbon structure that exhibits a ratio of the intensity of the above-mentioned D band to the intensity of the above-mentioned G band (hereinafter referred to as "Biman D / G ratio") of 1.6 or more in a Raman spectrum obtained by Raman spectroscopy.

[0046] In this case, the Raman D / G ratio of the carrier of the present invention is more preferably 1.7 or more, even more preferably 1.8 or more, even more preferably 1.9 or more, even more preferably 2.0 or more. In addition, the Raman D / G ratio of the carrier of the present invention is more preferably 2.1 or more, more preferably 2.2 or more, and particularly preferably 2.3 or more.

[0047] Furthermore, for example, the Raman D / G ratio of the carrier of the present invention may be 4.0 or less, 3.5 or less, 3.0 or less, 2.8 or less, 2.6 or less, 2.5 or less, 2.4 or less, or 2.3 or less. Furthermore, for example, the Raman D / G ratio of the carrier of the present invention may be 2.2 or less, or 2.1 or less. The Raman D / G ratio of the carrier of the present invention can be specified by freely combining any one of the above lower limits with any one of the above upper limits.

[0048] Here, the Raman D / G ratio of a carbon material represents the amount of edges or defects in the graphene layers within its carbon structure. That is, as the amount of edges or defects in the graphene layers increases, the Raman D / G ratio of the carbon material increases. In this regard, edges and defects serve as sites for supporting catalyst metal particles. Therefore, as the amount of edges or defects in the graphene layers increases, the carbon structure's ability to support catalyst metal particles increases.

[0049] Furthermore, as the number of edges or defects in the graphene layer increases, the hydrophilicity of the carbon structure improves. For example, when metal-supported catalysts are applied to fuel cells, the improved hydrophilicity of the carbon structure improves its ability to retain produced water.

[0050] Therefore, a carbon structure exhibiting a Raman D / G ratio equal to or greater than the above lower limit value helps to improve the durability and / or catalytic activity of a metal-supported catalyst comprising catalyst metal particles supported on a carrier of the present invention (for example, power generation performance (including power generation performance under low humidity conditions) when the metal-supported catalyst is applied to a battery).

[0051] On the other hand, a carbon structure exhibiting an excessively large Raman D / G ratio has a reduced durability because the amount of edges or defects thereof is excessively large. In contrast, a carbon structure exhibiting a moderately large Raman D / G ratio has an appropriate amount of edges or defects. Therefore, a carbon structure exhibiting a Raman D / G ratio equal to or smaller than the above upper limit value contributes to improvement in the durability of a supported metal catalyst comprising catalyst metal particles supported on the support of the present application.

[0052] The support of the present application preferably comprises a carbon structure exhibiting a ratio of the intensity of the above 2D band to the intensity of the above G band (hereinafter referred to as the "Raman 2D / G ratio") of 0.3 or more in a Raman spectrum obtained by Raman spectroscopy.

[0053] In this case, the Raman 2D / G ratio of the support of the present application is more preferably 0.4 or more, still more preferably 0.5 or more, still more preferably 0.6 or more, and particularly preferably 0.7 or more.

[0054] Further, for example, the Raman 2D / G ratio of the support of the present application can be 1.5 or less, can be 1.2 or less, can be 1.0 or less, can be 0.9 or less, can be 0.8 or less, or can be 0.7 or less. Further, for example, the Raman 2D / G ratio of the support of the present application can be 0.6 or less, can be 0.5 or less, can be 0.4 or less, or can be 0.3 or less. The Raman 2D / G ratio of the support of the present application can be specified by freely combining any one of the above lower limit values and any one of the above upper limit values.

[0055] In this context, the Raman 2D / G ratio of a carbon material indicates the number of layers in which graphene is stacked in the carbon structure of the carbon material. That is, when the intensity of the 2D band is higher than that of the G band (Raman 2D / G ratio > 1), graphene is formed by a single layer. When the intensity of the 2D band is the same as that of the G band (Raman 2D / G ratio = 1), the number of layers in which graphene is stacked is about 2. When the intensity of the 2D band is lower than that of the G band (Raman 2D / G ratio < 1), the number of layers in which graphene is stacked is 3 or more. The specific number of stacked layers is determined by the ratio of the intensity of the 2D band (the height of the top of the peak thereof) to the intensity of the G band (the height of the top of the peak thereof).

[0056] A carbon structure exhibiting an excessively small Raman 2D / G ratio, i.e., a carbon structure having an excessively large number of layers in a graphene stack, has reduced durability (particularly corrosion resistance) because the relative amount of its edges or defects (which serve as starting points for oxidative degradation) relative to its basal plane is excessively large. In contrast, a carbon structure exhibiting a Raman 2D / G ratio equal to or greater than the above lower limit value contributes to improved durability (particularly corrosion resistance) because the structure includes few graphene layers, wherein the number of layers in the graphene stack is controlled within an appropriate range (e.g., from about 2 to about 3), and thus the relative amount of its edges or defects relative to its exposed basal plane is controlled within an appropriate range.

[0057] On the other hand, edges and defects act as sites for supporting catalyst metal particles. Therefore, carbon structures exhibiting an excessively large Raman 2D / G ratio have poor ability to support catalyst metal particles because the relative amount of edges or defects relative to their basal plane is too small. In contrast, carbon structures exhibiting a moderately large Raman 2D / G ratio have excellent ability to support catalyst metal particles because they contain an appropriate amount of edges or defects.

[0058] Furthermore, the hydrophilicity of a carbon structure decreases as the relative amount of its edges or defects relative to its basal plane decreases. Therefore, for example, when a metal-supported catalyst is applied to a fuel cell, a carbon structure exhibiting an excessively large Raman 2D / G ratio has a poor ability to retain produced water. In contrast, a carbon structure exhibiting a moderately large Raman 2D / G ratio has an excellent ability to retain produced water because the structure has moderate hydrophilicity.

[0059] Therefore, a carbon structure exhibiting a Raman 2D / G ratio equal to or less than the above upper limit value helps to improve the durability and / or catalytic activity of a metal-supported catalyst comprising catalyst metal particles supported on a carrier of the present invention (for example, power generation performance (including power generation performance under low humidity conditions) when the metal-supported catalyst is applied to a battery).

[0060] The oxygen content of the carrier of the present invention is not particularly limited as long as the effects of the present invention are achieved. However, for example, the oxygen content is preferably 1.0 wt% or more, more preferably 1.5 wt% or more, even more preferably 2.0 wt% or more, even more preferably 2.4 wt% or more, even more preferably 2.6 wt% or more, even more preferably 2.8 wt% or more. Furthermore, the oxygen content of the carrier of the present invention is even more preferably 3.0 wt% or more, even more preferably 3.1 wt% or more, even more preferably 3.2 wt% or more, even more preferably 3.3 wt% or more, even more preferably 3.4 wt% or more, even more preferably 3.5 wt% or more, even more preferably 3.6 wt% or more, even more preferably 3.7 wt% or more, even more preferably 3.8 wt% or more, even more preferably 3.9 wt% or more, and particularly preferably 4.0 wt% or more.

[0061] In addition, for example, the oxygen content of the support of the present invention can be 20.0 wt% or less, can be 15.0 wt% or less, can be 12.0 wt% or less, can be 10.0 wt% or less, can be 9.5 wt% or less, can be 9.0 wt% or less, can be 8.5 wt% or less, can be 8.0 wt% or less, can be 7.5 wt% or less, can be 7.0 wt% or less, can be 6.5 wt% or less, can be 6.0 wt% or less, can be 5.5 wt% or less, can be 5.0 wt% or less, can be 4.8 wt% or less, can be 4.6 wt% or less, can be 4.4 wt% or less, can be 4.2 wt% or less, can be 4.0 wt% or less, can be 3.8 wt% or less, or can be 3.6 wt% or less. Furthermore, for example, the oxygen content of the support of the present invention may be 3.5 wt% or less, 3.4 wt% or less, 3.3 wt% or less, 3.2 wt% or less, or 3.1 wt% or less. The oxygen content of the support of the present invention can be specified by freely combining any of the above lower limits with any of the above upper limits. The oxygen content of the support of the present invention is obtained by elemental analysis (e.g., pyrolysis method).

[0062] In this article, the oxygen content obtained by elemental analysis of the carbon material affects the hydrophilicity of the carbon material. That is, as the oxygen content of the carbon material increases, the hydrophilicity of the carbon material is improved. In this respect, generally, as the Raman G half-width at half maximum, the Raman D half-width at half maximum and the Raman 2D half-width at half maximum of the carbon structure become smaller, or as the Raman 2D / G ratio of the carbon structure becomes larger, the hydrophilicity of the carbon structure decreases. However, even in the case where the carbon structure exhibits a small Raman G half-width at half maximum, the Raman D half-width at half maximum or the Raman 2D half-width at half maximum, and / or the carbon structure exhibits a large Raman 2D / G ratio, its hydrophilicity improves as its oxygen content increases. In addition, for example, when a metal-supported catalyst is applied to a fuel cell, a carbon material with high hydrophilicity has an excellent ability to retain produced water.

[0063] Therefore, a carbon structure exhibiting an oxygen content equal to or greater than the above lower limit value contributes to improving the catalytic activity of a metal-supported catalyst comprising catalyst metal particles supported on a carrier of the present invention (for example, power generation performance (including power generation performance under low humidity conditions) when the metal-supported catalyst is applied to a battery).

[0064] On the other hand, a carbon structure having an excessively large oxygen content has reduced durability (particularly corrosion resistance) because the number of its oxidation starting points is too large. In contrast, a carbon structure having an oxygen content equal to or less than the above upper limit value contributes to improved durability (particularly corrosion resistance) because the number of its oxidation starting points is not too large.

[0065] The BET specific surface area of ​​the carrier of the present invention is not particularly limited as long as the effects of the present invention are achieved. However, for example, the BET specific surface area is preferably 300 m 2 / g or more. The BET specific surface area of ​​the carrier of the present invention is more preferably 400m 2 / g or more, and more preferably 500m 2 / g or more, and more preferably 600m 2 / g or more, and more preferably 700m 2 / g or more, and more preferably 800m 2 / g or more, and more preferably 900m 2 / g or more. In addition, the BET specific surface area of ​​the carrier of the present invention is more preferably 1,000 m 2 / g or more, still more preferably 1,100m 2 / g or more, still more preferably 1,150m 2 / g or more, still more preferably 1,200m 2 / g or more, still more preferably 1,250m 2 / g or more, still more preferably 1,300m 2 / g or more, still more preferably 1,350m 2 / g or more, particularly preferably 1,400m 2 / g or above.

[0066] Furthermore, for example, the BET specific surface area of ​​the carrier of the present invention may be 3,300 m 2 / g or less, can be 3,000m 2 / g or less, can be 2,500m 2 / g or less, can be 2,000m 2 / g or less, can be 1,800m 2 / g or less, or can be 1,600m 2 / g or less. In addition, for example, the BET specific surface area of ​​the carrier of the present invention may be 1,500 m 2 / g or less, can be 1,450m 2 / g or less, can be 1,400m 2 / g or less, can be 1,350m 2 / g or less, can be 1,300m 2 / g or less, can be 1,250m 2 / g or less, can be 1,200m 2 / g or less, can be 1,150m 2 / g or less, can be 1,100m 2 / g or less, can be 1,000m 2 / g or less, can be 950m 2 / g or less, or can be 900m 2 / g or less. The BET specific surface area of ​​the carrier of the present invention can be specified by freely combining any of the above lower limits with any of the above upper limits. The BET specific surface area of ​​the carrier of the present invention is obtained by the BET method from its nitrogen adsorption isotherm, which is obtained by a nitrogen adsorption method at a temperature of 77K.

[0067] An increase in the BET specific surface area of ​​a carbon support helps improve the durability and / or catalytic activity of a metal-supported catalyst comprising catalytic metal particles supported on the carbon support because the increase in the BET surface area increases the number of sites for supporting the catalytic metal particles.

[0068] In the carrier of the present invention, the volume of pores each having a pore diameter of 5 nm or more and 70 nm or less (hereinafter referred to as "pore volume (5-70 nm")) is preferably 0.50 cm 3 In this case, the pore volume (5-70 nm) of the carrier of the present invention is more preferably 0.45 cm3 / g or less, still more preferably 0.40cm 3 / g or less, still more preferably 0.35cm 3 / g or less, still more preferably 0.30cm 3 / g or less, still more preferably 0.25cm 3 / g or less, still more preferably 0.20cm 3 / g or less, still more preferably 0.15cm 3 / g or less, still more preferably 0.12cm 3 / g or less, still more preferably 0.10cm 3 / g or less, still more preferably 0.09cm 3 / g or less, still more preferably 0.08cm 3 / g or less. In addition, the pore volume (5-70nm) of the carrier of the present invention is more preferably 0.07cm 3 / g or less, and more preferably 0.06cm 3 / g or less, particularly preferably 0.05cm 3 / g or less.

[0069] Furthermore, for example, the pore volume (5-70 nm) of the carrier of the present invention may be 0.00 cm 3 / g or above, can be 0.01cm 3 / g or above, can be 0.02cm 3 / g or more, or can be 0.03cm 3 / g or more. In addition, the pore volume (5-70nm) of the carrier of the present invention can be 0.04cm 3 / g or above, can be 0.05cm 3 / g or above, can be 0.06cm 3 / g or above, can be 0.07cm 3 / g or more, or can be 0.08cm 3 / g or more. The pore volume (5-70 nm) of the carrier of the present invention can be specified by freely combining any of the above lower limits with any of the above upper limits. The pore volume (5-70 nm) of the carrier of the present invention is obtained from its nitrogen adsorption isotherm by the DFT method, the nitrogen adsorption isotherm being obtained at a temperature of 77 K by a nitrogen adsorption method.

[0070] For example, when a metal-supported catalyst comprising catalyst metal particles supported on a carbon carrier is applied to a fuel cell, the pores in the carbon carrier each have a pore size of 5 nm or more and 70 nm or less, which is relatively large and each has a poor ability to retain produced water. Therefore, in each pore, the proton path is hardly formed by produced water. In addition, the catalyst metal particles supported in the pores each having a pore size of 5 nm or more and 70 nm or less are easily covered by the electrolyte, so their catalytic activity is easily reduced. Therefore, a porous carbon structure having a pore volume (5-70 nm) equal to or less than the above-mentioned upper limit value helps to improve the catalytic activity of the metal-supported catalyst comprising the catalyst metal particles supported on the carrier of the present invention (for example, power generation performance (particularly power generation performance under low humidity conditions) when the metal-supported catalyst is applied to a battery).

[0071] In the carrier of the present invention, the volume of pores each having a pore diameter of less than 5 nm (hereinafter referred to as "pore volume (less than 5 nm)") is preferably 0.20 cm 3 In this case, the pore volume (less than 5 nm) of the carrier of the present invention is more preferably 0.30 cm 3 / g or more, and more preferably 0.35cm 3 / g or more, and more preferably 0.40cm 3 / g or more. In addition, the pore volume (less than 5nm) of the carrier of the present invention is more preferably 0.45cm 3 / g or more, and more preferably 0.50cm 3 / g or more, still more preferably 0.55cm 3 / g or more, and more preferably 0.60cm 3 / g or more, particularly preferably 0.65cm 3 / g or above.

[0072] Furthermore, for example, the pore volume (less than 5 nm) of the support of the present invention may be 1.20 cm 3 / g or less, can be 1.10cm 3 / g or less, can be 1.00cm 3 / g or less, can be 0.95cm 3 / g or less, can be 0.90cm 3 / g or less, can be 0.85cm 3 / g or less, can be 0.80cm 3 / g or less, or can be 0.75cm 3 / g or less. In addition, the pore volume (less than 5nm) of the carrier of the present invention can be 0.70cm 3 / g or less, can be 0.65cm 3 / g or less, can be 0.60cm 3 / g or less, can be 0.55cm 3 / g or less, or can be 0.50cm 3 / g or less. The pore volume (less than 5 nm) of the carrier of the present invention can be specified by freely combining any of the above lower limits with any of the above upper limits. The pore volume (less than 5 nm) of the carrier of the present invention is obtained by the DFT method from its nitrogen adsorption isotherm, which is obtained by a nitrogen adsorption method at a temperature of 77 K.

[0073] Each of the pores having a pore size of less than 5 nm (which is relatively small) has an excellent ability to support catalyst metal particles having a relatively small particle size and high catalytic activity. In addition, for example, since the pores in the carbon support each having a pore size of less than 5 nm have an excellent ability to retain produced water, when a metal-supported catalyst comprising catalyst metal particles supported on such a carbon support is applied to a fuel cell, a proton path is easily formed through the produced water in the pore. In addition, the catalyst metal particles supported in the pores each having a pore size of less than 5 nm are hardly covered by the electrolyte. Therefore, a porous carbon structure having a pore volume (less than 5 nm) equal to or greater than the above lower limit value helps to improve the catalytic activity of the metal-supported catalyst comprising the catalyst metal particles supported on the support of the present invention (for example, power generation performance (particularly power generation performance under low humidity conditions) when the metal-supported catalyst is applied to a battery).

[0074] On the other hand, a carbon support having an excessively large pore volume (less than 5 nm) has reduced corrosion resistance because its carbon structure becomes sparse. Conversely, a carbon structure having a pore volume (less than 5 nm) equal to or less than the above upper limit contributes to improving the corrosion resistance of the support of the present invention because the structure is dense.

[0075] In the carrier of the present invention, the above pore volume (less than 5nm) (cm 3 / g) relative to the above pore volume (5-70nm) (cm 3 / g) (hereinafter referred to as "pore volume ratio (5 / (5-70))" (-) is preferably 4.0 or more. In this case, the pore volume ratio (5 / (5-70)) of the carrier of the present invention is more preferably 4.5 or more, more preferably 5.0 or more, and more preferably 6.0 or more. Furthermore, the pore volume ratio (5 / (5-70)) of the carrier of the present invention is still more preferably 6.5 or more, still more preferably 7.0 or more, still more preferably 7.5 or more, still more preferably 8.0 or more, still more preferably 8.5 or more, still more preferably 9.0 or more, still more preferably 9.5 or more, still more preferably 10.0 or more, still more preferably 10.5 or more, still more preferably 11.0 or more, still more preferably 11.5 or more, and particularly preferably 12.0 or more.

[0076] Furthermore, for example, the pore volume ratio (5 / (5-70)) of the carrier of the present invention may be 50.0 or less, may be 40.0 or less, may be 35.0 or less, or may be 30.0 or less. Furthermore, the pore volume ratio (5 / (5-70)) of the carrier of the present invention may be 25.0 or less, may be 20.0 or less, may be 15.0 or less, may be 10.0 or less, may be 9.0 or less, or may be 8.0 or less. The pore volume ratio (5 / (5-70)) of the carrier of the present invention can be specified by freely combining any one of the above lower limits and any one of the above upper limits.

[0077] In a carbon support having an excessively small pore volume ratio (5 / (5-70)), that is, in a carbon support having an excessively large pore volume (5-70 nm) compared to its pore volume (less than 5 nm), for example, when a metal-supported catalyst comprising catalyst metal particles supported on the carbon support is applied to a fuel cell, a proton path is hardly formed in its pores, and the catalyst metal particles supported in the pores are easily covered by an electrolyte. In contrast, in a carbon support having a large pore volume ratio (5 / (5-70)), a proton path is easily formed in its pores, and the catalyst metal particles supported in the pores are hardly covered by an electrolyte. Therefore, a porous carbon structure having a pore volume ratio (5 / (5-70)) equal to or greater than the above lower limit value contributes to improving the catalytic activity of a metal-supported catalyst comprising catalyst metal particles supported on a support of the present invention (for example, power generation performance (particularly power generation performance under low humidity conditions) when the metal-supported catalyst is applied to a battery).

[0078] On the other hand, a carbon support having an excessively large pore volume ratio (5 / (5-70)), that is, a carbon support having an excessively large pore volume (less than 5 nm) compared to its pore volume (5-70 nm), has reduced durability because the catalyst metal particles are easily supported on the outer surface of the carbon support rather than in its pores. In contrast, a porous carbon structure having a pore volume ratio (5 / (5-70)) equal to or less than the above upper limit value contributes to improving the durability of the metal-supported catalyst including the catalyst metal particles supported on the support of the present invention because the catalyst metal particles are effectively supported in its pores.

[0079] The carrier of the present invention preferably has a pore mode diameter of 7.0 nm or less. In this case, the pore mode diameter of the carrier of the present invention is more preferably 6.0 nm or less, even more preferably 5.0 nm or less, even more preferably 4.5 nm or less, even more preferably 4.0 nm or less, even more preferably 3.5 nm or less, and particularly preferably 3.0 nm or less.

[0080] In addition, for example, the pore mode diameter of the carrier of the present invention may be 0.5 nm or more, may be 1.0 nm or more, may be 1.5 nm or more, or may be 2.0 nm or more. In addition, the pore mode diameter of the carrier of the present invention may be 2.5 nm or more, or may be 3.0 nm or more. The pore mode diameter of the carrier of the present invention can be specified by freely combining any one of the above lower limits with any one of the above upper limits. The pore mode diameter of the carrier of the present invention is obtained by the DFT method from its nitrogen adsorption isotherm, which is obtained by the nitrogen adsorption method at a temperature of 77 K.

[0081] In the carbon support with excessively large pore mode diameter, for example, when the metal-loaded catalyst including the catalyst metal particles supported on the carbon support is applied to a fuel cell, the electrolyte is easily infiltrated into its pores, so the catalyst metal particles supported in the pores are covered by the electrolyte. Therefore, the utilization rate of the catalyst metal particles is easily reduced. On the contrary, in the carbon support with small pore mode diameter, the catalyst metal particles supported in its pores are almost not covered by the electrolyte, because the electrolyte almost does not infiltrate into the pores. Therefore, the porous carbon structure with a pore mode diameter equal to or less than the above-mentioned upper limit value contributes to improving the catalytic activity (for example, power generation performance in the case where the metal-loaded catalyst is applied to a battery) of the metal-loaded catalyst including the catalyst metal particles supported on the support of the present invention.

[0082] On the other hand, a carbon support having an excessively small pore mode diameter has reduced durability because the catalyst metal particles are not sufficiently supported in the pores thereof, and thus the catalyst metal particles are easily supported on the outer surface of the carbon support. In contrast, a porous carbon structure having a pore mode diameter equal to or greater than the above lower limit value contributes to improving the durability of a metal-supported catalyst including catalyst metal particles supported on the support of the present invention because the catalyst metal particles are effectively supported in the pores thereof.

[0083] The carrier of the present invention preferably includes a carbon structure that exhibits a carbon structure having a carbon density of 40 cm-1 in its nitrogen adsorption isotherm obtained at a temperature of 77 K by a nitrogen adsorption method. 3 / g or less (hereinafter referred to as "hysteresis (0.5P / P0)"), wherein the difference is obtained by subtracting the nitrogen adsorption amount from the nitrogen desorption amount at a relative pressure (P / P0) of 0.5(-), wherein the relative pressure (P / P0) is the ratio of the adsorption equilibrium pressure (P) to the saturated vapor pressure (P0).

[0084] In this case, the hysteresis (0.5P / P0) of the carrier of the present invention is more preferably 45 cm 3 / g or less, and more preferably 40cm 3 / g or less, and more preferably 35cm 3 / g or less, and more preferably 30cm 3 / g or less, and more preferably 25cm 3 / g or less, and more preferably 20cm 3 / g or less, and more preferably 18cm 3 / g or less, particularly preferably 15cm 3 / g or less.

[0085] Furthermore, for example, the hysteresis (0.5P / P0) of the carrier of the present invention may be 0 cm 3 / g or more, or can be 1cm 3 / g or more. In addition, the hysteresis (0.5P / P0) of the carrier of the present invention can be 5cm 3 / g or above, can be 10cm 3 / g or above, can be 15cm 3 / g or above, can be 20cm 3 / g or more, or can be 25cm 3 The hysteresis (0.5P / P0) of the carrier of the present invention can be specified by freely combining any one of the above lower limits and any one of the above upper limits.

[0086] The carrier of the present invention preferably includes a carbon structure that exhibits a 20 cm-2 adsorption capacity in its nitrogen adsorption isotherm obtained at a temperature of 77 K by a nitrogen adsorption method. 3 / g or less (hereinafter referred to as "hysteresis (0.8P / P0)"), wherein the difference is obtained by subtracting the nitrogen adsorption amount from the nitrogen desorption amount at a relative pressure (P / P0) of 0.8 (-).

[0087] In this case, for example, the hysteresis (0.8P / P0) of the carrier of the present invention is more preferably 15 cm 3 / g or less, and more preferably 10cm 3 / g or less. In addition, the hysteresis (0.8P / P0) of the carrier of the present invention is more preferably 9cm 3 / g or less, and more preferably 8cm 3 / g or less, and more preferably 7cm 3 / g or less, and more preferably 6cm 3 / g or less, and more preferably 5cm 3 / g or less, and more preferably 4cm 3 / g or less, particularly preferably 3cm 3 / g or less.

[0088] Furthermore, for example, the hysteresis (0.8P / P0) of the carrier of the present invention may be 0 cm 3 / g or more, can be 1cm 3 / g or above, can be 2cm 3 / g or more, or can be 3cm 3 / g or more. In addition, the hysteresis (0.8P / P0) of the carrier of the present invention can be 4cm 3 / g or more, or can be 5cm 3 The hysteresis (0.8P / P0) of the carrier of the present invention can be specified by freely combining any one of the above lower limits and any one of the above upper limits.

[0089] In this article, as the interconnection between the pores in the carbon carrier becomes higher, the hysteresis shown by the nitrogen adsorption isotherm of the carbon carrier decreases, and therefore the hysteresis (0.5P / P0) and hysteresis (0.8P / P0) of the carbon carrier become smaller. Therefore, the porous carbon structure (that is, porous carbon structure with high interconnectivity) showing a hysteresis (0.5P / P0) equal to or less than the above-mentioned upper limit value and / or a hysteresis (0.8P / P0) equal to or less than the above-mentioned upper limit value helps to improve the durability and / or catalytic activity of the metal-supported catalyst, for example, when the metal-supported catalyst including the catalyst metal particles supported on the carrier of the present invention is applied to a fuel cell, because the water produced in the hole is effectively discharged. Hysteresis (0.5P / P0) represents the interconnectivity between the holes each having a relatively small pore size, and hysteresis (0.8P / P0) represents the interconnectivity between the holes each having a relatively large pore size.

[0090] The carrier of the present invention is preferably a carbon material having any combination of two or more of the above-mentioned characteristics. That is, for example, the carrier according to one aspect of the embodiment of the present invention preferably includes a carbon structure that, in addition to a BET specific surface area within a specific range and a true density within a specific range, exhibits one or more characteristics selected from the group consisting of the following characteristics (i) to (iii) in its Raman spectrum obtained by Raman spectroscopy: (i) a Raman G half-maximum half-width within a specific range; (ii) a Raman D half-maximum half-width within a specific range; and (iii) a Raman 2D half-maximum half-width within a specific range.

[0091] In this case, the carrier of the present invention may include a carbon structure exhibiting only one selected from the group consisting of features (i) to (iii), may include a carbon structure exhibiting a combination of any two selected from the group consisting of features (i) and (ii), features (i) and (iii), or features (ii) and (iii), or may include a carbon structure exhibiting all of features (i) to (iii).

[0092] Specifically, for example, the carrier of the present invention may have 300 m 2 / g or more and a BET specific surface area of ​​2.1 g / cm 3 or more, and comprising a carbon structure exhibiting one or more of the following characteristics (i) to (iii) in its Raman spectrum obtained by Raman spectroscopy: (i) 37 cm -1 or less Raman G half-maximum half-width; (ii) 38cm -1 or less; and (iii) 57 cm -1 or less Raman 2D half-width at half maximum.

[0093] When the carrier of the present invention has a relatively large BET specific surface area, a relatively large true density and a relatively small Raman half-width at half maximum (selected from one or more of the following groups: Raman G half-width at half maximum; Raman D half-width at half maximum; and Raman 2D half-width at half maximum), the carrier of the present invention effectively contributes to achieving both the durability and catalytic activity of the metal-loaded catalyst because the carrier of the present invention includes a carbon structure that satisfies the following: the structure has a surface area that effectively supports catalyst metal particles; the volume of its closed pores that cannot support catalyst metal particles is small; and the structure has high crystallinity.

[0094] Furthermore, for example, a support according to another aspect of an embodiment of the present invention preferably includes a carbon structure that exhibits, in addition to a BET specific surface area within a specific range and a true density within a specific range, one or more selected from the following characteristics (iv) and (v) in its Raman spectrum obtained by Raman spectroscopy: (iv) a Raman D / G ratio within a specific range; and (v) a Raman 2D / G ratio within a specific range.

[0095] In this case, the carrier of the present invention may include a carbon structure exhibiting only one selected from the characteristics (iv) and (v), or may include a carbon structure exhibiting both the characteristics (iv) and (v).

[0096] Specifically, for example, the carrier of the present invention may have 300 m 2 / g or more and a BET specific surface area of ​​2.1 g / cm 3 or more, and includes a carbon structure exhibiting one or more selected from the following features (iv) and (v) in its Raman spectrum obtained by Raman spectroscopy: (iv) a Raman D / G ratio of 1.6 or more; and (v) a Raman 2D / G ratio of 0.3 or more.

[0097] When the carrier of the present invention has a relatively large BET specific surface area, a relatively large true density and a relatively large Raman D / G ratio and / or 2D / G ratio, the carrier of the present invention effectively contributes to achieving the durability and catalytic activity of the metal-loaded catalyst because the carrier of the present invention includes a carbon structure that satisfies the following conditions: the structure has a surface area that effectively supports catalyst metal particles; the volume of its closed pores that cannot support catalyst metal particles is small; and the structure is conducive to supporting catalyst metal particles.

[0098] In addition, for example, a support according to another aspect of an embodiment of the present invention preferably includes a carbon structure that exhibits, in addition to a BET specific surface area within a specific range and a true density within a specific range, one or more selected from the group consisting of the following features (i) to (iii), and one or more selected from the group consisting of the following features (iv) and (v) in its Raman spectrum obtained by Raman spectroscopy: (i) Raman G half-width at half maximum within a specific range; (ii) Raman D half-width at half maximum within a specific range; (iii) Raman 2D half-width at half maximum within a specific range; (iv) Raman D / G ratio within a specific range; and (v) Raman 2D / G ratio within a specific range.

[0099] In this case, the carrier of the present invention may include a carbon structure that exhibits only one selected from features (i) to (iii) and one or both of features (iv) and (v). In addition, the carrier of the present invention may include a carbon structure that exhibits a combination of any two selected from features (i) to (iii) (features (i) and (ii), features (i) and (iii), or features (ii) and (iii)), and one or both of features (iv) and (v). In addition, the carrier of the present invention may include a carbon structure that exhibits all of features (i) to (iii) and one or both of features (iv) and (v).

[0100] Specifically, for example, the carrier of the present invention may have 300 m 2 / g or more and a BET specific surface area of ​​2.1 g / cm 3 or more, and exhibiting a carbon structure having, in its Raman spectrum obtained by Raman spectroscopy, one or more selected from the group consisting of the following characteristics (i) to (iii) and one or more selected from the group consisting of the following characteristics (iv) and (v): (i) 37 cm -1 or less Raman G half-maximum half-width; (ii) 38cm -1 or less Raman D half-width at half maximum; (iii) 57 cm -1 (iv) a Raman 2D half-width at half maximum of 1.6 or less; (v) a Raman 2D / G ratio of 0.3 or more.

[0101] In addition, for example, a support according to another aspect of an embodiment of the present invention preferably includes a carbon structure, which, in addition to an oxygen content within a specific range, exhibits one or more features selected from the group consisting of the following features (i) to (v) in its Raman spectrum obtained by Raman spectroscopy: (i) Raman G half-width at half maximum within a specific range; (ii) Raman D half-width at half maximum within a specific range; (iii) Raman 2D half-width at half maximum within a specific range; (iv) Raman D / G ratio within a specific range; and (v) Raman 2D / G ratio within a specific range.

[0102] In this case, the carrier of the present invention may include a carbon structure exhibiting only one selected from the group consisting of characteristics (i) to (v), may include a carbon structure exhibiting a combination of any two selected from the group consisting of characteristics (i) to (v), may include a carbon structure exhibiting a combination of any three selected from the group consisting of characteristics (i) to (v), may include a carbon structure exhibiting a combination of any four selected from the group consisting of characteristics (i) to (v), or may include a carbon structure exhibiting all of characteristics (i) to (v).

[0103] Specifically, for example, the carrier of the present invention may have an oxygen content of 2.6 wt% or more and include a carbon structure that exhibits one or more selected from the group consisting of the above-mentioned characteristics (i) to (v) in its Raman spectrum obtained by Raman spectroscopy: (i) 37 cm -1 or less Raman G half-maximum half-width; (ii) 38cm -1 or less Raman D half-width at half maximum; (iii) 57 cm -1 (iv) a Raman 2D half-width at half maximum of 1.6 or less; (v) a Raman 2D / G ratio of 0.3 or more.

[0104] Furthermore, the support of the present invention may include a carbon structure which, in addition to an oxygen content within a specific range, exhibits one or more of the above-mentioned characteristics (i) to (iii) in its Raman spectrum obtained by Raman spectroscopy: (i) a Raman G half-width at half maximum within a specific range; (ii) a Raman D half-width at half maximum within a specific range; and (iii) a Raman 2D half-width at half maximum within a specific range.

[0105] Specifically, for example, the carrier of the present invention may have an oxygen content of 1.0 wt% or more and include a 57 cm -1 or below the Raman 2D half-width at half maximum of carbon structures.

[0106] Furthermore, the support of the present invention may include a carbon structure that, in addition to an oxygen content within a specific range, exhibits one or more of the above-mentioned characteristics (iv) and (v) in its Raman spectrum obtained by Raman spectroscopy: (iv) a Raman D / G ratio within a specific range; and (v) a Raman 2D / G ratio within a specific range.

[0107] In addition, the support of the present invention may include a carbon structure that, in addition to an oxygen content within a specific range, exhibits one or more features selected from the group consisting of the following features (i) to (iii) in its Raman spectrum obtained by Raman spectroscopy, and exhibits one or more features selected from the group consisting of the following features (iv) and (v) in its Raman spectrum obtained by Raman spectroscopy: (i) Raman G half-width at half maximum within a specific range; (ii) Raman D half-width at half maximum within a specific range; (iii) Raman 2D half-width at half maximum within a specific range; (iv) Raman D / G ratio within a specific range; and (v) Raman 2D / G ratio within a specific range.

[0108] Furthermore, the carrier of the present invention preferably has, for example, a BET specific surface area within a specific range, a true density within a specific range, and an oxygen content within a specific range.

[0109] In addition, for example, as a characteristic regarding its pore volume, the carrier of the present invention may have one or more selected from the following: a pore volume within a specific range (5-70 nm); a pore volume within a specific range (less than 5 nm); and a pore volume ratio within a specific range (5 / (5-70)).

[0110] That is, in this case, the carrier of the present invention may have only one of the following three pore volume characteristics: pore volume within a specific range (5-70 nm); pore volume within a specific range (less than 5 nm); and pore volume ratio within a specific range (5 / (5-70)). Alternatively, the carrier of the present invention may have a combination of any two of the above three pore volume characteristics, i.e., pore volume within a specific range (5-70 nm) and pore volume within a specific range (less than 5 nm), pore volume within a specific range (5-70 nm) and pore volume ratio within a specific range (5 / (5-70)), or pore volume within a specific range (less than 5 nm) and pore volume ratio within a specific range (5 / (5-70)). Alternatively, the carrier of the present invention may have all (three) pore volume characteristics.

[0111] The carrier of the present invention is preferably a carbonized material. The carbonized material is obtained by carbonizing a raw material containing an organic substance. For example, the organic substance content in the raw material used for carbonization can be 5% by weight or more and 90% by weight or less, preferably 10% by weight or more and 80% by weight or less.

[0112] The organic substance in the raw material is not particularly limited as long as the organic substance is carbonized. The organic compound in the organic substance may be a polymer (eg, a thermosetting resin and / or a thermoplastic resin) and / or may be an organic compound having a relatively small molecular weight.

[0113] Specifically, the organic substance can be, for example, one or more selected from the group consisting of: polyacrylonitrile; polyacrylonitrile-polyacrylic acid copolymer; polyacrylonitrile-polymethyl acrylate copolymer; polyacrylonitrile-polymethacrylic acid copolymer; polyacrylonitrile-polymethacrylic acid-polymethylallyl sulfonic acid copolymer; polyacrylonitrile-polymethyl methacrylate copolymer; phenol resin; polyfurfuryl alcohol; furan; furan resin; phenol formaldehyde resin; melamine; melamine resin; epoxy resin; nitrogen-containing chelate resin (for example, one or more selected from the group consisting of: polyamine type chelate resin; iminodiacetic acid type chelate resin; aminophosphoric acid type chelate resin; and aminomethylphosphonic acid type chelate resin); polyamide-imide resin; pyrrole; polypyrrole; polyvinylpyrrole; 3-methylpolypyrrole; propylene Nitrile; polyvinylidene chloride; thiophene; oxazole; thiazole; pyrazole; vinylpyridine; polyvinylpyridine; pyridazine; pyrimidine; piperazine; pyran; morpholine; imidazole; 1-methylimidazole; 2-methylimidazole; quinoxaline; aniline; polyaniline; succinic acid dihydrazide; adipic acid dihydrazide; polysulfone; polyaminobismaleimide; polyimide; polyvinyl alcohol; polyvinyl butyral; benzimidazole; polybenzimidazole; polyamide; polyester; polylactic acid; polyether; polyetheretherketone; cellulose; carboxymethylcellulose; lignin; chitin; chitosan; pitch; silk; wool; polyamino acid; nucleic acid; DNA; RNA; hydrazine; hydrazide; urea; salene; polycarbazole; polybismaleimide; triazine; polyacrylic acid; polyacrylate; polymethacrylate; polymethacrylic acid; polyurethane; polyamidoamine; and polycarbodiimide.

[0114] The carrier of the present invention preferably contains nitrogen. That is, the carrier of the present invention preferably contains nitrogen atoms (e.g., doped nitrogen atoms) in its carbon structure. The nitrogen-containing carrier of the present invention is preferably a carbonized material containing nitrogen. The nitrogen-containing carbonized material is obtained, for example, by carbonizing a raw material containing a nitrogen-containing organic substance. The nitrogen-containing organic substance preferably contains a nitrogen-containing organic compound. The nitrogen-containing organic compound is not particularly limited as long as the organic compound contains nitrogen atoms in its molecule. The nitrogen in the carrier of the present invention may be nitrogen introduced by a nitrogen doping treatment.

[0115] For example, the nitrogen content of the support of the present invention may be 0.10 wt% or more, preferably 0.15 wt% or more, more preferably 0.20 wt% or more, even more preferably 0.25 wt% or more, and particularly preferably 0.30 wt% or more. For example, the nitrogen content of the support of the present invention may be 10.00 wt% or less. The nitrogen content of the carbon support is determined by elemental analysis (specifically, combustion) of the carbon support.

[0116] The support of the present invention is preferably a carbonized material obtained by carbonizing a raw material containing an organic substance and a metal. In this case, the support of the present invention may be a carbonized material that has been subjected to a metal removal treatment after carbonization. The metal removal treatment is a treatment for reducing the amount of raw material-derived metals in the carbonized material. Specifically, the metal removal treatment is preferably, for example, an acid washing treatment and / or an electrolytic treatment.

[0117] When the support of the present invention is a carbonized material obtained by carbonizing a raw material containing an organic substance and a metal, the support of the present invention may contain a metal derived from the raw material for carbonization (hereinafter sometimes referred to as "raw metal"). In this case, the support of the present invention contains metal within the skeleton forming a porous structure. Even when the support of the present invention is a carbonized material produced by a metal removal process as described above, the raw metal remains within the skeleton of the support of the present invention. In this case, the weight of the metal within the skeleton of the support of the present invention may be greater than the weight of the metal on the surface of the skeleton of the support of the present invention.

[0118] The metal within the skeleton of the carrier of the present invention can be detected by, for example, subjecting the skeleton to surface etching and analyzing the cross-section exposed by the etching. That is, in this case, when a single particle of the carrier of the present invention is subjected to etching, metal is detected in the cross-section of the particle exposed by the etching. The metal in the carrier of the present invention can be detected, for example, by inductively coupled plasma atomic emission spectroscopy of the carrier of the present invention.

[0119] For example, the metal content of the support of the present invention (the ratio of the weight of the metal in the support of the present invention to the weight of the support of the present invention on which the catalyst metal particles have not been loaded) may be 0.000% by weight or more, 0.001% by weight or more, 0.002% by weight or more, or 0.003% by weight or more. In addition, for example, the metal content of the support of the present invention may be 1% by weight or less, 0.5% by weight or less, 0.1% by weight or less, 0.05% by weight or less, 0.01% by weight or less, 0.008% by weight or less, or 0.005% by weight or less. The metal content of the support of the present invention can be specified by freely combining any one of the above lower limits with any one of the above upper limits. The metal content of the support of the present invention is obtained, for example, by inductively coupled plasma atomic emission spectroscopy of the support of the present invention.

[0120] The raw material metal is preferably a transition metal. That is, the raw material metal is preferably a transition metal belonging to Groups III to XII in the periodic table, and particularly preferably a transition metal belonging to the fourth period of Groups III to XII in the periodic table.

[0121] The raw material metal may be a transition metal other than platinum. In addition, the raw material metal may be a transition metal other than a noble metal (e.g., ruthenium (Ru), palladium (Pd), rhodium (Rh), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au)).

[0122] Specifically, the raw material metal can be, for example, one or more selected from the group consisting of scandium (Sc); titanium (Ti); vanadium (V); chromium (Cr); manganese (Mn); iron (Fe); cobalt (Co); nickel (Ni); copper (Cu); zinc (Zn); yttrium (Y); zirconium (Zr); niobium (Nb); molybdenum (Mo); ruthenium (Ru); rhodium (Rh); palladium (Pd); silver (Ag); lanthanides (e.g., gadolinium (Gd)); and actinides, and is preferably selected from one or more of the group consisting of: Fe; Co; Ni; Cu; and Zn, more preferably selected from one or more of the group consisting of: Fe; Co; Ni; and Zn, and particularly preferably selected from one or more of the group consisting of: Co; Ni; and Zn.

[0123] The support of the present invention may not contain platinum (Pt). In addition, the support of the present invention may not contain any precious metals. That is, the support of the present invention may not contain, for example, ruthenium (Ru), palladium (Pd), rhodium (Rh), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au).

[0124] Carbonization in the production of the carbonized material is performed by heating the raw material to a temperature at which the organic matter in the raw material is carbonized. The carbonization temperature is not particularly limited as long as the raw material is carbonized at that temperature. The carbonization temperature is, for example, preferably 1,200°C or higher, more preferably 1,300°C or higher, more preferably 1,400°C or higher, and particularly preferably 1,500°C or higher.

[0125] In addition, for example, the carbonization temperature may be 3,000°C or less, preferably 2,500°C or less. In addition, the carbonization temperature may be 2,400°C or less, may be 2,300°C or less, may be 2,200°C or less, may be 2,100°C or less, may be 2,000°C or less, may be 1,900°C or less, may be 1,800°C, 800°C, may be 1,700°C or less, or may be 1,600°C, 600°C. The carbonization temperature may be specified by heating the raw material at a temperature above any of the upper limits. The temperature increase rate to reach the carbonization temperature is not particularly limited and may be, for example, 0.5°C / min or more and 300°C / min or less. Carbonization is preferably performed in an inert atmosphere such as a nitrogen atmosphere.

[0126] Carbonization can be carried out under normal pressure (atmospheric pressure), but is preferably carried out under pressure (under a pressure higher than atmospheric pressure). When carbonization is carried out under pressure, the pressure of the atmosphere used for carbonization can be, for example, 0.05 MPa or more in terms of gauge pressure, and is preferably 0.15 MPa or more, more preferably 0.20 MPa or more, still more preferably 0.40 MPa or more, particularly preferably 0.50 MPa or more in terms of gauge pressure. The upper limit of the atmospheric pressure used for carbonization is not particularly limited, but the pressure can be, for example, 10 MPa or less (in terms of gauge pressure).

[0127] The support of the present invention is preferably a carbonized material that has been subjected to graphitization treatment after carbonization. That is, the support of the present invention is preferably a carbonized material obtained by, for example, carbonizing a raw material containing an organic substance and further subjecting it to graphitization treatment.

[0128] The graphitization treatment is performed by heating the carbonized material at a temperature at which graphitization is performed. The heating temperature at which the carbonized material is heated in the graphitization treatment is not particularly limited as long as graphitization is performed in the carbonized material at that temperature. However, the heating temperature is preferably a temperature higher than the carbonization temperature for obtaining the carbonized material.

[0129] Specifically, the heating temperature in the graphitization treatment may be, for example, 1,300° C. or higher, preferably 1,400° C. or higher, more preferably 1,500° C. or higher, still more preferably 1,600° C. or higher, still more preferably 1,650° C. or higher, particularly preferably 1,700° C. or higher.

[0130] In addition, for example, the heating temperature in the graphitization treatment may be 1,750°C or above, may be 1,800°C or above, may be 1,850°C or above, may be 1,900°C or above, may be 1,950°C or above, may be 2,000°C or above, may be 2,050°C or above, may be 2,100°C or above, may be 2,150°C or above, or may be 2,200°C or above.

[0131] Furthermore, for example, the heating temperature in the graphitization treatment may be 3,000° C. or lower, may be 2,500° C. or lower, may be 2,400° C. or lower, may be 2,300° C. or lower, may be 2,250° C. or lower, or may be 2,200° C. or lower.

[0132] In addition, for example, the heating temperature in the graphitization treatment may be 2,150°C or less, may be 2,050°C or less, may be 2,000°C or less, may be 1,950°C or less, may be 1,900°C or less, may be 1,850°C or less, may be 1,800°C or less, may be 1,750°C or less, or may be 1,700°C or less.

[0133] The heating temperature in the graphitization treatment can be specified by freely combining any one of the above lower limits with any one of the above upper limits. The temperature increase rate to reach the heating temperature in the graphitization treatment is not particularly limited and can be, for example, 0.5°C / min or more and 300°C / min or less. The graphitization treatment is preferably performed in an inert atmosphere such as a nitrogen atmosphere.

[0134] When the carrier of the present invention is a carbonized material that has been subjected to graphitization after carbonization, the carbonized material after graphitization is preferably not subjected to pulverization. That is, in the production of the carrier of the present invention, for example, the following process is preferred: the carbonized material obtained by carbonizing the raw material is subjected to pulverization to adjust its particle size (e.g., median diameter); then the pulverized carbonized material is graphitized; and the carbonized material after graphitization is not subjected to pulverization.

[0135] The support of the present invention is preferably a carbonized material that has been subjected to an oxidation treatment after a graphitization treatment. That is, the support of the present invention is preferably a carbonized material obtained by, for example, subjecting a carbonized material obtained by carbonizing a raw material containing an organic substance to a graphitization treatment and then further subjecting the resultant to an oxidation treatment.

[0136] The oxidation treatment is carried out by heating the carbonized material in an oxygen-containing atmosphere at a temperature at which oxidation is carried out. The atmosphere in which the oxidation treatment is carried out is not particularly limited as long as the atmosphere contains oxygen. However, for example, it is preferably carried out in air (in the atmosphere). The heating temperature at which the carbonized material is heated in the oxidation treatment is not particularly limited as long as oxidation is carried out in the carbonized material at that temperature. However, the heating temperature is preferably a temperature lower than the carbonization temperature for obtaining the carbonized material.

[0137] Specifically, the heating temperature in the oxidation treatment may be, for example, 300° C. or higher, preferably 320° C. or higher, more preferably 350° C. or higher, still more preferably 380° C. or higher, still more preferably 400° C. or higher, particularly preferably 420° C. or higher.

[0138] In addition, the heating temperature in the oxidation treatment can be, for example, 650°C or less, preferably 600°C or less, more preferably 550°C or less, still more preferably 500°C or less, particularly preferably 480°C to 80°C. The particularly preferred heating temperature can be, for example, as long as any one of the above-mentioned upper limits is specified at the temperature.

[0139] The support of the present invention is preferably a carbon material exhibiting catalytic activity. In other words, in this case, the support of the present invention is preferably a carbon catalyst that exhibits catalytic activity alone. The support of the present invention used as a carbon catalyst is preferably a carbonized material obtained by carbonizing a raw material containing an organic substance and a metal as described above.

[0140] The catalytic activity of the support of the present invention is preferably, for example, reduction activity and / or oxidation activity, more preferably oxygen reduction activity and / or hydrogen oxidation activity, and particularly preferably at least oxygen reduction activity.

[0141] The carrier of the present invention is preferably used as a carbon carrier for supporting catalyst metal particles. In this regard, a metal-supported catalyst according to an embodiment of the present invention (hereinafter referred to as "the catalyst of the present invention") includes the carrier of the present invention and the catalyst metal particles supported on the carrier of the present invention.

[0142] The catalyst of the present invention is prepared by supporting the catalyst metal particles on the carrier of the present invention. That is, for example, the carrier of the present invention is impregnated with a precursor of the metal used to construct the catalyst metal particles, and then the carrier of the present invention impregnated with the precursor is subjected to a reduction treatment. Thus, the catalyst metal particles each containing a metal are supported on the carrier of the present invention.

[0143] The catalyst metal particles are not particularly limited as long as the metal particles exhibit catalytic activity. However, the catalyst metal particles are preferably metal particles that exhibit reduction activity and / or oxidation activity, more preferably metal particles that exhibit oxygen reduction activity and / or hydrogen oxidation activity, and particularly preferably metal particles that exhibit at least oxygen reduction activity.

[0144] Specifically, the catalyst metal particles are preferably metal particles containing a noble metal (hereinafter referred to as "noble metal particles"). The noble metal particles contain pure noble metal (noble metal to prevent alloy formation) and / or noble metal alloys (alloys of noble metals and metals other than noble metals (hereinafter referred to as "non-noble metals")). Noble metal alloys are alloys of one or more noble metals and one or more non-noble metals.

[0145] The noble metal is preferably one or more selected from the group consisting of ruthenium (Ru), palladium (Pd), rhodium (Rh), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au). More preferably, it is one or more selected from the group consisting of Ru, Pd, Rh, Ir, and Pt, with Pt being particularly preferred. Specifically, the noble metal particles are particularly preferably platinum particles (each containing platinum). Each platinum particle contains pure platinum (platinum to prevent alloying) and / or a platinum alloy (an alloy of platinum and a non-noble metal).

[0146] The non-noble metal used to form the noble metal alloy is not particularly limited, as long as the non-noble metal forms an alloy with the noble metal. However, the non-noble metal is preferably a transition metal other than the noble metal. Specifically, the non-noble metal in the noble metal alloy is, for example, preferably one or more selected from titanium (Ti), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), niobium (Nb) and cerium (Ce), more preferably one or more selected from Fe, Co and Ni, and particularly preferably one or more selected from Co and Ni.

[0147] When the carrier of the present invention is a carbonized material of a raw material containing an organic substance and a raw material metal, the catalyst metal particles supported on the carrier of the present invention may contain the same metal as the raw material metal, or may not contain the same metal as the raw material metal.

[0148] The catalyst of the present invention preferably has a ratio of the weight of the precious metal in the catalyst of the present invention (more specifically, the precious metal in the catalyst metal particles) to the weight of the catalyst of the present invention (hereinafter referred to as the "precious metal content") of 10% by weight or more. The precious metal content of the catalyst of the present invention is, for example, more preferably 20% by weight or more, even more preferably 30% by weight or more, even more preferably 35% by weight or more, even more preferably 40% by weight or more, and particularly preferably 45% by weight or more.

[0149] In addition, for example, the precious metal content of the catalyst of the present invention may be 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less. The precious metal content of the catalyst of the present invention can be specified by freely combining any of the above lower limits with any of the above upper limits. The precious metal content of the catalyst of the present invention is obtained by inductively coupled plasma (ICP) atomic emission spectroscopy.

[0150] An electrode according to an embodiment of the present invention (hereinafter referred to as "the electrode of the present invention") includes the catalyst of the present invention. That is, the electrode of the present invention includes a battery electrode containing an electrode substrate and the catalyst of the present invention supported on the electrode substrate. Specifically, the electrode of the present invention includes, for example, an electrode substrate and a catalyst layer containing the catalyst of the present invention, the layer being formed on the electrode substrate.

[0151] The electrode of the present invention is preferably a battery electrode. That is, the electrode of the present invention is preferably an electrode for a fuel cell (such as a polymer electrolyte fuel cell), an air battery, a water electrolysis cell (such as a polymer electrolyte water electrolysis cell), a redox flow battery, or a halogen battery.

[0152] The electrode of the present invention can be a cathode or an anode, but is preferably a cathode. That is, the electrode of the present invention is a cathode or an anode of a fuel cell, an air battery, a water electrolysis cell, a redox flow battery or a halogen battery, preferably a cathode.

[0153] A battery according to an embodiment of the present invention (hereinafter referred to as a "battery of the present invention") includes the electrode of the present invention. Specifically, the battery of the present invention is preferably a fuel cell (e.g., a polymer electrolyte fuel cell), an air battery, a redox flow battery, or a halogen battery including the electrode of the present invention. The battery of the present invention preferably includes a membrane electrode assembly (MEA) including the electrode of the present invention.

[0154] The battery of the present invention is a battery comprising the electrode of the present invention as a cathode or anode, preferably a battery comprising the electrode of the present invention as a cathode. That is, the battery of the present invention is a fuel cell, air battery, redox flow battery, or halogen battery comprising the electrode of the present invention as a cathode or anode, preferably a fuel cell, air battery, redox flow battery, or halogen battery comprising the electrode of the present invention as a cathode.

[0155] Next, specific examples according to the embodiment of the present invention will be described. Example

[0156] [Preparation of Carbon Support: Example C1 to Example C4] Commercially available Ketjen Black (EC600JD, manufactured by Lion Specialty Chemicals Co., Ltd.) was used as the carbon support KB of Example C1. Furthermore, the carbon support KB was subjected to air oxidation treatment by heating in air at 450° C. for 1 hour. The carbon material obtained by the air oxidation treatment was used as the carbon support KB-AO of Example C2.

[0157] The carbon support KB was graphitized by heating at 2,000°C in a nitrogen atmosphere at normal pressure. The carbon material obtained by the graphitization treatment was used as the carbon support KB-G2000 in Example C3. The carbon support KB-G2000 obtained in Example C3 was air-oxidized by heating in air at 450°C for 1 hour. The carbon material obtained by the air-oxidation treatment was used as the carbon support KB-G2000AO in Example C4.

[0158] [Preparation of carbon support: Example C5] 1.0 g of polyacrylonitrile, 1.0 g of 2-methylimidazole, 3.3 g of zinc chloride (ZnCl2) and 30 g of dimethylformamide were mixed. The solvent was removed from the resulting mixture by drying. The dried mixture was injected by heating at 250° C. in an atmosphere.

[0159] The injected mixture was carbonized by heating at 1,500°C in a nitrogen atmosphere at a gauge pressure of 0.90 MPa (increased pressure). Dilute hydrochloric acid was added to the carbonized material obtained by carbonization, and the mixture was stirred. The suspension containing the carbonized material was then filtered through a filter membrane, and the carbonized material was washed with distilled water until the filtrate became neutral. In this way, metal removal treatment was performed by acid washing.

[0160] The carbonized material after metal removal treatment was pulverized with a fine pulverizer until its median particle size reached 0.4 μm or less. The pulverized carbonized material was dried in a vacuum to remove water. The carbonized material thus obtained was used as the carbon support C1500 of Example C5.

[0161] [Preparation of Carbon Support: Example C6 to Example C9] The carbon support C1500 obtained in Example C5 was graphitized by heating at 1,700° C., 1,900° C., 2,000° C., or 2,200° C. in a nitrogen atmosphere under normal pressure. The carbonized materials obtained by the graphitization treatment at 1,700° C., 1,900° C., 2,000° C., and 2,200° C. were used as the carbon support C1500-G1700 of Example C6, the carbon support C1500-G1900 of Example C7, the carbon support C1500-G2000 of Example C8, and the carbon support C1500-G2200 of Example C9, respectively.

[0162] [Preparation of Carbon Support: Examples 1 to 4] The carbon supports C1500-G1700, C1500-G1900, C1500-G2000, and C1500-G2200 obtained in Examples C6 to C9 were each subjected to an oxidation treatment by heating at 450° C. in air for 1 hour. The carbonized materials obtained by the oxidation treatment after the graphitization treatment were used as the carbon support C1500-G1700AO of Example 1, the carbon support C1500-G1900AO of Example 2, the carbon support C1500-G2000AO of Example 3, and the carbon support C1500-G2200AO of Example 4, respectively.

[0163] [Constant volume expansion method (true density)] The true density of the carbon support was measured by the constant volume expansion method in accordance with JIS M 8717. Specifically, the carbon support was loaded into a volume of 1.8 cm 3 The volume of helium eliminated from the sample chamber by the Boyle's law was calculated using an ultra-pycnometer (UP-1200e, manufactured by Anton Paar GmbH). This measurement was performed three times for each carbon support, and the arithmetic mean of the volumes obtained by the three measurements was obtained as the volume of the carbon support. Then, the weight (g) of the carbon support measured with an electronic balance was divided by the volume (cm) of the carbon support obtained as described above. 3 ) to calculate the true density of the carbon support (g / cm 3 ).

[0164] [Elemental analysis (oxygen content)] The oxygen content of the carbon support was measured by elemental analysis (pyrolysis method). Specifically, 2 mg of the carbon support was pyrolyzed on carbon-coated platinum at 1,000°C in a helium / hydrogen atmosphere (hydrogen: 5% to 8% by volume), and the oxygen-containing compounds (gases) generated by the pyrolysis were analyzed using an organic trace element analyzer (2400 II, PerkinElmer, Inc.). The oxygen content (wt%) of the carbon support was thus obtained.

[0165] [Raman spectroscopy] The carbon support was analyzed by Raman spectroscopy. Raman spectra were measured using a HORIBA micro-laser Raman spectrometer (LabRAM, HORIBA Jobin Yvon). The laser used for measurement had an excitation wavelength of 532 nm and an output of 50 mW, and the measurement was performed under exposure conditions of 90 seconds x 2 integrations through a neutral density filter D3. Thus, a Raman spectrum was obtained.

[0166] The obtained Raman spectra were baseline corrected. That is, by determining the -1 Raman shift (cm -1 ) and the scattering intensity near 2,000 cm -1 Raman shift (cm -1 ) is used as a baseline, and the baseline is subtracted from each intensity of the scattering spectrum to perform baseline correction. Herein, the baseline-corrected Raman spectrum obtained for the carbon support C1500-G1700AO of Example 1 is shown as an example of a Raman spectrum. Figure 1 middle.

[0167] Then, identification at 1,580cm -1 Near the Raman shift (specifically, at 1,550 cm -1 or above and 1,610cm -1 Then, from the intensity I corresponding to the G band, g Raman shift (cm -1 )A g Subtract the intensity I corresponding to the G band from g Raman shift (cm) of half the intensity of the G band at the top of the peak -1 )B g Therefore, the Raman G half-peak half-width (cm -1 That is, the Raman G half-peak half-width of the carbon support is calculated by the following equation: Raman G half-peak half-width (cm -1 )=A g (cm -1 )-B g (cm -1 )).

[0168] Next, identify the -1 Near the Raman shift (specifically, at 1,320 cm -1 or above and 1,360cm -1 Then, from the intensity I corresponding to the D band, d Raman shift (cm -1 )A d Subtract the intensity I corresponding to the D band from d Raman shift (cm) of half the intensity of the D band at the top of the peak -1 )B d Therefore, the Raman D half-width at half maximum (cm -1 That is, the Raman D half-peak half-width of the carbon support is calculated by the following equation: Raman D half-peak half-width (cm -1 )=A d (cm-1 )-B d (cm -1 )).

[0169] In addition, recognition at 2,700 cm -1 Near the Raman shift (specifically, at 2,670 cm -1 or above and 2,730cm -1 Then, from the intensity I corresponding to the 2D band, 2d Raman shift (cm -1 )A 2d Subtract the intensity I corresponding to the 2D band from 2d Raman shift (cm) of half the intensity of the 2D band at the top of the peak -1 )B 2d Therefore, the Raman 2D half-width at half maximum (cm -1 That is, the Raman 2D half-maximum width at half maximum of the carbon support was calculated by the following equation: Raman 2D half-maximum width at half maximum (cm -1 )=A 2d (cm -1 )-B 2d (cm -1 )).

[0170] In addition, by changing the intensity of the D band I d Divide by the intensity of the G band I g To calculate the Raman D / G ratio. That is, the Raman D / G ratio of the carbon support is calculated by the following equation: Raman D / G ratio = I d / I g .

[0171] Furthermore, by transforming the intensity of the 2D band I 2d Divide by the intensity of the G band I g To calculate the Raman 2D / G ratio. That is, the Raman 2D / G ratio of the carbon support is calculated by the following equation: Raman 2D / G ratio = I 2d / I g .

[0172] [Nitrogen adsorption method] The specific surface area and pore volume of the carbon support, the hysteresis in the nitrogen adsorption isotherm, and the pore mode diameter were measured by a nitrogen adsorption method using a specific surface area / pore distribution measuring apparatus (TriStar II 3020 manufactured by Shimadzu Corporation) and analysis software (TriStar II 3020) included in the apparatus.

[0173] That is, first, 0.1 g of the carbon support was heated at 100 °C and 6.7 × 10 -2Pa for 3 hours to remove moisture adsorbed on the carbon support. Next, a nitrogen adsorption isotherm at 77 K was obtained by the BET method. The nitrogen adsorption isotherm at 77 K was obtained by measuring the change in the amount of nitrogen adsorbed on the carbon support as the pressure of nitrogen gas at 77 K changed.

[0174] exist Figure 2 In the figure, the nitrogen adsorption isotherm obtained for the carbon support C1500-G1700AO of Example 1 is shown as an example of a nitrogen adsorption isotherm obtained at 77 K by the BET method. Figure 2 In the adsorption isotherm shown, the axis of the abscissa indicates relative pressure (P / P0)(-), which is the ratio of the adsorption equilibrium pressure (P) to the saturated vapor pressure (P0) (1.01×10 5 Pa), and the axis of ordinate indicates the nitrogen adsorption amount (cm 3 / g). Figure 2 As shown, an adsorption side isotherm (adsorption isotherm measured when the relative pressure increases) (solid circle marks in the figure) and a desorption side isotherm (adsorption isotherm measured when the relative pressure decreases) (open circle marks in the figure) are obtained.

[0175] Then, in the nitrogen adsorption isotherm obtained for each carbon support, the nitrogen adsorption amount was subtracted from the nitrogen desorption amount at a relative pressure (P / P0) of 0.5. Thus, the hysteresis (0.5P / P0) (cm 3 / g), which is the difference between the amount of nitrogen desorption and the amount of nitrogen adsorption. Similarly, the amount of nitrogen adsorption was subtracted from the amount of nitrogen desorption at a relative pressure (P / P0) of 0.8. Thus, the hysteresis (0.8P / P0) (cm 3 / g), which is the difference between the nitrogen desorption amount and the nitrogen adsorption amount.

[0176] In addition, the BET specific surface area (m 2 / g). In addition, by the DFT method, the volume (cm 3 The volume of pores of each carbon support having a pore diameter of less than 5 nm (pore volume (less than 5 nm)) (cm 3 Similarly, by calculating the volume (cm2) of the corresponding pores each having a pore diameter of 5 nm or more and 70 nm or less, 3 / g) was integrated to calculate the volume of pores each having a pore diameter of 5 nm or more and 70 nm or less (pore volume (5-70 nm)) (cm 3 / g).

[0177] Furthermore, the ratio of the pore volume (less than 5 nm) to the pore volume (5-70 nm) of each carbon support was calculated by dividing the pore volume (less than 5 nm) by the pore volume (5-70 nm) (pore volume ratio (5 / (5-70)))(-).

[0178] In addition, the pore size distribution was obtained from the nitrogen adsorption isotherm by the DFT method at a temperature of 77 K. The pore size distribution obtained for the carbon support KB (open circle mark) of Example C1 and the carbon support KB-G2000 (filled circle mark) of Example C3 is shown in FIG. Figure 3A In addition, the pore size distributions obtained for the carbon support C1500 of Example C5 (open circle mark), the carbon support C1500-G1900 of Example C7 (closed circle mark), and the carbon support C1500-G1900AO of Example 2 (closed square mark) are shown in FIG. Figure 3B middle.

[0179] exist Figure 3A and Figure 3B In each of the graphs, the axis of abscissa represents the pore diameter D (nm), and the axis of ordinate represents the logarithmic differential pore volume ("dV / dlogD" in the graph) (cm 3 / g). In addition, the pore diameter (nm) at which the logarithmic differential pore volume becomes the maximum value in this pore size distribution of each carbon support was obtained as the pore mode diameter (nm) of the carbon support.

[0180] [Preparation of Metal-Supported Catalyst] A metal-supported catalyst is prepared by loading catalyst metal particles onto each of the above-mentioned carbon supports. Specifically, 1 g of the carbon support obtained in each of Examples C5 to C9 and Examples 1 to 4 is mixed with 10 g of an aqueous solution containing a certain amount of chloroplatinic acid (HPtCl) as a platinum precursor so that its platinum concentration becomes 10 wt % (platinum content: 1 g). First, the mixture is stirred at a gauge pressure (reduced pressure) of -0.1 MPa for 1 hour. Next, the mixture is stirred at a gauge pressure (increased pressure) of 0.15 MPa for 1 hour. In addition, the mixture is stirred at normal pressure for 18 hours. Afterwards, the resulting mixed liquid is dried at 100 ° C at a gauge pressure (reduced pressure) of -0.1 MPa. In addition, the mixed liquid is maintained in nitrogen at 150 ° C so that its solvent component is volatilized.

[0181] First, the obtained solid was subjected to a heat treatment (gas phase reduction treatment) at 350° C. for 180 minutes in a hydrogen atmosphere (hydrogen: 100% by volume). Subsequently, the treated solid was subjected to a heat treatment at 700° C. for 180 minutes in a nitrogen atmosphere (nitrogen: 100% by volume). Thus, a metal-supported catalyst including a carbon support and platinum particles as catalyst metal particles supported on the carbon support was obtained.

[0182] [Power generation test and potential cycle test] In order to evaluate one aspect of the performance of the metal-supported catalyst, a power generation test and a potential cycle test of a fuel cell including an electrode containing a metal-supported catalyst were performed. In the potential cycle test, the durability of the metal-supported catalyst, particularly its resistance to load fluctuation (load fluctuation tolerance), was evaluated. Specifically, first, a battery cathode with a catalyst layer was produced, the catalyst layer comprising the metal-supported catalyst formed thereon. That is, an electrolyte (equivalent EW=820) (in an amount such that the weight ratio of the metal-supported catalyst to the carbon support was 1.1) was added to 0.25 g of the metal-supported catalyst prepared as described above, and each 2 g of distilled water and 1-propanol were added to prepare an electrolyte solution. The electrolyte solution and 25 g of balls were placed in a tank and mixed with a ball mill at 200 rpm for 50 minutes. Therefore, a slurry composition for a catalyst layer containing a uniformly dispersed metal-supported catalyst was obtained.

[0183] The obtained slurry composition for a catalyst layer was applied to a gas diffusion layer ("29BC", manufactured by SGL Carbon Japan Co., Ltd.) having an area of ​​5 cm 2 The platinum content of the catalyst metal particles supported on the metal-supported catalyst per unit area of ​​the battery electrode becomes 0.2 mg-Pt / cm 2 , and dried to form a catalyst layer on the gas diffusion layer. Thus, a battery cathode having a catalyst layer containing a metal-supported catalyst formed thereon is obtained.

[0184] Next, a fuel cell comprising an electrode having a catalyst layer containing a metal-supported catalyst formed thereon was produced. That is, a battery cathode having a catalyst layer (positive electrode catalyst layer) containing the metal-supported catalyst prepared as described above formed thereon was used as a positive electrode.

[0185] On the other hand, a negative electrode was produced as follows. 0.5 g of a commercial platinum-supported catalyst Pt / C (a catalyst containing platinum particles supported on a carbon support: UNPC40-II, manufactured by Ishifuku Metal Industry Co., Ltd.), 10 g of 5% Nafion (trademark), 2 g of distilled water, and 25 g of balls were placed in a jar and mixed with a ball mill at 200 rpm for 50 minutes to prepare a slurry Pt / C composition. A battery anode including a catalyst layer (negative electrode catalyst layer) formed of the slurry Pt / C composition was produced in the same manner as the above-mentioned positive electrode, except that the Pt / C composition was applied to the gas diffusion layer (5 cm 2 ) so that the platinum content per unit area becomes 0.1 mg-Pt / cm2 .

[0186] Then, a polymer electrolyte membrane ("Nafion (trademark) 211", manufactured by DuPont) was arranged between the above-mentioned positive electrode catalyst layer and the above-mentioned negative electrode catalyst layer, and the resultant was subjected to pressure bonding under the conditions of 150°C and 1 MPa for 3 minutes. Thus, an MEA was produced. A pair of gaskets were bonded to the MEA, and the resultant was sandwiched between a pair of separators to produce a fuel cell unit cell for a power generation test and a potential cycle test. Then, the unit cell was installed in a fuel cell automatic evaluation system (manufactured by Toyo Corporation). First, a power generation test was performed, and then a potential cycle test was performed.

[0187] In the power generation test, saturated humidified air (oxygen) (relative humidity: 100%) was supplied to the positive electrode side of the unit cell at 2.5 L / min under a back pressure of 150 kPa, and saturated humidified hydrogen (relative humidity: 100%) was supplied to the negative electrode side of the unit cell at 1.0 L / min, the cell temperature was set to 75°C, and the open circuit voltage was measured for 5 minutes. Thereafter, when the cell current density was increased from 4.0 A / cm 2 to 0A / cm 2 After 3 minutes, measure the battery voltage. Then, at 0.2A / cm 2 The voltage (mV) measured at a current density of 0.2A / cm2 at a relative humidity of 100% is taken as the “beginning of life (BOL)”. 2 )(100% RH)”, which was used as an indicator of initial catalytic activity. In addition, at 1.0 A / cm 2 The voltage (mV) measured at a current density of 1.0 A / cm2 at a relative humidity of 100% is taken as the “BOL (1.0 A / cm2)”. 2 )(100% RH)" was obtained and used as another indicator of the initial catalytic activity.

[0188] Subsequently, humidified air (oxygen) (relative humidity: 40%) was supplied to the positive electrode side of the unit cell at 2.5 L / min under a back pressure of 150 kPa, and humidified hydrogen (relative humidity: 40%) was supplied to the negative electrode side of the unit cell at 1.0 L / min, the cell temperature was set to 75°C, and the open circuit voltage was measured for 5 minutes. Thereafter, when the cell current density was increased from 4.0 A / cm 2 to 0A / cm 2 After 3 minutes, measure the battery voltage. Then, at 0.2A / cm 2 The voltage (mV) measured at a current density of 0.2A / cm2 at a relative humidity of 40% is taken as the “BOL (0.2A / cm2)”. 2)(40% RH)" (40% is used as an index of initial catalytic activity under low humidity conditions. Furthermore, the value (mV) obtained by subtracting "BOL (0.2 A / cm 2 )(100% RH) from "BOL (0.2 A / cm 2 )(40% RH) is obtained as "voltage decrease (mV)" upon decrease in humidity.

[0189] After that, the cell temperature was set to 75°C. Saturated humidified nitrogen gas (relative humidity: 100%) was supplied to both sides of the unit cell at 0.5 L / min under a back pressure of 150 kPa, and saturated humidified hydrogen gas (relative humidity: 100%) was supplied to the anode side of the unit cell at 0.5 L / min. The potential cycle test was performed by repeating the following rectangular wave cycle: first, the potential was held at 0.6 V for 10 seconds, and then the potential was held at 0.95 V for 10 seconds.

[0190] Then, the above-described rectangular wave cycle was performed 10,000 times, and then the power generation test was performed again. In the power generation test after the potential cycle test, the voltage (mV) measured at a current density of 0.2 A / cm 2 under a relative humidity of 100% was obtained as "end of life (EOL) (0.2 A / cm 2 )(100% RH).

[0191] [Start-stop test] Furthermore, in order to evaluate another aspect of the performance of the metal-supported catalyst, a start-stop test of a fuel cell including an electrode including the metal-supported catalyst was performed. That is, the durability of the metal-supported catalyst, and in particular, its corrosion resistance (corrosion resistance ability) was evaluated by the change in voltage before and after the start-stop test. Specifically, the MEA was produced by arranging a solid polymer electrolyte membrane (manufactured by DuPont, "Nafion (trademark) 211") between the positive electrode catalyst layer and the negative electrode catalyst layer produced in the same manner as in the above-described power generation test and potential cycle test; and subjecting the resultant to pressure bonding under conditions of 150°C and 1 MPa for 3 minutes. A pair of gaskets was bonded to the MEA, and the resultant was further sandwiched between a pair of separators. Thus, a fuel cell unit cell for the start-stop test was produced. Then, the unit cell was placed in a fuel cell automatic evaluation system (manufactured by Toyo Corporation), and the start-stop test was performed.

[0192] That is, the start-stop test was performed by repeating the following triangular wave cycle: the battery temperature was set to 80°C; saturated humidified nitrogen gas was supplied to each of the two sides of the unit cell at a back pressure of 35 kPa (relative humidity: 100%) at 1.0 L / min; saturated humidified hydrogen gas was supplied to its anode side (relative humidity: 100%) at 1.0 L / min; and its potential was scanned from 1.0 V to 1.5 V at a scan rate of 500 mV / sec.

[0193] The above triangle wave cycle was performed 1,000 times, and then the power generation test was performed. Then, in the power generation test after the start-stop test, the power generation test was performed at 0.2A / cm 2 The voltage (mV) measured at a current density of 100% at a relative humidity of 100% was taken as the voltage after the start-stop test (0.2 A / cm 2 ) was obtained. Similarly, in the power generation test after the start-stop test, at 1.0 A / cm 2 The voltage (mV) measured at a current density of 1.0 A / cm2 at a relative humidity of 100% was taken as the voltage after the start-stop test (1.0 A / cm2). 2 )"get.

[0194] [result] The results of the evaluation of the characteristics of the carbon support were Figure 4A and Figure 4B In addition, Figure 4C The evaluation results of the performance of the metal-supported catalysts are shown in FIG.

[0195] like Figure 4C As shown, the BOL (0.2 A / cm 2 )(100% RH) is significantly smaller than the BOL (0.2 A / cm2) of Example C5 which was not graphitized. 2 ), the carbon supports of Examples C6 to C9 were each subjected to graphitization treatment but not subjected to any oxidation treatment. In contrast, the BOL (0.2 A / cm 2 ) (100% RH) was significantly greater than those of Examples C6 to C9 and equal to or greater than those of Example C5. The carbon supports of Examples 1 to 4 had each been subjected to an oxidation treatment after the graphitization treatment. Among them, the BOL (0.2 A / cm2) of each metal-supported catalyst including the carbon supports of Examples 2 and 3 was 2 )(100% RH) is particularly large.

[0196] BOL (0.2 A / cm 2) (40% RH) is significantly less than the BOL of Example C5. In contrast, the BOL of each of Examples 1 to 4 (0.2 A / cm 2 )(40% RH) was significantly greater than the BOL of Examples C6 to C9 and equal to or greater than the BOL of Example C5. 2 )(40% RH) is significantly greater than that of Example C5, and the BOL of Example 1 (0.2 A / cm 2 ) is particularly large.

[0197] As the humidity decreases from 100% RH to 40% RH, the voltage drop (mV) of each of Examples C6 to C9 is equal to or greater than that of Example C5, and in particular, the voltage drop of Examples C8 and C9 is significantly greater. In contrast, the voltage drop (mV) of Examples 1 to 4 is less than that of Example C5, and is significantly less than that of Examples C6 to C9, respectively. Among them, the voltage drop (mV) of each of Examples 1 and 2 is significantly less than that of Example C5, and the voltage drop of Example 1 is particularly small.

[0198] BOL (1.0 A / cm2) of each of Examples C6 to C9 2 ) (100% RH) is significantly less than the BOL of Example C5. In contrast, the BOL (1.0 A / cm 2 ) (100% RH) was equal to or greater than the BOL of Example C5, and significantly greater than the BOL of Examples C6 to C9. 2 ) (100% RH) is significantly greater than that of Example C5, and the BOL (1.0 A / cm 2 ) is particularly large.

[0199] The EOL (0.2 A / cm2) of each of Examples C6 and C7 2 ) (100% RH) is significantly greater than that of Example C5, but the EOL (0.2 A / cm 2 ) is significantly smaller than Example C5. In contrast, the EOL (0.2 A / cm 2 ) (100% RH) is significantly greater than that of Example C5. In addition, the EOL (0.2 A / cm 2 )(100% RH) were significantly greater than those of Examples C8 and C9, respectively.

[0200] The voltage after the start-stop test (0.2 A / cm 2) is significantly greater than the voltage of Example C5. The voltage after the start-stop test of Examples 1 to 4 (0.2 A / cm 2 ) are significantly greater than the voltage of Example C5, and are respectively greater than the voltages of Examples C6 to C9. Among them, the voltages after the start-stop test of Examples 2 to 4 (0.2 A / cm 2 ) are significantly larger than the voltages of Examples C7 to C9, respectively, and the voltage of Example 4 is particularly large.

[0201] The voltage after the start-stop test (1.0 A / cm 2 ) is greater than the voltage of Example C5. The voltage after the start-stop test of Examples 1 to 4 (1.0 A / cm 2 ) are significantly greater than the voltage of Example C5, and are significantly greater than the voltages of Examples C6 to C9. Among them, the voltages after the start-stop test of Examples 2 to 4 (1.0 A / cm 2 ) is significantly large, and the voltage of Example 4 is particularly large.

[0202] As can be seen from the foregoing, the metal-loaded catalyst including the carbon support of Example 1 exhibits a small "voltage drop," which indicates a decrease in catalytic activity with decreasing humidity, and exhibits a small voltage drop at BOL (0.2 A / cm 2 ) showed high catalytic activity at low humidity (40% RH) as reflected in the above. In addition, the metal-supported catalyst including the carbon support of Example 1 showed a particularly large BOL (1.0 A / cm 2 )(100%RH).

[0203] The metal-supported catalysts including the carbon supports of Examples 2 and 3 each achieved a high level of initial catalytic activity as reflected in the BOL (0.2 A / cm 2 )(100% RH) and BOL(1.0A / cm 2 ) (100% RH) and the corrosion resistance of the carbon support (which is reflected in the voltage after the start-stop test (0.2 A / cm 2 ) and the voltage after the start-stop test (1.0A / cm 2 ) in each of ).

[0204] The metal-supported catalyst including the carbon support of Example 4 exhibited an extremely high level of corrosion resistance of the carbon support, as reflected in the voltage (0.2 A / cm 2 ) and start-stop test voltage (1.0A / cm 2 ) in each of them.

[0205] like Figure 4AAs shown, the true density of the carbon supports of Examples 1 to 4, each of which was subjected to oxidation treatment after graphitization, was significantly greater than the true density of the carbon supports of Examples C6 to C9, each of which was not subjected to oxidation treatment. In other words, the true density of each carbon support was significantly increased by oxidation treatment. Among them, the true density of Examples 1 to 3 was particularly high. On the other hand, the true density of Examples C1, C3, and C4 was low.

[0206] The oxygen content of the carbon supports of Examples 1 to 4 was significantly greater than that of Examples C6 to C9, respectively. In other words, the oxygen content of each carbon support was significantly increased by oxidation treatment. Among them, the oxygen content of Example 1 was particularly high. On the other hand, the oxygen content of Examples C3 and C4 was low.

[0207] The Raman G half-width at half maximum of each carbon support of Examples 1 to 4 is smaller than the Raman G half-width at half maximum of Examples C1 to C5. The Raman D half-width at half maximum of each carbon support of Examples 1 to 4 is significantly smaller than the Raman D half-width at half maximum of Examples C1, C2, and C5. Among them, the Raman D half-width at half maximum of each of Examples 3 and 4 is particularly small. The Raman 2D half-width at half maximum of each carbon support of Examples 1 to 4 is smaller than the Raman 2D half-width at half maximum of Examples C1 to C6.

[0208] The Raman D / G ratios of the carbon supports of Examples 1 to 4 were greater than those of Examples C6 to C9, respectively. This indicates that the Raman D / G ratios of each carbon support were increased by oxidation treatment. Furthermore, the Raman D / G ratios of Examples C1 to C5 were small. The Raman 2D / G ratios of the carbon supports of Examples 1 to 4 were greater than those of Examples C1, C2, and C5. Among these, the Raman 2D / G ratios of Examples 3 and 4 were particularly large.

[0209] like Figure 4B As shown, the BET specific surface areas of the carbon supports of Examples 1 to 4 are respectively greater than those of Examples C6 to C9. In other words, the BET specific surface area of ​​each carbon support is increased by oxidation. Among them, the BET specific surface area of ​​Example 1 is particularly large.

[0210] The pore volumes (5-70 nm) of the carbon supports of Examples 1 to 4 were significantly smaller than those of Examples C1 to C4 and comparable to those of Examples C5 to C9. On the other hand, the pore volumes (less than 5 nm) of the carbon supports of Examples 1 to 4 were significantly larger than those of Examples C1 to C4. Furthermore, the pore volumes (less than 5 nm) of Examples 1 to 4 were significantly larger than those of Examples C6 to C9, respectively. In other words, the pore volumes (less than 5 nm) of each carbon support were significantly increased by oxidation treatment.

[0211] The pore volume ratios (5 / (5-70)) of the carbon supports of Examples 1 to 4 were significantly greater than those of Examples C1 to C4. Furthermore, the pore volume ratios (5 / (5-70)) of Examples 1, 3, and 4 were significantly greater than those of Examples C6, C8, and C9, respectively. Among these, the pore volume ratio (5 / (5-70)) of Example 1 was particularly large.

[0212] The pore mode diameters of the carbon supports of Examples 1 to 4 were significantly smaller than those of Examples C1 to C4. Furthermore, the pore mode diameters of Examples 1 to 3 were comparable to those of Examples C5 to C9. On the other hand, the pore mode diameter of Example 4 was larger than those of Examples C5 to C9.

[0213] The hysteresis (0.5P / PO) and hysteresis (0.8P / PO) of the carbon supports of Examples 1 to 4 were significantly smaller than those of Examples C1 to C4. In addition, the hysteresis (0.5P / PO) of Examples 1 to 4 was greater than that of Examples C6 to C9. On the other hand, the hysteresis (0.8P / PO) of Examples 1 to 4 was comparable to that of Examples C6 to C9.

Claims

1. A carbon support for supporting catalyst metal particles, wherein: The BET specific surface area of ​​the carbon support is 300 m 2 / g or above, The true density of the carbon support is 2.1 g / cm 3 or above, and The carbon support comprises a carbon structure, and the carbon structure exhibits one or more selected from the following features (i) and (ii) in a Raman spectrum obtained by Raman spectroscopy: (i) At 1,340 cm -1 The intensity of the D band with a peak near the top of the Raman shift is relatively close to that at 1,580 cm -1 The ratio of the intensity of the G band having the peak top near the Raman shift is 1.6 or more; and (ii) at 2,700 cm -1 The intensity of the 2D band with a peak near the top of the Raman shift is relative to that at 1,580 cm -1 The ratio of the intensity of the G band having a peak top near the Raman shift peak is 0.3 or more. 2 . The carbon support according to claim 1 , wherein the carbon support comprises the carbon structure exhibiting the characteristic (i). 3 . The carbon support according to claim 1 , wherein the carbon support comprises the carbon structure exhibiting the characteristic (ii). The carbon support according to claim 1 , wherein the carbon support has an oxygen content of 1.0 wt % or more.

5. The carbon support according to claim 1, wherein the carbon support comprises the carbon structure showing a Raman spectrum at 1,580 cm -1 The half-maximum width of the G band near the peak top is 37 cm -1 or below.

6. The carbon support according to claim 1, wherein the carbon support comprises the carbon structure showing a Raman spectrum at 1,340 cm -1 The half-maximum width of the D band near the peak top is 38 cm -1 or below.

7. The carbon support according to claim 1, wherein the carbon support comprises the carbon structure showing a Raman spectrum at 2,700 cm -1 The half-maximum width of the 2D band with a peak top near the Raman shift is 57 cm -1 or below.

8. The carbon carrier according to claim 1, wherein the volume of pores having a pore diameter of 5 nm or more and 70 nm or less of the carbon carrier is 0.50 cm 3 / g or less.

9. The carbon support according to claim 1, wherein the volume of pores having a pore diameter of less than 5 nm of the carbon support is 0.20 cm 3 / g or greater. 10 . The carbon carrier according to claim 1 , wherein the ratio of the volume of pores having a pore diameter of less than 5 nm to the volume of pores having a pore diameter of 5 nm or more and 70 nm or less of the carbon carrier is 4.0 or more. 11 . The carbon support according to claim 1 , wherein the carbon support has a pore mode diameter of 7.0 nm or less.

12. The carbon support according to claim 1, wherein the carbon support comprises a carbon structure showing a nitrogen adsorption isotherm of 40 cm-1 at a temperature of 77 K obtained by a nitrogen adsorption method. 3 / g or less, wherein the difference is obtained by subtracting the nitrogen adsorption amount from the nitrogen desorption amount at a relative pressure P / P0 of 0.5(-), the relative pressure P / P0 being the ratio of the adsorption equilibrium pressure P to the saturated vapor pressure P0.

13. The carbon support according to claim 1, wherein the carbon support comprises a carbon structure that exhibits a 20 cm-1 / ... in a nitrogen adsorption isotherm obtained at a temperature of 77 K by a nitrogen adsorption method. 3 / g or less, wherein the difference is obtained by subtracting the nitrogen adsorption amount from the nitrogen desorption amount at a relative pressure P / P0 of 0.8(-), wherein the relative pressure (P / P0) is the ratio of the adsorption equilibrium pressure P to the saturated vapor pressure P0.

14. A metal-supported catalyst comprising: The carbon support according to any one of claims 1 to 13; and Catalyst metal particles are supported on the carbon support.

15. An electrode comprising the metal-supported catalyst according to claim 14.

16. A battery comprising the electrode according to claim 15.

Images