WO2015088025A1 - 固体高分子形燃料電池用の担体炭素材料及び金属触媒粒子担持炭素材料、並びにこれらの製造方法 - Google Patents
固体高分子形燃料電池用の担体炭素材料及び金属触媒粒子担持炭素材料、並びにこれらの製造方法 Download PDFInfo
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- WO2015088025A1 WO2015088025A1 PCT/JP2014/083043 JP2014083043W WO2015088025A1 WO 2015088025 A1 WO2015088025 A1 WO 2015088025A1 JP 2014083043 W JP2014083043 W JP 2014083043W WO 2015088025 A1 WO2015088025 A1 WO 2015088025A1
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- Prior art keywords
- carbon material
- metal
- fuel cell
- metal catalyst
- polymer electrolyte
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a carrier carbon material and a metal catalyst particle-supporting carbon material for a polymer electrolyte fuel cell, and methods for producing them.
- a polymer electrolyte fuel cell has a catalyst layer serving as an anode and a catalyst layer serving as a cathode with a proton-conducting electrolyte membrane sandwiched therebetween, and a gas diffusion layer disposed on the outside with the catalyst layer sandwiched therebetween.
- the basic structure is a structure in which a separator is arranged outside, and this basic structure is called a unit cell.
- a fuel cell is usually configured by stacking as many unit cells as necessary to achieve a required output.
- oxygen, air, or the like such as oxygen or air is supplied to the cathode side from the gas flow paths of the separators respectively arranged on the anode side and the cathode side.
- An oxidizing gas is supplied to the anode side, and a reducing gas such as hydrogen is supplied to the anode side.
- the supplied oxidizing gas and reducing gas are supplied to the catalyst layer through the gas diffusion layers, respectively.
- An electric current is taken out by utilizing an energy difference (potential difference) between a chemical reaction occurring in the catalyst layer and a chemical reaction occurring in the cathode catalyst layer.
- ion exchange resins typified by perfluorosulfonic acid polymers are used as polymer electrolyte materials.
- these polymer electrolyte materials exhibit high proton conductivity for the first time in a wet environment, and the proton conductivity decreases in a dry environment. Therefore, in order to operate the fuel cell efficiently, it is indispensable to maintain the polymer electrolyte material in a sufficiently wet state. Water vapor is supplied together with the gas supplied to the cathode side and the anode side, and the humidification condition is always maintained. To be maintained.
- Non-Patent Document 1 that the hydrophilic functional groups of the carbon support tend H 2 O is accumulated in the catalyst layer to adsorb H 2 O, reducing the diffusion of oxygen gas, the so-called flooding There is a description that it is presumed to be a factor.
- the metal catalyst particles in the metal catalyst particle-supporting carbon material are in a “highly dispersed state” on the carbon material as a support, and It is necessary to be supported in a fixed state.
- the “highly dispersed state” means that the metal catalyst particles are not separated from each other at a certain distance on the carbon material as a carrier so that the oxidizing gas can be diffused and water can be discharged. It is a state of being distributed like this.
- a carbon material as a support on which metal catalyst particles are supported is referred to as a “support carbon material”.
- the characteristics required for the support carbon material are as follows.
- the carrier carbon material has few hydrophilic functional groups.
- the support carbon material has a large surface area so that the metal catalyst particles are supported in a highly dispersed state on the support carbon material.
- the carrier carbon material has an appropriate amount of sites in order to fix the metal catalyst particles to the carrier carbon material in a highly dispersed state.
- the characteristic of (a) is to reduce the occurrence of flooding by reducing the number of hydrophilic functional groups containing hydrogen at the ends of functional groups such as hydroxyl groups and carboxyl groups in the support carbon material
- the characteristic of (b) is that the metal catalyst particles are dispersed in the support carbon material at a certain distance from each other so as not to be separated more than necessary so that the oxidizing gas can be diffused and water can be discharged.
- the characteristic of (c) is: The site for fixing the metal catalyst particles to the support carbon material in a highly dispersed state should be present appropriately.
- Patent Document 1 As a method for achieving the characteristics, a fluorinated group that is a hydrophobic functional group is introduced as a modifying group on the surface of a carrier carbon material made of carbon particles such as carbon black, thereby reducing the occurrence of flooding. Proposed.
- Patent Document 2 a support carbon material such as commercially available activated carbon or carbon black is used to optimize the structure of the catalyst layer so that gas diffusion is good, thereby generating the catalyst layer on metal catalyst particles even under high humidification conditions.
- a polymer electrolyte fuel cell that prevents the water from blocking the diffusion path of oxygen gas and exhibits high cell performance regardless of humidification conditions.
- Patent Document 3 discloses a carrier carbon material manufactured by the following method as a material having the characteristics (b) and (c). That is, acetylene gas is blown into a solution containing a metal or a metal salt to generate a metal acetylide (acetylide generation step), and the metal acetylide is heated at a temperature of 60 to 80 ° C. for 12 hours or more to form the metal into metal particles A first heat treatment step of producing a segregated and encapsulated metal particle inclusion intermediate, and heating the metal particle inclusion intermediate at a temperature of 160 to 200 ° C.
- a cleaning process cleaning process in which carbon material intermediates are cleaned by dissolving and removing other unstable carbon compounds, and the carbon cleaned in the dissolving and cleaning process
- Patent Document 2 has an advantage that high battery performance can be expressed regardless of humidification conditions, but under high humidification conditions, the hydrophilicity of the surface of a carrier carbon material such as commercially available activated carbon or carbon black. Adsorption of H 2 O on the functional functional group is unavoidable, and there is a problem that H 2 O tends to accumulate in the catalyst layer.
- the inventors have confirmed the battery performance under high humidification conditions for a commercially available carrier carbon material, but the flooding or metal catalyst particles are not supported in a highly dispersed state on the carrier carbon material. It has been found that no carrier carbon material satisfying all of the above characteristics (a), (b), and (c) has existed until now.
- an object of the present invention is to obtain a carrier carbon material that satisfies all of the above characteristics (a), (b), and (c).
- the inventors have found that in order to satisfy the above characteristics (a) It has been conceived that it is necessary to reduce the hydrogen content (% by mass). This is because the hydrogen content in the support carbon material corresponds to the hydrogen content at the end of the hydrophilic functional group. Further, in order to satisfy the characteristic (b), it is necessary to increase the BET surface area (m 2 / g) calculated from the nitrogen adsorption BET specific surface area, and further satisfy the characteristic (c). In order to achieve this, it is necessary that the edge portion of the graphite exhibiting an interaction between the support carbon material and the metal catalyst particles be present in an appropriate amount, that is, that the crystallite of the graphite is in an appropriate range. I came up with it.
- the edge portion of the graphite refers to the end portion of the crystallite
- I D / I G is a peak intensity in the range of 1200 to 1400 cm ⁇ 1 , which is called a D-band obtained from a Raman spectrum (hereinafter referred to as “D-band”).
- I D a relative intensity ratio between the peak intensities in the range of 1500-1700 cm ⁇ 1
- G-band a relative intensity ratio between the peak intensities in the range of 1500-1700 cm ⁇ 1
- I G a relative intensity ratio between the peak intensities in the range of 1500-1700 cm ⁇ 1
- the present inventors used hot concentrated sulfuric acid in place of the aqueous nitric acid solution (concentrated nitric acid) in the dissolution cleaning process (cleaning process), and the third heating.
- concentration nitric acid concentrated nitric acid
- the present inventors have succeeded in developing a support carbon material and a metal catalyst particle-supported carbon material suitable for producing a polymer electrolyte fuel cell excellent in high humidification operation performance, and completed the present invention.
- An adsorption BET specific surface area (m 2 / g, hereinafter sometimes referred to as “S”) is 600 m 2 / g or more and 1500 m 2 / g or less, and is referred to as a D-band obtained from a Raman spectrum.
- the hydrogen content is 0.004 mass% or more and 0.006 mass% or less, and the relative intensity ratio (I D / I G ) determined from the Raman spectrum is 1.4 or more and 2.0 or less.
- the carrier carbon material for a polymer electrolyte fuel cell according to (1) which is characterized in that it is present.
- the nitrogen adsorption BET specific surface area is 800 m 2 / g or more and 1400 m 2 / g or less, and the relative intensity ratio (I D / I G ) determined from the Raman spectrum is 1.4 or more and 2.0 or less.
- the carrier carbon material for a polymer electrolyte fuel cell according to (1) which is characterized in that it is present.
- the hydrogen content is 0.004 mass% or more and 0.006 mass% or less
- the nitrogen adsorption BET specific surface area is 800 m 2 / g or more and 1400 m 2 / g or less
- a relative value obtained from a Raman spectrum The solid carbon fuel cell support carbon material according to (1) above, wherein the mechanical strength ratio (I D / I G ) is 1.4 or more and 2.0 or less.
- the carrier carbon material according to any one of (1) to (4) obtained by the method according to claim 6 is dispersed in a liquid dispersion medium, and platinum is added to the obtained dispersion liquid.
- a metal complex or salt mainly containing a metal and a reducing agent are added, and metal ions are reduced in a liquid phase to precipitate fine metal catalyst particles mainly containing platinum.
- a metal catalyst particle-supported carbon material for polymer electrolyte fuel cells characterized in that the carbon catalyst particle-supported carbon material for polymer electrolyte fuel cells as described in (5) above is produced by supporting the carrier carbon material. Manufacturing method.
- the obtained hydrogen content (H) needs to be 0.004% by mass or more and 0.010% by mass or less, preferably 0.004% by mass or more. It is 0.006 mass% or less.
- this H is less than 0.004% by mass, there are few hydrophilic functional groups present in the support carbon material, which is effective for flooding, but the hydrophilicity of the support carbon material is excessively lost.
- the proton conductivity of the polymer membrane which is achieved because of being in a humid environment, is reduced, and good battery performance cannot be obtained when used in a fuel cell.
- a method capable of analyzing a trace amount of hydrogen may be used.
- an inert gas melting-thermal conductivity method is exemplified.
- a carrier carbon material as a sample is placed in a graphite crucible, heated to a predetermined temperature (for example, 800 ° C. or higher), hydrogen generated is separated from other gases, and a thermal conductivity detector is used. Measure the amount of hydrogen.
- the nitrogen adsorption BET specific surface area (S) needs to be 600 m 2 / g or more and 1500 m 2 / g or less, preferably 800 m 2 / g or more. 1400 m 2 / g or less.
- the support carbon material does not have a surface area necessary for supporting the metal catalyst particles in a highly dispersed state, and the metal catalyst particles supported on the support carbon material are not bonded to each other. The distance between the particles becomes narrow, the diffusibility of the oxidizing gas becomes insufficient, and the battery performance decreases when used for a fuel cell.
- the peak intensity ( ID ) in the range of 1200 to 1400 cm ⁇ 1 which is called D-band obtained from the Raman spectrum, and 1500 which is called G-band.
- the value of the relative intensity ratio (I D / I G , Raman relative intensity ratio) with the peak intensity (I G ) in the range of ⁇ 1700 cm ⁇ 1 needs to be 1.0 or more and 2.0 or less, Preferably they are 1.4 or more and 2.0 or less. If the value of the Raman relative intensity ratio ( ID / IG ) is less than 1.0, the amount of the graphite edge portion is insufficient, and the metal catalyst particles are difficult to be fixed to the support carbon material.
- the Raman relative intensity ratio ( ID / IG ) exceeds 2.0, the amount of the graphite edge portion becomes excessively large and chemically weakened. Under the operating conditions of the solid polymer fuel cell, The carrier carbon material is easily oxidized and consumed, and the durability of the fuel cell is lowered.
- the Raman spectrum may be obtained using a commercially available laser Raman spectrophotometer.
- the reduction in the hydrogen content (H) indicates a reduction in the amount of the hydrophilic functional group that causes flooding, which greatly contributes to the battery performance of the fuel cell, and particularly the battery performance under high humidification conditions. This greatly affects the power generation performance.
- the increase in the nitrogen adsorption BET specific surface area (S) greatly contributes to the cell performance of the fuel cell, and the fluctuation range of the numerical value is large compared to the Raman relative intensity ratio (I D / I G ). This is a precondition for supporting metal catalyst particles in a highly dispersed state on the material.
- the hydrogen content (H) is 0.004 mass% to 0.006 mass%
- the nitrogen adsorption BET specific surface area (S) is 800 m 2 / g to 1400 m 2 / g
- the Raman relative intensity ratio (I D When a fuel cell is produced using a carrier carbon material having / I G ) of 1.4 or more and 2.0 or less, better battery performance can be achieved.
- the hydrophilicity thereof is not excessively lost, so that the proton conductivity of the polymer membrane achieved just because it is in a humid environment is not reduced,
- the occurrence of flooding can be effectively suppressed, and it has a surface area sufficient to highly disperse the metal catalyst particles supported on the support carbon material and an edge portion of graphite, and is supported on the support carbon material.
- the distance between the formed metal catalyst particles is wide, the diffusibility of the oxidizing gas is sufficiently secured, and a fuel cell excellent in battery performance can be produced.
- the metal catalyst particles used are mainly composed of Pt, and the catalyst metal may be Pt alone, Other catalyst metals may be included in addition to this Pt.
- the catalyst metal other than Pt that can be added is one or two selected from Co, Ni, Fe, Pd, Au, Ru, Rh, Ir, and the like added for the purpose of improving the activity of the metal catalyst. Mixtures of seeds or more can be exemplified, and the addition amount of the catalyst metal other than Pt is the ratio of the number of atoms of the catalyst metal other than Pt to the total number of atoms of the catalyst metal in the metal catalyst particles (atomic composition percentage).
- the addition amount of the catalyst metal other than Pt is higher than 50 at%, the ratio of the additive element on the surface of the metal catalyst particles is increased, and the battery performance is deteriorated by being dissolved under the operation of the fuel cell.
- the loading ratio (% by mass) of the metal catalyst particles in the metal catalyst particle-supporting carbon material of the present invention is 10 to 60% by mass, preferably 20 to 50% by mass with respect to the total mass of the metal catalyst particles and the carrier carbon material. It is good to be in the range. This is because when a polymer electrolyte fuel cell is formed using a metal catalyst particle-supported carbon material as a catalyst layer, diffusion of a reducing gas such as hydrogen or an oxidizing gas such as oxygen that is a fuel when generating electricity is essential. Is a condition for improving the diffusion of the reducing gas or oxidizing gas in the catalyst layer.
- the loading ratio of the metal catalyst particles has a correlation with the distance between the metal catalyst particles, and when the amount of the metal catalyst particles in the catalyst layer is equal, if the loading ratio of the metal catalyst particles is low, the catalyst layer As the thickness increases, the diffusibility of the oxidizing gas decreases and the battery performance decreases. However, if the loading ratio of the metal catalyst particles is low, the inter-particle distance between the metal catalyst particles becomes long. Therefore, the metal catalyst particles do not agglomerate. On the contrary, when the loading ratio of the metal catalyst particles is high, the catalyst layer tends to be thin and the diffusion of the oxidizing gas tends to be easy. As the distance between the particles becomes shorter, the metal catalyst particles agglomerate and the surface area of the metal catalyst particles decreases, which causes a problem that the diffused oxidizing gas cannot be efficiently reacted on the surface of the metal catalyst particles.
- the method for producing the carrier carbon material of the present invention is not particularly limited, and for example, it is produced by the following method. That is, acetylene gas is blown into a solution containing a metal or metal salt to produce metal acetylide (acetylide production step).
- the produced metal acetylide is heated at a temperature of 60 ° C. or more and 80 ° C. or less to segregate the metal as metal particles, thereby obtaining a metal particle inclusion intermediate in which the metal particles are included (first heat treatment step).
- the heating time in the first heat treatment step is usually 12 hours or longer, preferably 12 to 24 hours.
- the metal particle inclusion intermediate thus obtained is then heated at a temperature of 160 ° C. or more and 200 ° C. or less to explode the metal particle inclusion intermediate and eject the metal particles from the metal particle inclusion intermediate.
- a carbon material intermediate (second heat treatment step).
- the heating time in this second heat treatment step is usually 10 to 30 minutes, preferably 20 to 30 minutes.
- the carbon material intermediate obtained in the second heat treatment step is then brought into contact with hot concentrated sulfuric acid, and metal particles and other unstable carbon compounds adhering to the ejection surface in the second heat treatment step. Etc. are dissolved and washed to remove the carbon material intermediate, and the hydrogen content (H) of the carbon material intermediate is reduced by the dehydration action of hot concentrated sulfuric acid (cleaning treatment step).
- This carbon material intermediate cleaning treatment using hot concentrated sulfuric acid is performed using concentrated sulfuric acid having a sulfuric acid concentration of 90% by mass or more, preferably 96% by mass or more, more preferably 98% by mass or more, and a temperature of 120 ° C. or more, preferably The heating is performed at 140 ° C. or higher, more preferably 160 ° C.
- hot concentrated sulfuric acid means concentrated sulfuric acid having a temperature (treatment temperature) of concentrated sulfuric acid of 120 ° C. or higher, preferably 140 ° C. or higher, more preferably 160 ° C. or higher. If the sulfuric acid concentration is less than 90% by mass, the dehydrating action of concentrated sulfuric acid is low, and the reactivity with respect to the surface of the carrier carbon material is high. The latter is specifically because H 2 O added when diluting the sulfuric acid concentration reacts with the surface of the support carbon material and the edge portion of graphite tends to increase. Therefore, if the sulfuric acid concentration is less than 90% by mass, it is inappropriate in the present invention.
- a high sulfuric acid concentration is preferable in the present invention, and concentrated sulfuric acid having a sulfuric acid concentration of 100% by mass can be suitably used.
- Concentrated sulfuric acid temperature is less than 120 ° C., the reactivity to the surface of the carrier carbon material is poor, and the surface area tends to decrease, so that it can be dissolved in metal particles or other unstable carbon compounds.
- the temperature of the concentrated sulfuric acid has no particular upper limit and can be applied up to the boiling point of sulfuric acid (290 ° C.).
- this third heat treatment step if the heating temperature is less than 1000 ° C., hydrophilic functional groups such as hydroxyl groups and carboxyl groups remain in the obtained carrier carbon material without being completely removed, and H The value exceeds 0.010, and in a fuel cell manufactured using this carrier carbon material, water generated on the metal catalyst particles supported on the carrier carbon material inhibits diffusion of the oxidizing gas, so-called May cause flooding problems. Conversely, when heated above 2100 ° C., the value of the nitrogen adsorption BET specific surface area (S) may not reach 600 m 2 / g, which is necessary for supporting the metal catalyst particles on the support carbon material in a highly dispersed state. A large surface area cannot be obtained.
- S nitrogen adsorption BET specific surface area
- the method for producing the metal catalyst particle-supporting carbon material for the polymer electrolyte fuel cell of the present invention is not particularly limited, but examples thereof include the following methods. That is, first, the carrier carbon material produced as described above is dispersed in a liquid dispersion medium, and a metal complex or salt containing platinum as a main component and a reducing agent are added to the obtained dispersion. In this method, metal ions are reduced in the liquid phase to deposit fine metal catalyst particles mainly composed of platinum, and the deposited metal catalyst particles are supported on the carrier carbon material.
- the metal catalyst particles supported in a highly dispersed state on the support carbon material have a size of about 1 to 6 nm, and it is mechanical or physical to produce metal catalyst particles of this size with a uniform particle size. This is impossible, and is produced by reducing metal ions chemically. That is, as described above, a metal catalyst particle is generated by reducing a metal complex or metal salt mainly composed of platinum with a reducing agent in a liquid phase.
- applicable reducing agents include sodium borohydride, potassium borohydride, lithium borohydride, hydrazine, aldehydes such as formaldehyde, alcohols such as ethanol and propanol, polyols such as ethylene glycol, and citric acid.
- Carboxylic acids such as oxalic acid and formic acid can be used.
- a compound that covers the catalyst surface such as a colloid agent
- the carrier carbon material should be dispersed in advance in a liquid dispersion medium.
- the control of the particle diameter of the metal catalyst particles to be generated can be optimized by using the reducing agent strength, the concentration of the metal catalyst particles, the concentration of the support carbon material, and the like as control factors.
- the above-mentioned carrier carbon material for a polymer electrolyte fuel cell of the present invention has the above-mentioned characteristics (a), “the carrier carbon material has few hydrophilic functional groups”, and the characteristics (b), “a metal catalyst as the carrier carbon material.
- the support carbon material has a large surface area for supporting the particles in a highly dispersed state, and the characteristic “c” of the support carbon material for fixing the metal catalyst particles in the highly dispersed state on the support carbon material.
- Has a moderate amount of sites '', and the metal catalyst particle-supported carbon material for a polymer electrolyte fuel cell of the present invention is used for a fuel cell operated under highly humidified conditions. Demonstrate battery performance.
- Patent Document 2 by optimizing the structure of the catalyst layer so that gas diffusion is good, high battery performance is exhibited even under humid conditions, but the carrier carbon material of the present invention is used. Even when used, by optimizing the structure of the catalyst layer so that gas diffusion is good as in the case of Patent Document 2, high battery performance can be exhibited even under humid conditions.
- the carrier carbon material and the metal catalyst particle-supported carbon material for the polymer electrolyte fuel cell of the present invention are used in a fuel cell as compared with the conventional commercially available carrier carbon material and metal catalyst particle-supported carbon material, High battery performance under high humidification conditions.
- FIG. 1 shows the treatment temperature and hydrogen content in the third heat treatment step for Examples 1 to 27 of the present invention, Comparative Example 13 of Patent Document 3, and Comparative Example 37 of Patent Document 2. It is a graph which shows the result of having investigated the relationship with quantity (H).
- FIG. 2 shows the treatment temperature and nitrogen adsorption in the third heat treatment step in the case of Examples 1 to 27 of the present invention, the case of Comparative Example 13 of Patent Document 3, and the case of Comparative Example 37 of Patent Document 2. It is a graph which shows the result of having investigated the relationship with a BET specific surface area (S).
- FIG. 3 shows the processing temperature and Raman relative values in the third heat treatment step for Examples 1 to 27 of the present invention, Comparative Example 13 of Patent Document 3, and Comparative Example 37 of Patent Document 2. It is a graph which shows the result of having investigated the relationship with intensity ratio ( ID / IG ).
- FIG. 4 is a TEM image showing the platinum catalyst particle-supporting carbon material (I D / I G : 1.7) of Example 4.
- FIG. 5 is a TEM image showing the platinum catalyst particle-supporting carbon material (I D / I G : 0.74) of Comparative Example 34.
- Second heat treatment step The silver particle-containing intermediate obtained in the first heat treatment step is continuously raised to a temperature of 160 to 200 ° C. without removing it from the vacuum heating vessel. The mixture was heated at this temperature for 20 minutes, and silver particles were ejected from the silver particle inclusion intermediate by explosion to obtain a carbon material intermediate.
- Comparative Examples 28 to 34 In Comparative Examples 28 to 34, a commercially available carrier carbon material (trade name: EC600JD manufactured by Lion Co., Ltd.) was used, and a third heat treatment was performed at the treatment temperature shown in Table 2. A carrier carbon material was obtained.
- a commercially available carrier carbon material (trade name: EC600JD manufactured by Lion Co., Ltd.) was used, and a third heat treatment was performed at the treatment temperature shown in Table 2. A carrier carbon material was obtained.
- Comparative Examples 34 to 36 In Comparative Example 34, a commercially available carrier carbon material (trade name: Denka Black FX-35 manufactured by Denki Kagaku Kogyo Co., Ltd.) was used as the carrier carbon material of Comparative Example 34 as it was. In Comparative Example 35, a commercially available carrier carbon material (trade name: YP50F, manufactured by Kuraray Chemical Co., Ltd.) was used as the carrier carbon material of Comparative Example 35 as it was. In Comparative Example 36, a commercially available carrier carbon material (trade name: EC600JD manufactured by Lion Corporation) is used as it is as the carrier carbon material of Comparative Example 36, and corresponds to the carrier carbon material of Patent Document 2. It is.
- the hydrogen content (H) is as follows. The measurement was performed as described above. The measurement was performed using a gas analyzer (manufactured by RECO, model RH402) according to an inert gas melting thermal conductivity method. First, about 1 g of the sample carrier carbon material is measured, heated to 800 ° C. with a graphite crucible, the amount of hydrogen generated at that time is measured, and the hydrogen content (H) value ( mass%) was calculated.
- FIG. 1 shows the processing temperature in the third heat treatment step for Examples 1 to 27 of the present invention, Comparative Example 13 of Patent Document 3, and Comparative Example 37 of Patent Document 2.
- H hydrogen content
- the carrier carbon materials of Examples 1 to 27 of the present invention all have a hydrogen content (H) value range of “0.004 to 0.010 mass. %
- the temperature of concentrated sulfuric acid (treatment temperature) was less than 120 ° C.
- the nitrogen adsorption BET specific surface area (S) is as follows. It was measured. Measurement is made by measuring approximately 50 mg of the sample carrier carbon material, vacuum-drying it at 90 ° C., and using the resulting sample after drying using an automatic specific surface area measurement device (BELSORP36, manufactured by Nippon Bell) and nitrogen gas. The specific surface area was determined by a one-point method based on the BET method.
- Example 1 to 27 are shown in Table 1, and the results of Comparative Examples 1 to 37 are shown in Table 2. Further, FIG. 2 shows the processing temperature in the third heat treatment step in Examples 1 to 27 of the present invention, Comparative Example 13 in Patent Document 3, and Comparative Example 37 in Patent Document 2. The result of having investigated the relationship with nitrogen adsorption BET specific surface area (S) is shown. As is apparent from the results shown in Tables 1 and 2 and FIG.
- the carrier carbon materials of Examples 1 to 27 of the present invention are all in the range of the value of the nitrogen adsorption BET specific surface area (S) “600 to 1500 m 2 /
- the third heat treatment was performed at a treatment temperature of 2200 ° C.
- the third heat treatment was performed at a processing temperature of 1700 to 2000 ° C. using a commercially available product EC600JD.
- this value range of the nitrogen adsorption BET specific surface area (S) “600 to 1500 m 2 / g” was not satisfied.
- Measurement is made by measuring approximately 3 mg of the sample carbon material, using a laser Raman spectrophotometer (NRS-7100, manufactured by JASCO Corporation), excitation laser 532 nm, laser power 100 mW (sample irradiation power: 0.1 mW) , Microscopic arrangement: Backscattering, slit: 100 ⁇ m ⁇ 100 ⁇ m, objective lens: ⁇ 100, spot diameter: 1 ⁇ m, exposure time: 30 sec, observation wave number: 3200 to 750 cm ⁇ 1 , integration number: carried out under measurement conditions of 2 times, From the Raman spectrum obtained by the measurement, a peak intensity ( ID ) in the range of 1200 to 1400 cm ⁇ 1 called D-band and a peak intensity (I G ) in the range of 1500 to 1700 cm ⁇ 1 called G-band. The relative intensity ratio (I D / I G ) was calculated. The measurement was performed three times, and the average value of the three times was used as measurement data.
- NPS-7100 laser Ram
- FIG. 3 shows the processing temperature in the third heat treatment step in Examples 1 to 27 of the present invention, Comparative Example 13 in Patent Document 3, and Comparative Example 37 in Patent Document 2.
- ID / IG Raman relative intensity ratio
- FIG. 4 shows the results of Example 4
- FIG. 5 shows the results of Comparative Example 34. Accordingly, when platinum catalyst particles are supported on a carrier carbon material having an I D / I G of less than 1.0 (Comparative Example 34), there are few sites where the platinum catalyst particles are fixed, and some platinum catalysts are used. There are areas where the particles are not fixed.
- the catalyst layer slurries of Examples 1 to 27 and Comparative Examples 1 to 37 thus obtained were respectively applied to one side of a Teflon (registered trademark) sheet by a spray method, followed by 10 minutes in an argon stream at 80 ° C. And dried in an argon stream at 120 ° C. for 1 hour to obtain a catalyst layer for a polymer electrolyte fuel cell.
- Each catalyst layer is prepared by setting the conditions such as spraying so that the platinum usage is 0.20 mg / cm 2, and the platinum usage is the Teflon (registered trademark) sheet before and after spray application. The dry mass was measured and calculated from the difference.
- electrolyte membranes each having a size of 2.5 cm square were cut out from the obtained catalyst layers for the polymer electrolyte fuel cells of Examples 1 to 27 and Comparative Examples 1 to 37, and the catalyst layers were separated from the electrolyte membranes.
- An electrolyte membrane Nafion 112 is sandwiched between two electrodes of the same type so that they come into contact with each other, hot pressed for 10 minutes at 130 ° C. and 90 kg / cm 2 , then cooled to room temperature, and then a Teflon (registered trademark) sheet. Only the catalyst layer was carefully peeled off, and the anode and cathode catalyst layers were fixed to the Nafion membrane.
- each MEA was incorporated into a fuel cell, and a fuel cell measuring device was installed.
- the fuel cell performance was evaluated by the following procedure. At this time, air was supplied to the cathode, pure hydrogen was supplied to the anode, and the amount of gas necessary for power generation of 1000 mA / cm 2 was set to 100%, so that the utilization rates were 40% and 70%, respectively. . At this time, the gas pressure was 0.1 MPa, and the cell temperature was 80 ° C.
- Examples 28 to 39 and Comparative Examples 38 to 46 Each of the above except that the following operations were performed when preparing the platinum catalyst particle-supporting carbon material using the four types of support carbon materials obtained in Example 4 and Comparative Examples 1, 7, and 15. In the same manner as in Examples and Comparative Examples, MEA was prepared, and this MEA was incorporated into a fuel cell to evaluate battery performance.
- platinum catalyst particle-supporting carbon material sodium borohydride having a strong reducing power is used as a reducing agent, and an aqueous solution obtained by dissolving chloroplatinic acid and a catalyst metal chloride other than platinum is used. After adding a carrier carbon material and sufficiently dispersing with an ultrasonic disperser to prepare a dispersion, a large excess of an aqueous solution of sodium borohydride was poured into the dispersion at a temperature of 60 ° C. with stirring, and the solution was chlorinated.
- Platinum catalyst particle-carrying carbon materials having metal catalyst particle loadings and compositions shown in Table 3 were prepared by reducing platinum acid and chlorides of catalyst metals other than platinum.
- Example 34 to 39 and Comparative Examples 41 to 46 in order to increase the degree of alloying, the dried catalyst was heat-treated in an inert atmosphere at 800 ° C. for 5 minutes. At that time, in order to suppress the coarsening of the particles, it was heated as quickly as possible, and after the heat treatment, it was cooled rapidly. The results are shown in Table 3.
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Abstract
Description
(a)担体炭素材料に親水性官能基が少ないこと。
(b)担体炭素材料に金属触媒粒子を高分散状態で担持させるために、担体炭素材料が大きな表面積を有すること。
(c)担体炭素材料に前記金属触媒粒子を高分散状態に固定するために、担体炭素材料が適度な量のサイトを有すること。
すなわち、金属又は金属塩を含む溶液中にアセチレンガスを吹き込み、金属アセチリドを生成させる工程(アセチリド生成工程)と、前記金属アセチリドを60~80℃の温度で12時間以上加熱し、金属を金属粒子として偏析させ内包させた金属粒子内包中間体を作製する第1の加熱処理工程と、前記金属粒子内包中間体を160~200℃の温度で10~30分間加熱し、前記金属粒子内包中間体から金属粒子を噴出させた炭素材料中間体を得る第2の加熱処理工程と、前記第2の加熱処理工程で得られた炭素材料中間体を硝酸水溶液、特に濃硝酸と接触させ、噴出した金属粒子やその他の不安定な炭素化合物を溶解除去して炭素材料中間体を清浄化する溶解洗浄処理工程(洗浄処理工程)と、前記溶解洗浄処理工程で清浄化された炭素材料中間体を真空中、不活性ガス雰囲気中、又は空気雰囲気中、180~200℃の温度で24~48時間加熱し、担体炭素材料を得る第3の加熱処理工程とを有する固体高分子形燃料電池用の担体炭素材料の製造方法である。
(1) 多孔質炭素材料であって、水素含有量(質量%、以下「H」と表記することがある。)が0.004質量%以上0.010質量%以下の範囲にあって、窒素吸着BET比表面積(m2/g、以下「S」と表記することがある。)が600m2/g以上1500m2/g以下であり、且つ、ラマン分光スペクトルから得られるD-バンドと呼ばれる1200~1400cm-1の範囲のピーク強度(ID)と、G-バンドと呼ばれる1500~1700cm-1の範囲のピーク強度(IG)との相対的強度比(ID/IG、以下「ラマン相対強度比」と略称することがある。)が1.0以上2.0以下であることを特徴とする固体高分子形燃料電池用担体炭素材料。
(3) 前記窒素吸着BET比表面積が800m2/g以上1400m2/g以下であって、ラマン分光スペクトルより求まる相対的強度比(ID/IG)が1.4以上2.0以下であることを特徴とする前記(1)に記載の固体高分子形燃料電池用担体炭素材料。
(5) 前記(1)~(4)のいずれかに記載の固体高分子形燃料電池用担体炭素材料に、Pt単独、又は、Ptを主成分とする金属触媒粒子が担持されていることを特徴とする固体高分子形燃料電池用金属触媒粒子担持炭素材料。
すなわち、金属又は金属塩を含む溶液中にアセチレンガスを吹き込み、金属アセチリドを生成させる(アセチリド生成工程)。
すなわち、先ず、以上のようにして製造された担体炭素材料を液体分散媒中に分散させ、得られた分散液中に、白金を主成分とした金属の錯体又は塩と還元剤とを添加し、液相で金属イオンを還元して白金を主成分とする微細な金属触媒粒子を析出させると共に、この析出した金属触媒粒子を前記担体炭素材料に担持させる方法である。
1.担体炭素材料の製造
(1) アセチリド生成工程
以下の実施例及び比較例では、担体炭素材料を製造するための前駆体である金属アセチリドの金属として、銀を選択した。
最初に、硝酸銀を1.1モル%の濃度で含むアンモニア水溶液(NH3濃度:1.9質量%)をフラスコに用意し、このフラスコ内の空気を不活性ガス(アルゴンや乾燥窒素等)で置換して酸素を除去した後、撹拌下に上記硝酸銀のアンモニア水溶液150mLに対してアセチレンガスを25mL/min.の流速で約4分間吹き付け、アンモニア水溶液中に銀アセチリドの固形物を沈殿させた。次いで、前記沈殿物をメンブレンフィルターで濾過し、得られた沈殿物をメタノールで洗浄し、更に洗浄後に若干のメタノールを加えてこの沈殿物中にメタノールを含浸させた。
次いで、前記メタノールを含浸した状態の沈殿物を直径6mm程度の試験管にそれぞれ50mgずつ小分けして入れ、これを真空加熱容器に入れて60~80℃の温度で12時間加熱し、銀粒子内包中間体を調製した。
上記第1の加熱処理工程で得られた銀粒子内包中間体を真空加熱容器内から取り出すことなく、そのまま真空中で連続して160~200℃の温度まで昇温させ、この温度で20分間加熱し、爆発により銀粒子内包中間体から銀粒子を噴出させ、炭素材料中間体を得た。
上記第2の加熱処理工程で得られた銀粒子噴出後の炭素材料中間体について、表1及び表2に示すように、96質量%の濃硫酸を200℃で1時間接触させて洗浄する熱濃硫酸洗浄処理、又は、濃硝酸に1時間接触させて洗浄する濃硝酸洗浄処理を実施し、炭素材料中間体の表面に残存した銀粒子やその他不安定な炭素化合物を除去し清浄化した。
上記洗浄処理工程で清浄化した炭素材料中間体について、不活性雰囲気中において表1及び表2に示す処理温度で2時間加熱し、実施例1~27及び比較例1~27の担体炭素材料を得た。なお、比較例13は特許文献3の担体炭素材料に相当するものである。
比較例28~34においては、市販品の担体炭素材料(ライオン(株)社製商品名:EC600JD)を用い、表2に示す処理温度で第3の加熱処理を施し、比較例28~34の担体炭素材料とした。
比較例34においては、市販品の担体炭素材料(電気化学工業(株)社製商品名:デンカブラックFX-35)をそのまま比較例34の担体炭素材料とした。
比較例35においては、市販品の担体炭素材料(クラレケミカル(株)社製商品名:YP50F)をそのまま比較例35の担体炭素材料とした。
比較例36においては、市販品の担体炭素材料(ライオン(株)社製商品名:EC600JD)をそのまま比較例36の担体炭素材料としたものであり、特許文献2の担体炭素材料に相当するものである。
以上のようにして調製された実施例1~27及び比較例1~37の担体炭素材料について、その水素含有量(H)を以下のようにして測定した。
測定はガス分析装置(RECO製、RH402型)を用い、不活性ガス融解熱伝導度法に従って行った。先ず、試料の担体炭素材料を約1g測り採り、これを黒鉛るつぼで800℃に加熱し、その際に発生した水素量を測定し、測定された水素量から水素含有量(H)の値(mass%)を算出した。
表1及び表2と図1に示す結果から明らかなように、本発明の実施例1~27の担体炭素材料が何れも水素含有量(H)の値の範囲「0.004~0.010mass%」を満たしているのに対し、濃硫酸を用いて洗浄処理を行った比較例1~12のうち、濃硫酸の温度(処理温度)が、120℃未満の比較例1及び3の場合、第3の加熱処理時の処理温度が2200℃の比較例4~6の場合、及び第3の加熱処理時の処理温度が900℃又は800℃の比較例7~10の場合や、濃硝酸を用いて洗浄処理を行った比較例13、15~27の場合や、濃硫酸を用いて洗浄処理を行った比較例14の場合や、更には、市販品を用いた場合のうち、市販品EC600JDに対して1700℃の処理温度で第3の加熱処理を行った比較例32以外の場合には、水素含有量(H)の値の範囲「0.004~0.010mass%」を満足しなかった。
上記実施例1~27及び比較例1~37の担体炭素材料について、その窒素吸着BET比表面積(S)を以下のようにして測定した。
測定は、試料の担体炭素材料を約50mg測り採り、これを90℃で真空乾燥し、得られた乾燥後の試料について、自動比表面積測定装置(日本ベル製、BELSORP36)を使用し、窒素ガスを用いたガス吸着法にて測定し、BET法に基づく1点法にて比表面積を決定した。
表1及び表2と図2に示す結果から明らかなように、本発明の実施例1~27の担体炭素材料が何れも窒素吸着BET比表面積(S)の値の範囲「600~1500m2/g」を満たしているのに対し、濃硫酸の温度(処理温度)が、120℃未満の比較例1~3の場合、第3の加熱処理を2200℃の処理温度で行った比較例5、6の場合、濃硝酸を用いて洗浄処理を行った比較例13の場合、市販品EC600JDを用いて1700~2000℃の処理温度で第3の加熱処理を行った比較例32~34 の場合、及び、市販品デンカブラックFX-35を用いた比較例35の場合には、この窒素吸着BET比表面積(S)の値の範囲「600~1500m2/g」を満足しなかった。
上記実施例1~27及び比較例1~37の担体炭素材料について、そのラマン相対強度比(ID/IG)を以下のようにして測定した。
測定は、試料の担体炭素材料を約3mg測り採り、レーザラマン分光光度計(日本分光(株)製、NRS-7100型)を用い、励起レーザー532nm、レーザーパワー100mW(試料照射パワー:0.1mW)、顕微配置:Backscattering、スリット:100μm×100μm、対物レンズ:×100、スポット径:1μm、露光時間:30sec、観測波数:3200~750cm-1、積算回数:2回の測定条件で実施し、各測定で得られたラマンスペクトルからD-バンドと呼ばれる1200~1400cm-1の範囲のピーク強度(ID)と、G-バンドと呼ばれる1500~1700cm-1の範囲のピーク強度(IG)との相対的強度比(ID/IG)を算出した。測定は3回実施し、その3回の平均値を測定データとした。
表1及び表2と図3に示す結果から明らかなように、本発明の実施例1~27の担体炭素材料が何れもラマン相対強度比(ID/IG)の値の範囲「1.0~2.0」を満たしているのに対し、第3の加熱処理を2200℃の処理温度で行った比較例4の場合、硫酸濃度が90質量%未満の比較例11及び12の場合、市販品EC600JDを用いて1800℃又は2000℃の処理温度で第3の加熱処理を行った比較例33及び34の場合、及び、市販品YP50Fを用いた比較例36の場合には、このラマン相対強度比(ID/IG)の値の範囲「1.0~2.0」を満足しなかった。
上記各実施例1~27及び比較例1~37の担体炭素材料を蒸留水中に分散させ、この分散液にホルムアルデヒドを加え、40℃に設定したウォーターバスにセットし、分散液の温度がバスと同じ40℃になってから、撹拌下にこの分散液中にジニトロジアミンPt錯体硝酸水溶液をゆっくりと注ぎ入れた。その後、約2時間撹拌を続けた後、濾過し、得られた固形物の洗浄を行った。このようにして得られた固形物を90℃で真空乾燥した後、乳鉢で粉砕し、次いで水素雰囲気中250℃で1時間熱処理をして各実施例1~27及び比較例1~37の白金触媒粒子担持炭素材料を作製した。なお、前記白金触媒粒子担持炭素材料の白金触媒粒子の担持率は白金触媒粒子と担体炭素材料の合計質量に対して40質量%になるように調製した。
上記実施例4(ID/IG:1.7)及び比較例34(ID/IG:0.74)で調製された白金触媒粒子担持炭素材料を1mg測り採り、エタノール中に分散させた。得られた分散液を銅メッシュグリッド上に滴下し、1晩真空乾燥させ、透過型電子顕微鏡(FEI製、TECNAI)を用い、加速電圧200kV、観察視野2μm×2μmの条件で観察し、代表点として0.2μm×0.2μmの領域のTEM像を撮影した。
上記各実施例1~27及び比較例1~37の白金触媒粒子担持炭素材料を用い、また、アイオノマー溶液として5%-ナフィオン溶液(デュポン製、DE521)を用い、アルゴン気流中でこれら白金触媒粒子担持炭素材料と5%-ナフィオン溶液とを白金触媒粒子担持炭素材料の質量に対してナフィオン固形分の質量が1.2倍になるように配合し、軽く撹拌した後、超音波で白金触媒粒子担持炭素材料を粉砕し、得られた分散液中に白金触媒粒子担持炭素材料とナフィオンの合計の固形分濃度が2質量%となるように撹拌下に酢酸ブチルを加え、各実施例1~27及び比較例1~37の触媒層スラリーを作製した。
以上のようにして作製した各実施例1~27及び比較例1~37のMEAについて、各MEAを燃料電池セルに組み込み、燃料電池測定装置を用いて次の手順で燃料電池の性能を評価した。この際に、カソードには空気を、また、アノードには純水素を、1000mA/cm2の発電に必要なガス量を100%として、利用率がそれぞれ40%と70%となるように供給した。また、この際に、ガス圧は0.1MPaとし、また、セル温度は80℃とした。
実施例1~27の結果を表1に示すと共に比較例1~37の結果を表2に示す。
実施例4と、比較例1、7及び15とで得られた4種の担体炭素材料を使用し、白金触媒粒子担持炭素材料を調製する際に下記の操作を行ったこと以外は、上記各実施例及び比較例の場合と同様にして、MEAを調製し、また、このMEAを燃料電池セルに組み込んで電池性能の評価を行った。
結果を表3に示す。
Claims (7)
- 多孔質炭素材料であって、水素含有量が0.004質量%以上0.010質量%以下の範囲にあって、窒素吸着BET比表面積が600m2/g以上1500m2/g以下であり、且つ、ラマン分光スペクトルから得られるD-バンドと呼ばれる1200~1400cm-1の範囲のピーク強度(ID)と、G-バンドと呼ばれる1500~1700cm-1の範囲のピーク強度(IG)との相対的強度比(ID/IG)が1.0以上2.0以下であることを特徴とする固体高分子形燃料電池用担体炭素材料。
- 前記水素含有量が0.004質量%以上0.006質量%以下であって、ラマン分光スペクトルより求まる相対的強度比(ID/IG)が1.4以上2.0以下であることを特徴とする請求項1に記載の固体高分子形燃料電池用担体炭素材料。
- 前記窒素吸着BET比表面積が800m2/g以上1400m2/g以下であって、ラマン分光スペクトルより求まる相対的強度比(ID/IG)が1.4以上2.0以下であることを特徴とする請求項1に記載の固体高分子形燃料電池用担体炭素材料。
- 前記水素含有量が0.004質量%以上0.006質量%以下であり、窒素吸着BET比表面積が800m2/g以上1400m2/g以下であり、且つ、ラマン分光スペクトルより求まる相対的強度比(ID/IG)が1.4以上2.0以下であることを特徴とする請求項1に記載の固体高分子形燃料電池用担体炭素材料。
- 前記請求項1~4のいずれかに記載の固体高分子形燃料電池用担体炭素材料に、Pt単独、又は、Ptを主成分とする金属触媒粒子が担持されていることを特徴とする固体高分子形燃料電池用金属触媒粒子担持炭素材料。
- 前記請求項1~4のいずれかに記載の固体高分子形燃料電池用担体炭素材料を製造するための方法であり、
金属又は金属塩を含む溶液中にアセチレンガスを吹き込み、金属アセチリドを生成させるアセチリド生成工程と、
前記金属アセチリドを60℃以上80℃以下の温度で加熱し、金属粒子が内包された金属粒子内包中間体を作製する第1の加熱処理工程と、
前記金属粒子内包中間体を160℃以上200℃以下の温度で加熱し、前記金属粒子内包中間体から金属粒子を噴出させ、炭素材料中間体を得る第2の加熱処理工程と、
前記第2の加熱処理工程で得られた炭素材料中間体を熱濃硫酸と接触させ、炭素材料中間体を清浄化する洗浄処理工程と、
前記洗浄処理工程で清浄化された炭素材料中間体を真空中、不活性ガス雰囲気中、又は空気雰囲気中で、1000℃以上2100℃以下の温度に加熱して、担体炭素材料を得る第3の加熱処理工程とを有することを特徴とする固体高分子形燃料電池用担体炭素材料の製造方法。 - 前記請求項6に記載の方法で得られた前記請求項1~4のいずれかに記載の担体炭素材料を液体分散媒中に分散させ、得られた分散液中に、白金を主成分とする金属の錯体又は塩と還元剤とを添加し、液相で金属イオンを還元して白金を主成分とする微細な金属触媒粒子を析出させると共に、この析出した金属触媒粒子を前記担体炭素材料に担持させ、前記請求項5に記載の固体高分子形燃料電池用金属触媒粒子担持炭素材料を製造することを特徴とする固体高分子形燃料電池用金属触媒粒子担持炭素材料の製造方法。
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Also Published As
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US20160329571A1 (en) | 2016-11-10 |
JP6203286B2 (ja) | 2017-09-27 |
CA2932709A1 (en) | 2015-06-18 |
KR20160083909A (ko) | 2016-07-12 |
CN105814723A (zh) | 2016-07-27 |
JPWO2015088025A1 (ja) | 2017-03-16 |
KR101804714B1 (ko) | 2017-12-05 |
EP3082184A1 (en) | 2016-10-19 |
US10003085B2 (en) | 2018-06-19 |
CN105814723B (zh) | 2018-09-11 |
EP3082184B1 (en) | 2018-11-28 |
EP3082184A4 (en) | 2017-08-23 |
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