WO2012053638A1 - 固体高分子型燃料電池用電極触媒 - Google Patents
固体高分子型燃料電池用電極触媒 Download PDFInfo
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- WO2012053638A1 WO2012053638A1 PCT/JP2011/074300 JP2011074300W WO2012053638A1 WO 2012053638 A1 WO2012053638 A1 WO 2012053638A1 JP 2011074300 W JP2011074300 W JP 2011074300W WO 2012053638 A1 WO2012053638 A1 WO 2012053638A1
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- 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
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- 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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- 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
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- 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
- H01M4/9041—Metals or alloys
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- 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
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
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- 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
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- 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
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- 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
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- 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
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- 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
- H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
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- 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 an electrode catalyst used for a polymer electrolyte fuel cell (PEFC), a membrane electrode assembly using the same, and a polymer electrolyte fuel cell.
- PEFC polymer electrolyte fuel cell
- Solid polymer fuel cells using proton-conducting solid polymer membranes operate at a lower temperature than other types of fuel cells, such as solid oxide fuel cells and molten carbonate fuel cells, and are stationary. It is expected as a power source for automobiles and a power source for moving bodies such as automobiles, and its practical use has also begun.
- the average particle diameter of the catalyst metal is made larger than the average pore diameter of the fine pores of the conductive support so that the catalyst particles are placed in the fine pores of the support.
- the wasteful catalyst metal that does not come into contact with the electrolyte polymer is reduced, and the utilization efficiency of the expensive catalyst metal is increased.
- the present invention has been made paying attention to the above-described problems in the polymer electrolyte fuel cell, and the object of the present invention is to increase the reaction active area of the catalyst, increase the utilization efficiency of the catalyst, An object of the present invention is to provide a solid polymer fuel cell electrode catalyst capable of reducing the amount of expensive noble metal catalyst used. It is another object of the present invention to provide a membrane electrode assembly using such an electrode catalyst, and further a polymer electrolyte fuel cell.
- the present inventor repeats various studies, and when the solid proton conductive material (electrolyte polymer) comes into contact with the catalyst surface, the solid proton conductive material becomes a reactive substance such as oxygen. In comparison with this, it was noted that the reaction active area on the catalyst surface decreased because it was more easily adsorbed on the catalyst surface.
- the above object can be achieved by interposing a liquid proton conductive material typified by water between the solid proton conductive material and the catalyst while minimizing the direct contact between the solid proton conductive material and the catalyst. As a result, the present invention has been completed.
- the present invention is based on the above knowledge, and the electrode catalyst for a polymer electrolyte fuel cell of the present invention includes a catalyst, a solid proton conductive material, and a state in which these catalysts and the solid proton conductive material can conduct protons.
- a liquid conductive material holding part for holding a liquid proton conductive material connected to the catalyst, and a contact area of the catalyst with the solid proton conductive material is an area exposed to the liquid conductive material holding part of the catalyst. It is characterized by being smaller than.
- the reaction active area of the catalyst Is ensured and the utilization efficiency of the catalyst is improved, so that the amount of the catalyst used can be reduced while maintaining the power generation performance.
- the electrode catalyst for a polymer electrolyte fuel cell of the present invention comprises a liquid proton conductive material having a catalyst and a solid proton conductive material, and connecting the catalyst and the solid proton conductive material in a proton conductive state.
- a liquid conducting material holding part for holding is provided between the two.
- the contact area of the catalyst with the solid proton conductive material is smaller than the area exposed to the liquid conductive material holding portion of the catalyst, and more preferably, the catalyst and the solid proton conductive material are in a non-contact state. ing.
- solid proton conduction has a strong adsorption force on the catalyst surface and tends to cover the surface. It is necessary to secure a proton transport path while avoiding direct contact between the material and the catalyst.
- a liquid conductive material holding part is provided between the catalyst and the solid proton conductive material, and the liquid proton conductive material is introduced into the holding part, whereby a liquid is provided between the catalyst and the solid proton conductive material. A proton transport route through the proton conducting material is secured.
- the catalyst used for the electrode catalyst for the polymer electrolyte fuel cell of the present invention is not particularly limited, and various conventionally known metals represented by Pt (platinum) such as Pt, Ir (indium), Co (cobalt). ), Ni (nickel), Fe (iron), Cu (copper), Ru (ruthenium), Ag (silver), Pd (palladium), etc. can be used alone or in any combination.
- Pt platinum
- Ir indium
- Co cobalt
- Ni nickel
- Fe iron
- Cu copper
- Ru ruthenium
- Ag silver
- Pd palladium
- the shape and size of such a catalyst metal are not particularly limited, and those having the same shape and size as known catalyst metals can be used.
- the shape may be granular, scaly, layered, etc. As a typical example, in the case of granular, it is preferable to be in the range of about 1 to 30 nm, more preferably 2 to 5 nm.
- the solid proton conductive material used for the electrode catalyst of the present invention is not particularly limited, and various conventionally known materials can be used.
- the solid proton conductive material used in the present invention is roughly classified into a fluorine-based electrolyte containing fluorine atoms in the whole or a part of the polymer skeleton and a hydrocarbon electrolyte containing no fluorine atoms in the polymer skeleton.
- fluorine-based electrolytes include perfluorocarbon sulfonic acid polymers such as Nafion (registered trademark, manufactured by DuPont), Aciplex (registered trademark, manufactured by Asahi Kasei Corporation), and Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.).
- perfluorocarbon sulfonic acid polymers such as Nafion (registered trademark, manufactured by DuPont), Aciplex (registered trademark, manufactured by Asahi Kasei Corporation), and Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.).
- a suitable example is doperfluorocarbon sulfonic acid polymer.
- Such a fluorine-based electrolyte is generally excellent in durability and mechanical strength.
- hydrocarbon electrolyte examples include polysulfone sulfonic acid, polyaryl ether ketone sulfonic acid, polybenzimidazole alkyl sulfonic acid, polybenzimidazole alkyl phosphonic acid, polystyrene sulfonic acid, polyether ether ketone sulfonic acid, polyphenyl sulfone.
- An acid etc. are mentioned as a suitable example.
- Proton conductivity is important as a solid proton conductive material.
- EW Equivalent Weight
- the entire catalyst layer including proton conduction in the liquid conductive material holding part that separates the catalyst component and the solid ion conductive material is used. Since ionic conductivity is lowered, it is desirable that the EW is low.
- the EW of the solid proton conductive material is 1200 g / eq. The following is preferable, and 700 g / eq. The following is more preferable.
- EW Equivalent Weight
- the liquid conductive material holding part is formed between the catalyst and the solid proton conductive material, holds the liquid proton conductive material, and passes through the liquid proton conductive material. It means a space that connects the catalyst and the solid proton conductive material in a state capable of proton conduction.
- the liquid proton conductive material described above has ionic conductivity and exhibits a function of forming a proton transport path while being held in a liquid conductive material holding portion provided between the catalyst and the solid proton conductive material.
- a liquid conductive material holding portion provided between the catalyst and the solid proton conductive material.
- Specific examples include water, protic ionic liquid, aqueous perchloric acid solution, aqueous nitric acid solution, aqueous formic acid solution, and aqueous acetic acid solution.
- water when water is used as the liquid proton conductive material, water may be introduced into the liquid conductive material holding unit by moistening the catalyst layer with a small amount of liquid water or humidified gas before starting power generation. it can. Moreover, the produced water produced by the electrochemical reaction during the operation of the fuel cell can also be used. Therefore, in the state where the operation of the fuel cell is started, it is not always necessary to hold the liquid proton conductive material in the liquid conductive material holding portion of the electrode catalyst.
- an ionic liquid other than water As the liquid proton conducting material, it is desirable to disperse the ionic liquid, the solid proton conducting material, and the catalyst in the solution when preparing the catalyst ink.
- An ionic liquid can also be added when applied to the catalyst layer substrate.
- the catalyst can be supported on a conductive carrier made of various materials as required.
- the conductive carrier include a conductive porous carrier.
- the hole portion of the conductive porous carrier can be used as the liquid conductive material holding portion.
- Such a conductive porous carrier is not particularly limited as long as the liquid conductor holding portion can be formed inside or outside the carrier.
- activated carbon carbon black (Ketjen black, oil furnace black, channel black) Carbon black such as lamp black, thermal black, and acetylene black), porous metals such as Sn (tin) and Ti (titanium), and conductive metal oxides.
- carbon black Ketjen black, oil furnace black, channel black
- Carbon black such as lamp black, thermal black, and acetylene black
- porous metals such as Sn (tin) and Ti (titanium)
- ketjen black since it is easy to form a liquid conductor holding
- the conductive carrier include a non-porous conductive carrier, a nonwoven fabric made of carbon fibers constituting a gas diffusion layer, carbon paper, and carbon cloth.
- the catalyst can be supported on these non-porous conductive carriers, or directly attached to a non-woven fabric made of carbon fibers, carbon paper, carbon cloth, etc. constituting the gas diffusion layer of the membrane electrode assembly. It is.
- the surface distance between the catalyst and the solid proton conductive material is 0.28 nm or more, which is the diameter of oxygen ions constituting water molecules. Is desirable.
- water liquid proton conductive material
- the solid proton conductive material liquid conductive material holding part
- the surface distance between the catalyst and the solid proton conductive material is less than 30 nm. It is desirable.
- the total area of the catalyst in contact with the solid proton conductive material is the total area of the catalyst exposed to the liquid conductive material holding part. It is smaller than that.
- the comparison of these areas is, for example, the capacity of the electric double layer formed at the catalyst-solid proton conductive material interface and the catalyst-liquid proton conductive material interface with the liquid conductive material holding portion filled with the liquid proton conductive material. This can be done by determining the magnitude relationship. In other words, since the electric double layer capacity is proportional to the area of the electrochemically effective interface, the electric double layer capacity formed at the catalyst-solid proton conductive material interface is formed at the catalyst-liquid proton conductive material interface. If the electric double layer capacity is smaller, the contact area of the catalyst with the solid proton conductive material is smaller than the exposed area of the liquid conductive material holding part.
- the measurement method of the electric double layer capacity formed at the catalyst-solid proton conducting material interface and the catalyst-liquid proton conducting material interface in other words, between the catalyst-solid proton conducting material and between the catalyst-liquid proton conducting material.
- a method for determining the magnitude relationship between the contact areas of the catalyst that is, the magnitude relation between the contact area of the catalyst with the solid proton conducting material and the area exposed to the liquid conducting material holding part will be described.
- Electric double layer capacitor since that is directly proportional to the area of the electrochemically active surface, Cdl C-S (catalytic - electric double layer capacity of the solid proton conducting material interface) and Cdl C-L (catalyst If the electric double layer capacity at the interface of the liquid proton conducting material is determined, the relationship between the contact area of the catalyst with the solid proton conducting material and the liquid proton conducting material can be obtained.
- the contribution of the four types of interfaces to the electric double layer capacity (Cdl) can be separated as follows. First, the electric double layer capacity is measured under a high humidification condition such as 100% RH and a low humidification condition such as 10% RH or less.
- a high humidification condition such as 100% RH
- a low humidification condition such as 10% RH or less.
- examples of the measurement method of the electric double layer capacitance include cyclic voltammetry and electrochemical impedance spectroscopy.
- the catalyst when the catalyst is deactivated, for example, when Pt is used as the catalyst, the catalyst is deactivated by supplying CO gas to the electrode to be measured and adsorbing CO on the Pt surface.
- the contribution to the multilayer capacity can be separated. In such a state, the electric double layer capacity under high and low humidification conditions is measured by the same method as described above, and the contribution of the catalyst, that is, the above (1) and (2) is separated from these comparisons. be able to.
- the measured value (A) in the highly humidified state is the electric double layer capacity formed at all interfaces of the above (1) to (4)
- the measured value (B) in the low humidified state is the above (1) and (3). That is, the electric double layer capacitance formed at the interface.
- the measured value (C) in the catalyst deactivation / highly humidified state is the electric double layer capacity formed at the interface of the above (3) and (4)
- the measured value (D) in the catalyst deactivated / lowly humidified state is the above. This is the electric double layer capacitance formed at the interface (3).
- the difference between A and C is the electric double layer capacitance formed at the interface of (1) and (2)
- the difference between B and D is the electric double layer capacitance formed at the interface of (1).
- (AC)-(BD) the electric double layer capacity formed at the interface of (2) can be obtained.
- the contact area of the catalyst with the solid proton conductive material and the exposed area of the conductive material holding part can be obtained by, for example, TEM (transmission electron microscope) tomography.
- the membrane electrode assembly of a polymer electrolyte fuel cell has a gas diffusion electrode constituting an air electrode (cathode) and a fuel electrode (anode) on both sides of an electrolyte membrane made of a proton conductive solid polymer material by hot pressing. It has a joined structure.
- the gas diffusion electrode includes a catalyst layer containing the electrode catalyst of the present invention and a gas diffusion layer, and is joined so that the catalyst layer is located on the polymer electrolyte membrane side.
- Examples of the proton conductive solid polymer material constituting the polymer electrolyte membrane include the fluorine-based electrolyte and hydrocarbon-based electrolyte described above as the solid proton conductive material, specifically, perfluorocarbon sulfone such as Nafion and Aciplex. Acid polymers, polytrifluorostyrene sulfonic acid polymers, perfluorocarbon phosphonic acid polymers (fluorine electrolytes), polysulfone sulfonic acids, polyaryl ether ketone sulfonic acids, polybenzimidazole alkyl sulfonic acids, polybenzimidazole alkyl phosphones An acid, polystyrene sulfonic acid, etc. (hydrocarbon electrolyte) can be used. At this time, it is not always necessary to use the same solid proton conductive material used for the electrode catalyst.
- the gas diffusion layer has a function of supplying a reaction gas to the catalyst layer and collecting charges generated in the catalyst layer, and a nonwoven fabric made of carbon fiber, carbon paper, or carbon cloth is used.
- FIG. 1 is a schematic cross-sectional view showing an example of such a polymer electrolyte fuel cell.
- the fuel cell of the present embodiment includes a membrane electrode assembly, a pair of gas diffusion layers that sandwich the membrane electrode assembly, a membrane electrode assembly and a pair of gas diffusion layers, and is opposed to the gas diffusion layer. And a separator having a rib that forms a channel that is a gas flow path.
- the fuel cell shown in the figure has a membrane electrode assembly (MEA) formed by sandwiching an electrolyte membrane 10 made of a proton conductive solid polymer material between an anode side gas diffusion electrode 20a and a cathode side gas diffusion electrode 20c, It has a structure in which separators 30a and 30c on the anode side and cathode side are respectively arranged.
- the gas diffusion electrodes 20a and 20c are composed of catalyst layers 21a and 21c containing the electrode catalyst of the present invention and gas diffusion layers 22a and 22c, respectively.
- the separators 30a and 30c have gas flow paths Ca and Cc is provided.
- the solid polymer fuel cell of the present invention uses the above-mentioned electrode catalyst of the present invention, and includes two or more types of solid proton conductive materials having different EWs in the power generation surface.
- the solid proton conductive material having the lowest EW is preferably used in a region where the relative humidity of the gas in the flow path is 90% or less.
- the solid proton conductive material used in the region where the relative humidity of the gas in the flow path is 90% or less, that is, the EW of the solid proton conductive material having the lowest EW is desirably 900 or less. The above-mentioned effect becomes more certain and remarkable.
- the solid proton conductive material having the lowest EW in a region higher than the average temperature of the cooling water inlet and outlet. As a result, the resistance value is reduced regardless of the current density region, and the battery performance can be further improved.
- the solid proton conductive material having the lowest EW is within 3/5 from the gas supply port of at least one of the fuel gas and the oxidant gas with respect to the channel length. It is desirable to use in the area of the range.
- the ink prepared as described above was applied on a polytetrafluoroethylene (PTFE) substrate to a size of 5 cm ⁇ 5 cm by a screen printing method, and the amount of Pt supported was about 0.35 mg / It was made to be cm 2.
- PTFE polytetrafluoroethylene
- heat treatment was performed at 130 ° C. for 30 minutes to prepare a catalyst layer.
- the catalyst layer produced as described above was transferred to an electrolyte membrane (Nafion (registered trademark) NR211, manufactured by DuPont) to produce a membrane electrode assembly (MEA). The transfer was performed under conditions of 150 ° C., 10 min, and 0.8 MPa.
- FIG. 3 is an explanatory view schematically showing a cross-sectional structure of the electrode catalyst in the battery thus manufactured.
- catalyst (Pt) particles 2 are supported on the outer peripheral surface of the carbon carrier (Ketjen Black) 4 and the inner surface of the pores (liquid conductive material holding portion) 4a.
- the outer surface is covered with Nafion 3 as a solid proton conductive material.
- the contact area of the catalyst with the solid proton conducting material is greater than the contact area with the liquid proton conducting material by performing the following treatment on the fuel cell produced in the same manner as described above.
- the solid polymer fuel cell using the electrode catalyst of the present invention was prepared. That is, in the battery manufactured as described above, nitrogen gas conditioned at the working electrode heated to 80 ° C. and hydrogen gas conditioned at the same temperature were passed through the counter electrode. At this time, by adjusting the humidity to 10% RH in which the electric double layer capacity is sufficiently reduced due to the humidity dependency of the electric double layer capacity measured in advance, the catalyst-solid proton conductive material, carbon support- Only the solid proton conducting material interface is electrochemically effective.
- the catalyst particles supported on the outer periphery of the carbon support 4 and in contact with the solid proton conductive material 3 2 dissolves.
- the electrode of the present invention is obtained by dissolving and reducing the catalyst particles 2 in contact with the solid proton conductive material 3 at the outer peripheral portion of the support 4 by performing 150,000 cycles of such potential fluctuation (holding for 3 seconds at each potential).
- a polymer electrolyte fuel cell provided with catalyst 1 was obtained. Then, by the same method, the electric double layer capacity on the catalyst surface was measured and the battery performance was evaluated.
- each battery was heated to 30 ° C. with a heater, and the electric double layer capacity was measured in a state where nitrogen gas and hydrogen gas adjusted to the humidified state shown in Table 1 were supplied to the working electrode and the counter electrode, respectively.
- the electric double layer capacity as shown in Table 1, it was held at 0.45 V, and the potential of the working electrode was oscillated in the frequency range of 20 kHz to 10 mHz with an amplitude of ⁇ 10 mV.
- the real part and imaginary part of the impedance at each frequency are obtained from the response when the working electrode potential vibrates. Since the relationship between the imaginary part (Z ′′) and the angular velocity ⁇ (converted from the frequency) is expressed by the following equation, the reciprocal of the imaginary part is arranged with respect to ⁇ 2 to the angular velocity, and when the ⁇ 2 to the angular velocity is 0 The electric double layer capacitance C dl is obtained by extrapolating the value.
- Such measurement was sequentially performed in a low humidified state and a high humidified state (5% RH ⁇ 10% RH ⁇ 90% RH ⁇ 100% RH condition). Furthermore, after deactivating the Pt catalyst by flowing nitrogen gas containing CO at a concentration of 1% (volume ratio) at 1 NL / min for 15 minutes or more in the working electrode, the above high humidification and low humidification conditions as described above The electric double layer capacity was measured in the same manner. These results are shown in Table 2. In addition, the obtained electric double layer capacity was shown in terms of a value per area of the catalyst layer.
- the electric double layer capacity formed at the catalyst-solid proton conducting material (CS) interface and the catalyst-liquid proton conducting material (CL) interface was calculated. Shown in In the calculation, the measured values under the conditions of 5% RH and 100% RH were used as representatives of the electric double layer capacity in the low and high humidification states.
- the effective surface area of the catalyst is calculated from the amount of electricity generated by proton adsorption on the catalyst Pt using the electrochemical measurement system HZ-3000 described above, sweeping the potential of the measurement object under the conditions shown in Table 4. did.
- Example 1 As the conductive porous carrier, black pearl (specific surface area 1500 m 2 / g), which is a carbon carrier, is used, and a cobalt alloy metal having a particle diameter of 1 to 5 nm is supported as a catalyst so that the weight ratio is 50%. Thus, catalyst powder was obtained.
- ionomer dispersion which is a solid proton conductive material having a different weight equivalent weight (EW) of proton conductive group
- EW weight equivalent weight
- D2020 registered trademark
- a catalyst ink was prepared.
- heat treatment was performed at 130 ° C. for 30 minutes to prepare a catalyst layer.
- the catalyst layer produced as described above was transferred to an electrolyte membrane (Nafion (registered trademark) NR211, manufactured by DuPont) to produce a membrane electrode assembly (MEA).
- Example 2 An MEA was produced by repeating the same operation as in Example 1 except that only Nafion (registered trademark) D2020 was used as the ionomer dispersion as the solid proton conductive material.
- Example 1 An MEA was produced by repeating the same operation as in Example 1 except that graphitized ketjen black (specific surface area 150 m 2 / g) as a carbon carrier was used as the conductive porous carrier.
- Comparative Example 2 An MEA was produced by repeating the same operation as in Comparative Example 1 except that only Nafion (registered trademark) D2020 was used as the ionomer dispersion as the solid proton conductive material.
- the battery coverage was evaluated while calculating the catalyst coverage. In calculating the coverage, it was calculated from the ratio of the electric double layer capacity in the low humidified state to the high humidified state, and the measured values under the conditions of 5% RH and 100% RH were used as representative of the humidity state. .
- the electrode has a smaller capacity of the electric double layer formed at the interface with the solid proton conductive material of the catalyst than the capacity formed at the interface with the liquid proton conductive material.
- the effective surface area of the catalyst is calculated from the amount of electricity generated by adsorption of protons on the catalyst metal using the above-described electrochemical measurement system HZ-3000, sweeping the potential of the measurement target under the conditions shown in Table 4. did.
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Abstract
Description
そして、固体プロトン伝導材と触媒との直接接触を極力少なくする一方、水に代表される液体プロトン伝導材を固体プロトン伝導材と触媒との間に介在させることによって上記目的を達成することができることを見出し、本発明を完成するに到った。
本発明においては、触媒と固体プロトン伝導材の間に液体伝導材保持部を備えており、この保持部に液体プロトン伝導材が導入されることによって、触媒と固体プロトン伝導材の間に、液体プロトン伝導材を介したプロトン輸送経路が確保されることになる。
このような触媒金属の形状やサイズは特に限定されず、公知の触媒金属と同様の形状およびサイズのものを使用できる。形状としては、粒状、鱗片状、層状などのものが使用できるが、典型例として、粒状の場合には、1~30nm程度、さらには2~5nmの範囲内とすることが望ましい。
本発明に用いる固体プロトン伝導材は、ポリマー骨格の全部又は一部にフッ素原子を含むフッ素系電解質と、ポリマー骨格にフッ素原子を含まない炭化水素系電解質とに大別される。
なお、EW(Equivalent Weight)とは、プロトン伝導性を有するイオン交換基の当量重量を表す。
具体的には水、プロトン性イオン液体、過塩素酸水溶液、硝酸水溶液、ギ酸水溶液、酢酸水溶液などを挙げることができる。
また、燃料電池の作動時における電気化学反応によって生じた生成水を利用することもできる。したがって、燃料電池の運転開始の状態においては、必ずしも当該電極触媒の液体伝導材保持部に液体プロトン伝導材が保持されている必要はないことになる。
したがって、触媒を全て空孔内に担持させると共に、水に代表される液体プロトン伝導材を空孔内に導入することによって、触媒と固体プロトン伝導材との接触を完全に遮断しながら、触媒と固体プロトン伝導材の間にプロトン輸送経路を形成することができるようになる。
これらの中では、担体内部に液体伝導体保持部を形成し易いことから、導電性多孔質担体としてケッチェンブラックを使用することが望ましい。
すなわち、導電性担体として、非多孔質の導電性担体やガス拡散層を構成する炭素繊維から成る不織布やカーボンペーパー、カーボンクロスなども挙げられる。このとき、触媒をこれら非多孔質の導電性担体に担持したり、膜電極接合体のガス拡散層を構成する炭素繊維から成る不織布やカーボンペーパー、カーボンクロスなどに直接付着させたりすることも可能である。
このような距離を保持することによって、触媒と固体プロトン伝導材との非接触状態を保持しながら、触媒と固体プロトン伝導材の間(液体伝導材保持部)に水(液体プロトン伝導材)を介入させることができ、両者間の水によるプロトン輸送経路が確保されることになる。
これら面積の比較は、例えば、上記液体伝導材保持部に液体プロトン伝導材を満たした状態で、触媒-固体プロトン伝導材界面と触媒-液体プロトン伝導材界面に形成される電気二重層の容量の大小関係を求めることによって行うことができる。すなわち、電気二重層容量は、電気化学的に有効な界面の面積に比例するため、触媒-固体プロトン伝導材界面に形成される電気二重層容量の方が触媒-液体プロトン伝導材界面に形成される電気二重層容量よりも小さければ、触媒の固体プロトン伝導材との接触面積が液体伝導材保持部への露出面積よりも小さいことになる。
すなわち、本発明のような系の電極触媒においては、
(1)触媒-固体プロトン伝導材(C-S)
(2)触媒-液体プロトン伝導材(C-L)
(3)導電性多孔質担体-固体プロトン伝導材(Cr-S)
(4)導電性多孔質担体-液体プロトン伝導材(Cr-L)
の4種の界面が電気二重層容量(Cdl)として寄与し得る。
まず、例えば100%RHのような高加湿条件、及び10%RH以下のような低加湿条件下において、電気二重層容量をそれぞれ計測する。なお、電気二重層容量の計測手法としては、サイクリックボルタンメトリーや電気化学インピーダンス分光法などを挙げることができる。
さらに触媒を失活させること、例えば、Ptを触媒として用いた場合には、測定対象の電極にCOガスを供給してCOをPt表面上に吸着させることによる触媒の失活によって、その電気二重層容量への寄与を分離することができる。このような状態で、前述のように高加湿及び低加湿条件における電気二重層容量を同様の手法で計測し、これらの比較から、触媒の寄与、つまり上記(1)及び(2)を分離することができる。
すなわち、高加湿状態における測定値(A)が上記(1)~(4)の全界面に形成される電気二重層容量、低加湿状態における測定値(B)が上記(1)及び(3)の界面に形成される電気二重層容量ということになる。また、触媒失活・高加湿状態における測定値(C)が上記(3)及び(4)の界面に形成される電気二重層容量、触媒失活・低加湿状態における測定値(D)が上記(3)の界面に形成される電気二重層容量ということになる。
なお、触媒の固体プロトン伝導材との接触面積や、伝導材保持部への露出面積については、上記の他には、例えば、TEM(透過型電子顕微鏡)トモグラフィなどによっても求めることができる。
ガス拡散電極は、本発明の上記電極触媒を含む触媒層とガス拡散層から成り、上記触媒層が高分子電解質膜の側に位置するように接合されている。
すなわち、図1は、このような固体高分子型燃料電池の一例を示す概略断面図である。
ここで、上記ガス拡散電極20a及び20cは、本発明の電極触媒を含む触媒層21a、21cと、ガス拡散層22a、22cからそれぞれ構成され、上記セパレータ30a及び30cは、それぞれガス流路Ca及びCcを備えている。
〔1〕膜電極接合体(MEA)の作製
導電性多孔質担体として、表面開口径が10nm程度の空孔を有するカーボン担体を用い、これに触媒として粒径1~5nmの白金(Pt)を50%となるように担持させて、触媒粉末とした。なお、上記カーボン担体としては、ケッチェンブラック(粒径:30~60nm)を使用した。
この触媒粉末と、固体プロトン伝導材としてのアイオノマー分散液(Nafion(登録商標)D2020,EW=1100g/mol、DuPont社製)とをカーボン担体とアイオノマーの質量比が0.9となるよう混合した。さらに、溶媒としてプロピレングリコール溶液(50%)を固形分率(Pt+カーボン担体+アイオノマー)が19%となるよう添加して、触媒インクを調製した。
上記のようにして作製した触媒層を電解質膜(Nafion(登録商標)NR211,DuPont社製)へ転写して膜電極接合体(MEA)を作製した。なお、転写は150℃、10min、0.8MPaの条件で行った。
〔2-1〕比較例
上記のようにして作製した膜電極接合体の両面をガス拡散層(24BC,SGLカーボン社製)、さらにカーボンセパレーター、さらには金メッキした集電板で挟持し、電池を作製した。
このように作製した電池を本発明の電極触媒を使用していない比較例として、後述する方法によって、触媒の固体プロトン伝導材及び液体プロトン伝導材との界面に形成される電気二重層容量をそれぞれ測定すると共に、電池性能の評価を行った。
図において、カーボン担体(ケッチェンブラック)4の外周面及び空孔(液体伝導材保持部)4aの内部表面には、触媒(Pt)粒子2が担持されており、このようなカーボン担体4の外面は、固体プロトン伝導材としてのナフィオン3によって覆われている。
一方、上記同様に作製した燃料電池に対して、以下のような処理を施すことによって、触媒の固体プロトン伝導材との接触面積が液体プロトン伝導材との接触面積よりも小さくなるように調整し、本発明の電極触媒を用いた固体高分子型燃料電池とした。
すなわち、上記のように作製した電池において、80℃に加熱した作用極に調湿した窒素ガス、対極には同様に調湿した水素ガスをそれぞれ流通させた。このとき、予め計測しておいた、電気二重層容量の湿度依存性から、電気二重層容量が十分低下している10%RHに調湿することによって、触媒―固体プロトン伝導材、カーボン担体―固体プロトン伝導材界面のみが電気化学的に有効となる。
このような電位変動(各電位で3秒ずつ保持)を150000サイクル行うことによって、担体4の外周部において固体プロトン伝導材3と接触している触媒粒子2を溶解させて減じた本発明の電極触媒1(図2参照)を備えた固体高分子型燃料電池を得た。そして、同様の方法によって、触媒表面の電気二重層容量を測定すると共に、電池性能の評価を行った。
上記によって得られた実施例及び比較例電池について、電気化学インピーダンス分光法により、高加湿状態、低加湿状態、さらに触媒失活かつ高加湿状態及び低加湿状態における電気二重層容量をそれぞれ測定し、両電池の電極触媒における触媒の両プロトン伝導材との接触面積を比較した。
なお、使用機器としては、北斗電工株式会社製電気化学測定システムHZ-3000と、エヌエフ回路設計ブロック社製周波数応答分析器FRA5020を用い、表1に示す測定条件を採用した。
電気二重層容量の測定に際しては、表1に示したように、0.45Vで保持し、さらに、±10mVの振幅で、20kHz~10mHzの周波数範囲で作用極の電位を振動させた。
さらに、作用極に濃度1%(体積比)のCOを含む窒素ガスを1NL/分で15分以上流通させることによって、Pt触媒を失活させたのち、上記のような高加湿及び低加湿状態における電気二重層容量をそれぞれ同様に計測した。これらの結果を表2に示す。なお、得られた電気二重層容量は、触媒層の面積当たりの値に換算して示した。
なお、算出に当たっては、低加湿状態及び高加湿状態の電気二重層容量を代表するものとして、それぞれ5%RH及び100%RH条件における計測値を用いた。
燃料電池を80℃に保持し、酸素極には100%RHに調湿した酸素ガス、燃料極には100%RHに調湿した水素ガスをそれぞれ流通させ(これによって、カーボン担体(ケッチェンブラック)4の空孔(液体伝導材保持部4a)内に水が導入され、この水が液体プロトン伝導材として機能する)、電流密度が1.0A/cm2となるように電子負荷を設定し、15分保持した。
これに対して、固体プロトン伝導材との界面に形成される電気二重層容量の方が小さい本発明の電極触媒を適用した電池においては、322μA/cm2という高い電流密度が得られることが確認された。
〔実施例1〕
導電性多孔質担体として、カーボン担体であるブラックパール(比表面積1500m2/g)を用い、これに触媒として粒径1~5nmのコバルト合金金属をその重量比が50%となるように担持させて、触媒粉末とした。
この触媒粉末と、プロトン伝導基重量等量(EW)の異なる固体プロトン伝導材であるアイオノマー分散液として、Nafion(登録商標)D2020(EW=1100g/mol、DuPont社製)、及びパーフルオロスルホン酸アイオノマーIN201(EW=660g/mol、旭硝子株式会社製)を用い、上記触媒粉末中の導電性多孔質担体との質量比が0.9となるように別々に混合し、アイオノマーが異なる2種類の触媒インクを調製した。
上記のようにして作製した触媒層を電解質膜(Nafion(登録商標)NR211,DuPont社製)へ転写して膜電極接合体(MEA)を作製した。
固体プロトン伝導材としてのアイオノマー分散液として、Nafion(登録商標)D2020のみを使用したこと以外は、上記実施例1と同様操作を繰り返すことによって、MEAを作製した。
導電性多孔質担体として、カーボン担体であるグラファイト化ケッチェンブラック(比表面積150m2/g)を用いた以外は、実施例1と同様の操作を繰り返すことによってMEAを作製した。
固体プロトン伝導材としてのアイオノマー分散液として、Nafion(登録商標)D2020のみを使用したこと以外は、比較例1と同様の操作を繰り返すことによってMEAを作製した。
固体プロトン伝導材として、パーフルオロスルホン酸アイオノマーIN201(EW=660g/mol、旭硝子株式会社製)のみを使用したこと以外は、実施例1と同様の操作を繰り返すことによってMEAを作製した。
燃料電池を80℃に保持し、相対湿度100%から40%を代表的な湿度条件として、酸素極に調湿した酸素ガス、燃料極に調湿した水素ガスをそれぞれ流通させ、電圧値が0.9Vとなる触媒表面積あたりの電流密度値、ならびに電流密度が1.0A/cm2となるような電圧値を計測した。その結果を表5及び表5に示す。
2 Pt(触媒)
3 ナフィオン(固体プロトン伝導材)
4 カーボン担体(導電性多孔質担体)
4a 液体伝導材保持部
Claims (15)
- 触媒と、固体プロトン伝導材を有すると共に、上記触媒と固体プロトン伝導材をプロトン伝導可能な状態に連結する液体プロトン伝導材を保持する液体伝導材保持部を両者の間に備え、
上記触媒の固体プロトン伝導材との接触面積が、当該触媒の上記液体伝導材保持部に露出する面積よりも小さいことを特徴とする固体高分子型燃料電池用電極触媒。 - 導電性担体、前記導電性担体の表面に配置される触媒、固体プロトン伝導材、触媒と固体プロトン伝導材をプロトン伝導可能な状態に連結する液体プロトン伝導材を有し、
前記導電性担体は前記液体プロトン伝導材を保持する液体伝導材保持部を備え、
前記触媒の固体プロトン伝導材との接触面積が、前記触媒の前記液体伝導材保持部に露出する面積よりも小さいことを特徴とする固体高分子型燃料電池用電極触媒。 - 上記液体伝導材保持部に液体プロトン伝導材が保持されていることを特徴とする請求項1又は2に記載の固体高分子型燃料電池用電極触媒。
- 上記液体伝導材保持部に液体プロトン伝導材が満たされた状態において、触媒-固体プロトン伝導材界面に形成される電気二重層容量が、触媒-液体プロトン伝導材界面に形成される電気二重層容量よりも小さいことを特徴とする請求項2又は3に記載の固体高分子型燃料電池用電極触媒。
- 上記触媒が固体プロトン伝導材と非接触状態にあることを特徴とする請求項1~4のいずれか1つの項に記載の固体高分子型燃料電池用電極触媒。
- 触媒と、固体プロトン伝導材と、上記触媒を担持する導電性多孔質担体を有し、当該多孔質担体の空孔が上記液体伝導材保持部として機能することを特徴とする請求項1~5のいずれか1つの項に記載の固体高分子型燃料電池用電極触媒。
- 上記導電性多孔質担体がケッチェンブラックであることを特徴とする請求項6に記載の固体高分子型燃料電池用電極触媒。
- 上記固体プロトン伝導材のEWが1200以下であることを特徴とする請求項1~7のいずれか1つの項に記載の固体高分子型燃料電池用電極触媒。
- 上記触媒がPt、Ir、Co、Ni、Fe、Cu、Ru、Ag及びPdから成る群から選ばれた少なくとも1種の金属を含むことを特徴とする請求項1~8のいずれか1つの項に記載の固体高分子型燃料電池用電極触媒。
- 請求項1~9のいずれか1つの項に記載の電極触媒を有することを特徴とする固体高分子型燃料電池用膜電極接合体。
- 請求項10に記載の膜電極接合体と、
上記膜電極接合体を挟持する一対のガス拡散層と、
上記膜電極接合体及び一対のガス拡散層を挟持し、上記ガス拡散層との対峙面にガス流路を有するセパレータとを備えたことを特徴とする固体高分子型燃料電池。 - 発電面内にEWが異なる2種類以上の固体プロトン伝導材を含み、これらのうち最もEWが低い固体プロトン伝導材が上記ガス流路内ガスの相対湿度が90%以下の領域に用いられていることを特徴とする請求項11に記載の固体高分子型燃料電池。
- 最もEWが低い固体プロトン伝導材のEWが900以下であることを特徴とする請求項12に記載の固体高分子型燃料電池。
- 最もEWが低い固体プロトン伝導材が冷却水の入口と出口の平均温度よりも高い領域に用いられていることを特徴とする請求項12又は13に記載の固体高分子型燃料電池。
- 最もEWが低い固体プロトン伝導材が流路長に対して燃料ガス及び酸化剤ガスの少なくとも一方のガス供給口から3/5以内の範囲の領域に用いられていることを特徴とする請求項12~14のいずれか1つの項に記載の固体高分子型燃料電池。
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EP (1) | EP2631975B1 (ja) |
JP (1) | JP5522423B2 (ja) |
KR (1) | KR101502256B1 (ja) |
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WO (2) | WO2012053303A1 (ja) |
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KR20130059443A (ko) | 2013-06-05 |
EP2631975B1 (en) | 2019-03-06 |
WO2012053303A1 (ja) | 2012-04-26 |
JP5522423B2 (ja) | 2014-06-18 |
EP2631975A4 (en) | 2014-12-31 |
EP2631975A1 (en) | 2013-08-28 |
CN103181010B (zh) | 2015-07-29 |
CN103181010A (zh) | 2013-06-26 |
US9799903B2 (en) | 2017-10-24 |
KR101502256B1 (ko) | 2015-03-12 |
US20140199609A1 (en) | 2014-07-17 |
JPWO2012053638A1 (ja) | 2014-02-24 |
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