JP4133654B2 - Polymer electrolyte fuel cell - Google Patents

Polymer electrolyte fuel cell Download PDF

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JP4133654B2
JP4133654B2 JP2003270230A JP2003270230A JP4133654B2 JP 4133654 B2 JP4133654 B2 JP 4133654B2 JP 2003270230 A JP2003270230 A JP 2003270230A JP 2003270230 A JP2003270230 A JP 2003270230A JP 4133654 B2 JP4133654 B2 JP 4133654B2
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electrode
carrier
catalyst layer
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井上  昌彦
多田  智之
順二 松尾
恵子 江藤
英樹 海藤
一郎 田中
薫 福田
雅樹 谷
長之 金岡
あゆみ 龍
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本田技研工業株式会社
田中貴金属工業株式会社
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/50Fuel cells
    • Y02E60/52Fuel cells characterised by type or design
    • Y02E60/521Proton Exchange Membrane Fuel Cells [PEMFC]

Description

  The present invention relates to a polymer electrolyte fuel cell, and more particularly to a polymer electrolyte fuel cell using a graphitized support catalyst.

  A polymer electrolyte fuel cell is configured by stacking separators on both sides of a flat electrode structure. An electrode structure is generally a laminate in which a polymer electrolyte membrane is sandwiched between an electrode catalyst layer on the cathode side and an electrode catalyst layer on the anode side, and a gas diffusion layer is laminated outside each electrode catalyst layer. is there. According to such a fuel cell, for example, when a fuel gas is caused to flow through the gas passage of the separator disposed on the anode side and an oxidizing gas is caused to flow through the gas passage of the separator disposed on the cathode side, an electrochemical reaction occurs. Electric current is generated.

During operation of the fuel cell, the gas diffusion layer transmits electrons generated by the electrochemical reaction between the electrode catalyst layer and the separator, and simultaneously diffuses the fuel gas and the oxidizing gas. The anode-side electrode catalyst layer causes a chemical reaction to the fuel gas to generate protons (H + ) and electrons, while the cathode-side electrode catalyst layer generates water from oxygen, protons, and electrons, The electrolytic membrane causes protons to conduct ions. Then, electric power is taken out through the positive and negative electrode catalyst layers.

  The generation of protons and electrons occurring on the anode side is performed in the presence of a three-phase catalyst, carrier and electrolyte. That is, an electrolyte that conducts protons and a carrier that conducts electrons coexist, and the catalyst coexists to oxidize hydrogen gas.

  The electrode catalyst layer is generally prepared by mixing a carrier having a catalyst particle such as Pt supported on the surface and an electrolyte made of an ion conductive polymer in a solvent to prepare a catalyst paste. Alternatively, it is formed by coating and drying on a tetrafluoroethylene-hexafluoropropylene copolymer (FEP) sheet.

Further, as a carrier in a fuel cell, a technique for improving the durability of the carrier catalyst by graphitizing the carrier carrying the catalyst is known. Furthermore, since the electrode catalyst layer is excellent in water repellency and corrosion resistance as a support, the average lattice spacing d 002 of the [002] plane, the crystallite size Lc (002), and the specific surface area are within a specific range. Defined carbon particles have been reported (for example, see Patent Documents 1 to 4).

JP 2000-268828 A JP 2001-357857 A JP 2002-015745 A JP 2003-036859 A

However, even if the support is simply graphitized by heat treatment as in the past, large aggregates are formed and the thickness of the electrode catalyst layer becomes non-uniform, deforming the polymer electrolyte membrane and reducing power generation efficiency. It had the problem of letting it go. In addition, if the support is excessively graphitized, the pores in the electrode catalyst layer through which the gas supplied and the water generated in power generation pass cannot be satisfactorily formed, resulting in poor power generation performance. Had. For such a graphitization problem, simply defining the average lattice spacing d 002 of the [002] plane of the carbon particles, the crystallite size Lc (002), and the specific surface area within a specific range. It has not been solved.

  Accordingly, an object of the present invention is to provide a polymer electrolyte fuel cell that can obtain excellent durability by graphitization of a support and can obtain excellent power generation performance by controlling pores in an electrode catalyst layer. Yes.

The electrode for a polymer electrolyte fuel cell of the present invention has an electrode catalyst layer composed of a catalyst, a carrier, an electrolyte, and a pore forming agent, and the carrier has an average lattice plane distance d 002 of [002] plane of 0.338. ˜0.355 nm, specific surface area of 80 to 250 m 2 / g, bulk density of 0.30 to 0.45 g / ml, and 0.01 to 2.0 μm pores in the electrode catalyst layer The volume is 3.8 μl / cm 2 / mg-Pt or more, and the pore volume of 0.01 to 0.15 μm is 2.0 μl / cm 2 / mg-Pt or more.

In the polymer electrolyte fuel cell of the present invention, the catalyst has a specific surface area of 75 to 100 m 2 / g, the crystallite size of the catalyst particles is 2 to 5 nm, and the carrier has a catalyst loading ratio of 40. The average lattice spacing d 002 of the [002] plane after catalyst loading is 0.338 to 0.345 nm, and the peak of X-ray diffraction in the measurement of the average lattice spacing is simple. It is a preferred embodiment that it is a single peak.

According to the present invention, the average lattice spacing d 002 of the [002] plane is 0.338 to 0.355 nm, the specific surface area is 80 to 250 m 2 / g, and the bulk density is 0.30 to 0.45 g / ml. By using a pore-forming agent together with the carrier, the pore volume of 0.01 to 2.0 μm in the electrode catalyst layer is 3.8 μl / cm 2 / mg-Pt or more and 0.01 to 0.15 μm. The pore volume can be controlled to 2.0 μl / cm 2 / mg-Pt or more, and both excellent durability and excellent power generation performance can be obtained.

  In the polymer electrolyte fuel cell of the present invention, a cathode-side electrode catalyst layer and an anode-side electrode catalyst layer are laminated so as to sandwich a polymer electrolyte membrane, and further, a gas diffusion layer is formed outside these electrode catalyst layers. Are stacked to form an electrode structure, and a large number of these electrode structures are stacked via separators. In the present invention, constituent elements other than the electrode catalyst layer are not particularly limited, and therefore the electrode catalyst layer will be described in detail below.

The electrode catalyst layer in the polymer electrolyte fuel cell of the present invention is composed of a catalyst, a carrier, an electrolyte, and a pore former. The electrode catalyst layer of the present invention uses a pore-forming agent together with a carrier having specific physical property values, so that the pore volume of 0.01 to 2.0 μm in the electrode catalyst layer is 3.8 μl / cm 2 / mg. The pore volume of −Pt or more and 0.01 to 0.15 μm is controlled to 2.0 μl / cm 2 / mg-Pt or more. The pores of 0.01 to 0.15 μm are mainly for supplying fuel gas and oxidizing gas, and the pores of 0.15 to 2.0 μm discharge water generated by power generation. Is to do. By defining the volume of these pores, good power generation performance can be exhibited. The polymer electrolyte fuel cell of the present invention can be produced using a conventional method.

Hereinafter, each component in the present invention will be described.
(1) Catalyst The catalyst in the present invention is preferably platinum and a platinum alloy. Examples of the platinum alloy include ruthenium, rhodium, palladium osmium, iridium, gold, silver, chromium, iron, cobalt, nickel, molybdenum, tungsten, An alloy of platinum with aluminum, silicon, zinc, tin, or the like can be given. Moreover, it is preferable that the specific surface area of the catalyst in this invention is 75-100 m < 2 > / g. If the specific surface area is less than 75 m 2 / g, the amount of pores decreases and the battery characteristics deteriorate. On the other hand, if the specific surface area exceeds 100 m 2 / g, there is a problem in durability. Furthermore, the catalyst in the present invention preferably has a crystallite size of the catalyst particles of 2 to 5 nm. When the crystallite size is less than 2 nm, the catalytic activity is lowered. On the other hand, when the crystallite size is more than 5 nm, the battery surface characteristics are lowered due to a decrease in the catalyst surface area.

(2) Carrier As the carrier in the present invention, carbon particles such as carbon black can be suitably used, and the carbon particles are graphitized by heat treatment at 2000 to 3000 ° C. to obtain an average lattice of [002] plane. A graphitized support catalyst having an interplanar distance d 002 of 0.338 to 0.355 nm, a specific surface area of 80 to 250 m 2 / g, and a bulk density of 0.30 to 0.45 g / ml can be obtained. . Regarding the heat treatment for graphitization, it is preferable to appropriately select the temperature and time by an apparatus or the like. The d 002 of less than 0.338 nm, low voltage, battery characteristics is deteriorated. On the other hand, if d 002 exceeds 0.355Nm, durability of the electrode carrier will inferior. On the other hand, when the specific surface area is less than 80 m 2 / g, the dispersibility of the catalyst is inferior. On the other hand, when the specific surface area exceeds 250 m 2 / g, the reaction points of the support increase, and the support is easily corroded and has durability. It will be inferior. Furthermore, if the bulk density is less than 0.30 g / ml, the viscosity of the paste increases, whereas if the bulk density exceeds 0.45 g / ml, the viscosity of the paste is low, and in both cases, the dispersibility is poor, Stirring cannot be performed well, resulting in a non-uniform electrode.

The carrier in the present invention has a catalyst loading ratio of 40 to 60% by weight, an average lattice spacing d 002 of [002] plane after catalyst loading is 0.338 to 0.345 nm, and the average In a preferred embodiment, the X-ray diffraction peak in the measurement of the lattice spacing is a single peak. If the catalyst loading is less than 40% by weight, the battery characteristics increase due to the thick battery, while if it exceeds 60% by weight, the dispersibility of the catalyst deteriorates. On the other hand, if d 002 after catalyst loading is less than 0.338 nm, the amount of pores decreases, resulting in a decrease in battery characteristics. On the other hand, if d 002 exceeds 0.345 nm, there is a problem in durability. Furthermore, when the peak of the X-ray diffraction is not single, as the electrode, the battery characteristics deteriorate due to the decrease in the amount of pores, and as the catalyst, the battery is uneven due to non-uniform loading. The characteristics will deteriorate.

(3) Electrolyte As the electrolyte in the present invention, an ion conductive polymer such as a fluororesin ion exchange resin can be used. The weight ratio of the electrolyte to the carrier is desirably 1.4 or more. If the amount of electrolyte is small, the porosity increases and gas diffusivity is improved. On the other hand, the carrier carrying the catalyst is not sufficiently covered, and the point where the fuel gas and oxidizing gas are activated is reduced. As a result, the utilization rate of the catalyst decreases.

(4) Pore-forming agent The pore-forming agent in the present invention is desirably a fine fibrous material having a diameter of 0.4 μm or less. By adding such a fine fibrous material to the catalyst paste as a pore-forming agent, the fibers become pillars and take the load during pressing, and the compression load more than necessary acts on the carbon and the polymer electrolyte membrane. Since the gas channel is held without being crushed, the power generation efficiency is improved. Furthermore, as an advantage of using such a fibrous substance, the porosity of the catalyst layer after the pressing step can be freely controlled by the amount of the fibrous substance added.

  Examples of the fibrous material include inorganic fibers such as alumina whisker and silica whisker, carbon fibers such as vapor-grown carbon (carbon whisker), and polymer fibers such as nylon and polyimide. Carbon whiskers having electronic conductivity are preferably used. The carbon whisker is entangled with the catalyst material constituting the catalyst layer and the electron conductive material carrying the catalyst material, so that a new conductive path is developed in addition to the conductive path due to the point contact of this electron conductive material. The electron conductivity of the catalyst layer is improved. In addition, since the carbon whisker has electronic conductivity, the catalytic material can be supported on the surface of the carbon whisker for the purpose of improving the area density of the catalytic material in the electrode.

  In addition, the fibrous substance in the present invention preferably has a water repellent property or a surface that has been subjected to a water repellent treatment. As described above, since the fibrous material is entangled and exists in the electrode catalyst layer, pores are easily generated, and these pores function as gas channels. In the fuel cell, water vapor is generated in the electrode catalyst layer on the cathode side with power generation, and the water vapor is discharged out of the system through the diffusion layer formed on the surface side of the electrode catalyst layer. Here, when the water vapor is condensed, the water closes the gas channel, and the fluidity of the gas is remarkably lowered. Therefore, if the fibrous material has water repellency or the surface has been subjected to water repellency treatment, dew condensation is prevented and the pores, that is, the gas channels are prevented from being blocked, and the gas permeability is ensured.

  Furthermore, the fibrous substance in the present invention may be one having a hydrophilic property or one having a hydrophilic surface as described above from the viewpoint of preventing the gas channel from being blocked due to condensation as described above. According to this embodiment, when the water vapor generated by the power generation is condensed, the water spreads to the fibrous material by the capillary phenomenon and no liquid droplet is generated. For this reason, the projected area of water is reduced, and at the same time, the water moves to a dry portion and the blockage of the gas channel is prevented. For example, although the humidity on the downstream side of the gas channel is high and condensation tends to occur, condensation is prevented even in such a place, and the power generation performance is unlikely to deteriorate. In addition, capillary action causes a rapid movement of water from a place where water is excessive to a place where water is insufficient, thereby eliminating spontaneous water shortage inside the electrode. As a result, there is an effect that the occurrence of voltage fluctuation according to the humidification amount is suppressed.

  The content of the fibrous material according to the present invention in the electrode catalyst layer is preferably 5 to 25% by weight based on the total amount of the catalyst layer. The reason for this is that when the content is less than 5% by weight, the above-mentioned effects are hardly exhibited. On the other hand, when the content exceeds 25% by weight, the absolute amount of catalytic reaction points per volume decreases and the power generation efficiency decreases. Because it invites.

Next, the effects of the present invention will be described in detail by way of specific examples.
1. Production of Electrode Structure MEA <Example 1>
After graphitizing carbon black (trade name: Ketjen Black EC, manufactured by Mitsubishi Chemical Corp.) by heat treatment at 2800 ° C., platinum is supported so that the weight ratio with respect to carbon black is 1: 1. A catalyst was prepared. Next, 10 g of this graphitized support catalyst, 35 g of a 20% ion conductive polymer solution (trade name: Nafion DE2020, manufactured by DuPont), and 1.7 g of acicular carbon fiber (trade name: VGCF, manufactured by Showa Denko KK) Were mixed to prepare a cathode electrode paste. Next, this cathode electrode paste is applied and dried on a tetrafluoroethylene-hexafluoropropylene copolymer (FEP) sheet so that the amount of Pt is 0.3 mg / cm 2 , thereby producing a cathode electrode sheet C1. did.

On the other hand, 40 g of ion-conducting polymer (trade name: DE2021, manufactured by DuPont) and Pt—Ru-supported carbon particles (trade name: TEC61E54, Pt: Ru = 1) with a weight ratio of carbon black to catalyst of 46:54. : 1.5, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) 10.9 g was mixed to prepare an anode catalyst paste. This anode catalyst paste was applied onto an FEP sheet and dried so that the amount of catalyst was 0.15 mg / cm 2 , thereby obtaining an anode electrode sheet A1.

Further, 12 g of Teflon (registered trademark) powder (trade name: L170J, manufactured by Asahi Glass Co., Ltd.) and 18 g of carbon black powder (trade name: Vulcan XC72, manufactured by Cabot) were mixed with ethylene glycol to obtain a base layer paste. . Next, 2.3 mg / cm 2 of the base layer paste was applied and dried on carbon paper (trade name: TGP-H-060, manufactured by Toray Industries, Inc.) to obtain an anode and a cathode diffusion layer.

Next, the cathode electrode sheet C1 and the anode electrode sheet A1 were transferred onto both surfaces of a polymer electrolyte membrane (made by Nafion) by a decal method at a temperature of 140 ° C. and an integrated pressure of 30 kg / cm 2 , and the membrane-electrode composite A body CCM was produced, and the anode and cathode diffusion layers were laminated so as to sandwich the CCM, thereby forming the electrode structure MEA of Example 1. The transfer by the decal method means that the FEP sheet is peeled after the electrode sheet is thermocompression bonded to the polymer electrolyte membrane.

<Example 2>
In the production process of the cathode electrode sheet of Example 1, the temperature of the heat treatment of carbon black was changed from 2800 ° C. to 2000 ° C., and the cathode electrode sheet C 2 was produced in the same manner as in Example 1, except that the cathode electrode sheet C 2 was produced. An electrode structure MEA was produced.

<Comparative Example 1>
In the production process of the cathode electrode sheet of Example 1, the temperature of the heat treatment of carbon black was changed from 2800 ° C. to 3200 ° C., and the cathode electrode sheet C3 was produced in the same manner as in Example 1 except that the cathode electrode sheet C3 was produced. An electrode structure MEA was produced.

<Comparative example 2>
An electrode structure MEA of Comparative Example 2 was produced in the same manner as in Example 1 except that, in the production process of the cathode electrode sheet of Example 1, the cathode electrode sheet C4 was produced without performing heat treatment on carbon black.

<Comparative Example 3>
In the production process of the cathode electrode sheet of Example 1, 30 g of 1-propyl alcohol was further mixed to prepare a cathode electrode paste, and the cathode electrode sheet C5 was produced. An electrode structure MEA was produced.

<Comparative example 4>
In the production process of the cathode electrode sheet of Example 1, the same procedure as in Example 1 except that the cathode electrode paste was prepared by changing the acicular carbon fiber from 1.7 g to 1.5 g to produce the cathode electrode sheet C6. Thus, an electrode structure MEA of Comparative Example 4 was produced.

<Comparative Example 5>
In the production process of the cathode electrode sheet of Example 1, the acicular carbon fiber was changed from 1.7 g to 1.5 g, 30 g of 1-propyl alcohol was further mixed to prepare a cathode electrode paste, and the cathode electrode sheet C7 was prepared. An electrode structure MEA of Comparative Example 5 was produced in the same manner as Example 1 except that it was produced.

2. Power Generation Performance Evaluation For Examples 1-2 and Comparative Examples 1-5 produced as described above, the average lattice spacing d 002 of the [002] plane of the graphitized single catalyst, specific surface area, bulk density, and 0 The pore volumes of 0.01 to 2.0 μm and 0.01 to 0.15 μm were measured, and the results are shown in Table 1. Moreover, about Example 1 and Comparative Examples 3-5, the diagram which shows the pore volume with respect to the pore diameter of a graphitization support catalyst was shown in FIG. The pore volume is measured by mercury porosimetry.

Further, hydrogen gas and air were supplied to both surfaces of the electrode structures MEA of Examples 1-2 and Comparative Examples 1-5, cell temperature: 70 ° C., humidification amount: anode 80RH%, cathode 80RH%, utilization rate: anode Electric power was generated at a current density of 1 A / cm 2 under the conditions of 50% and cathode 50%, and the terminal voltage at this time was measured (initial voltage). In addition, under the above conditions, only the current density was set to 0.05 A / cm 2, and after 1000 hours of power generation, the terminal voltage at a current density of 1 A / cm 2 was measured in the same manner as the initial voltage measurement. These results are shown in Table 1.

As shown in FIG. 1, the graphitized carrier catalyst in Example 1 has a pore volume of 0.01 to 2.0 μm of 4.00 μl / cm 2 / mg-Pt and 0.01 to 0.15 μm. In contrast to the graphitized support catalyst in Comparative Example 3, the pore volume of 0.01 to 0.15 μm was too small, and the pore volume of Comparative Example 4 was 2.10 μl / cm 2 / mg-Pt. In the graphitized support catalyst at 0.01 to 2.0 μm, the pore volume of 0.01 to 2.0 μm is too small, and in the graphitized support catalyst in Comparative Example 5, the pore volume of 0.01 to 2.0 μm and 0.01 to 0. Both 15 μm pore volumes have been shown to be too small.

Further, as is apparent from Table 1, Examples 1 and 2 maintain a high terminal voltage even after 1000 hours from the start of power generation by limiting the physical property values of the graphitized support catalyst to a specific range. It was shown that it can. On the other hand, in Comparative Examples 1 to 5 in which the physical property values of the graphitized support catalyst deviated from the scope of the present invention, the terminal voltage decreased after 1000 hours from the start of power generation, or the terminal voltage at the initial stage of power generation was insufficient. It was shown that. That is, in Comparative Example 1, since the specific surface area is too small and the bulk density is too large, in Comparative Example 3, the pore volume of 0.01 to 0.15 μm is too small. Since the pore volume of .about.2.0 .mu.m is too small, in Comparative Example 5, the pore volume of 0.01 to 2.0 .mu.m and the pore volume of 0.01 to 0.15 .mu.m are too small. Therefore, these electrode structures cannot be put to practical use. Further, in Comparative Example 2, d 002 is too large, the specific surface area is too large, and the bulk density is too small, so that the terminal voltage after 1000 hours is lowered, and this electrode structure has power generation performance in continuous use. It was shown to be inferior.

It is a diagram which shows the pore volume with respect to the pore diameter of a graphitization support catalyst.

Claims (2)

  1. It has an electrode catalyst layer composed of a catalyst, a carrier, an electrolyte and a pore-forming agent, and the carrier has an average lattice spacing d 002 of [002] plane of 0.338 to 0.355 nm and a specific surface area of 80 to 250 m. 2 / g, the bulk density is 0.30 to 0.45 g / ml, and the pore volume of 0.01 to 2.0 μm in the electrode catalyst layer is 3.8 μl / cm 2 / mg-Pt or more. And a pore volume of 0.01 to 0.15 μm is 2.0 μl / cm 2 / mg-Pt or more.
  2. The catalyst has a specific surface area of 75 to 100 m 2 / g, the crystallite size of the catalyst particles is 2 to 5 nm, the carrier has a catalyst loading of 40 to 60% by weight, 002] plane average lattice spacing d 002 is 0.338 to 0.345 nm, and the peak of X-ray diffraction in the measurement of the average lattice spacing is a single peak. 2. The polymer electrolyte fuel cell according to 1.
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