Polymer electrolyte fuel cell

专利摘要:
In the polymer electrolyte fuel cell of the present invention, a layer comprising conductive fine particles is formed between the catalytic reaction layer and the gas diffusion layer of the electrode, and the catalyst particles and the carrier supporting the catalyst particles in the catalytic reaction layer are By providing a hydrogen ion diffusion layer on at least one of the surfaces, or by forming the catalyst reaction layer on at least a hydrophilic carbon material supporting the catalyst particles, the catalyst body and the water-repellent carbon material can be used for efficient electrode reaction. Excellent performance.
公开号:KR20010074511A
申请号:KR1020007014308
申请日:1999-06-10
公开日:2001-08-04
发明作者:교텐히사아키；야스모토에이이치；하토가즈히토；우치다마코토；스가와라야스시；간바라데루히사；모리타준지；오하라히데오；니시다가즈후미；사카이오사무；오노유키요시；다케베야스오
申请人:모리시타 요이찌；마쯔시다덴기산교 가부시키가이샤；
IPC主号:

专利说明:

Polymer electrolyte fuel cell {POLYMER ELECTROLYTE FUEL CELL}
[2] A fuel cell using a polymer electrolyte is an electrochemical device that generates power and heat simultaneously by electrochemically reacting a fuel gas containing hydrogen and an oxidant gas containing oxygen such as air.
[3] The structure of such a fuel cell first forms a catalytic reaction layer mainly composed of carbon powder carrying a platinum-based metal catalyst on both surfaces of a polymer electrolyte membrane selectively transporting hydrogen ions. Next, a gas diffusion layer having both air permeability and electron conductivity for fuel gas is formed on the outer surface of the catalytic reaction layer, and the gas diffusion layer and the catalytic reaction layer are combined to form an electrode. In this way, the electrode and the polymer electrolyte membrane are assembled together beforehand. This is called an electrode electrolyte membrane assembly (hereinafter referred to as "MEA"). In order not to leak the fuel gas or the oxidant gas to be supplied or to mix the two kinds of gases with each other, a polymer electrolyte membrane is sandwiched around the electrode and a gas seal material or a gasket is disposed. Then, a plurality of MEAs are laminated through a conductive separator plate to form a fuel cell as a so-called stacked battery.
[4] Next, the catalytic reaction layer in the electrode of the fuel cell will be described. The carbon powder carrying the metal catalyst is in the form of particles of several hundred angstroms to several microns. Using a mixture of the carbon powder and the dispersion of the polymer electrolyte, a catalytic reaction layer having a thickness of 30 to 100 microns is formed between the electrode and the solid electrolyte membrane by a coating method such as printing. In this catalytic reaction layer, electrochemical reaction of fuel gas or oxidant gas proceeds.
[5] For example, in an anode where hydrogen reacts, hydrogen gas is supplied to the electrode surface through a fuel gas flow path engraved on a separator plate. The electrode is usually made of a conductive material having air permeability such as carbon paper or carbon cloth, and hydrogen gas can penetrate the electrode to reach the catalytic reaction layer. The polymer electrolyte formed by drying and solidifying the solution of the polymer electrolyte adheres to the surface of the carbon powder carrying the catalyst. Hydrogen gas is oxidized in a so-called three-phase zone composed of a gas phase containing hydrogen gas, a solid phase of carbon carrying a catalyst, and a polymer electrolyte phase in close proximity. It becomes hydrogen ions and is released in the polymer electrolyte. Electrons generated by oxidation of hydrogen gas move through an electron conductive carbon powder to an external electric circuit. This electrochemical reaction proceeds in a wider area by dissolving hydrogen gas into the polymer electrolyte. Although the thickness of a catalytic reaction layer changes also with the manufacturing method, it is normally designed in the thickness of 30-100 microns in order to acquire favorable battery performance.
[6] (1) Utilization of catalyst in catalyst reaction layer
[7] However, the region contributing to the actual electrode reaction in the catalytic reaction layer is considered to be a portion of 20 microns in thickness in contact with the polymer electrolyte membrane. This is because it is difficult for the generated hydrogen ions to reach the polymer electrolyte membrane. In addition, in the state where the carbon powder carrying the catalyst is not in electrical contact with another carbon powder or conductive electrode, even though hydrogen ions can be easily moved, movement of electrons to the external circuit is hindered. As a result, the catalytic reaction layer formed by coating has a problem that many of the portions do not contribute to the electrode reaction, the performance is lowered, and a large amount of platinum is required to restore the performance.
[8] That is, it is desired to improve the catalytic reaction layer, to effectively contribute the platinum catalyst to the electrode reaction, and to improve the utilization efficiency of the platinum catalyst.
[9] (2) Contact resistance between catalyst reaction layer and gas diffusion layer
[10] As the electrode used in the polymer electrolyte fuel cell, as described above, a catalyst reaction layer made of a carbon powder carrying a noble metal is formed on a porous conductive electrode substrate serving as a gas diffusion layer. As the porous conductive base material, carbon paper made of carbon fiber, carbon cloth or the like is used. It is common for these electrodes to be ink-ized using an organic solvent such as isopropyl alcohol and to form a carbon fine powder carrying a precious metal on a substrate by using a screen printing method or a transfer method.
[11] In recent years, in view of workability, an electrode ink using an aqueous solvent instead of an organic solvent has been proposed. However, when using these methods, the carbon powder carrying the noble metal which is a catalyst in an electrode invades partly in the electrode base material which comprises a gas diffusion layer. Therefore, countermeasures such as using a relatively large amount of electrode catalyst or increasing the tightening pressure of the battery to maintain the conductivity of the junction between the gas diffusion layer and the catalytic reaction layer are necessary. For this reason, the method of apply | coating and forming an electrode catalyst layer on a polymer electrolyte membrane previously is also proposed. These electrodes and the polymer electrolyte membrane are bonded to each other by a method such as hot press.
[12] As described above, in the polymer electrolyte fuel cell, it is strongly required not only to increase the utilization rate of the catalyst in the catalytic reaction layer but also to reduce the contact resistance between the carbon catalyst and carbon cloth constituting the gas catalyst layer and the catalytic reaction layer. It is becoming.
[13] (3) Reaction efficiency of polymer electrolyte and catalyst
[14] In an electrode which is a component of a polymer electrolyte fuel cell, pores, which are supply paths of reaction gases (fuel gas and oxidant gas), a hydrogen ion thermoelectric polymer electrolyte, and an electrode substrate, which is an electron conductor, are formed. The so-called three-phase interface area is one of the important factors that determine the discharge performance of the battery.
[15] In order to increase this three-phase interface, attempts have been made to impart a layer formed by mixing and dispersing the material constituting the electrode base and the polymer electrolyte to the interface between the polymer electrolyte membrane and the porous electrode base. For example, in the techniques described in Japanese Unexamined Patent Publications No. 62-61118 and No. 62-61119, a mixture of a dispersion of a polymer electrolyte and a catalyst compound is applied to a polymer electrolyte membrane, hot pressed with an electrode base material, A method of reducing a catalytic compound is disclosed. Moreover, the method of carrying out hot press by apply | coating and adhering on an electrolyte membrane after reducing a catalyst compound is also proposed.
[16] Also, Japanese Unexamined Patent Application Publication No. 2-48632 proposes a method of forming a porous electrode base material, dispersing a solution in which a resin constituting an ion exchange membrane is dispersed on the electrode base material, and hot pressing the electrode and the ion exchange membrane. It is becoming. Further, Japanese Patent Laid-Open No. 3-l84266 proposes a method in which a polymer electrolyte powder is coated on a surface of a polymer resin powder, and Japanese Patent Laid-Open No. 3-295172 a method of mixing the polymer electrolyte powder in an electrode. Further, Japanese Patent Laid-Open No. 5-36418 proposes a method of mixing a polymer electrolyte, a catalyst, a carbon powder, and a fluorine resin to form a film to form an electrode. As the above technique, alcohols are used as a solution for forming a polymer electrolyte in an electrode.
[17] Further, in US Pat. No. 5211984, a dispersion obtained by dispersing a polymer electrolyte, a catalyst, and a carbon powder in the form of ink in glycerin or tetrabutylammonium salt as a solvent is prepared, and the dispersion is referred to as polytetrafluoroethylene (hereinafter referred to as "PTFE". A method of transferring the film to the surface of the polymer electrolyte membrane after coating and molding on the film is disclosed. In addition, a method of replacing the exchanger of the polymer electrolyte membrane with a Na-type substituent, applying the ink phase dispersion liquid to the surface of the membrane and drying it by heating to 125 ° C or higher, and replacing the exchanger with the second H-type has been reported.
[18] On the other hand, in order to realize high output density, which is a characteristic of the polymer electrolyte fuel cell, it is important to form a supply path (gas channel) of the reaction gas in the catalytic reaction layer and to increase the permeation and diffusion capability of the gas. Therefore, attempts have been made to add gas-repellent materials such as fluororesins to the catalytic reaction side to form gas channels. For example, Japanese Patent Laid-Open No. 5-36418 proposes a method of producing a catalyst layer by dispersing and kneading a PTFE powder and a carbon powder carrying a catalyst in a polymer electrolyte solution. Further, in Japanese Patent Laid-Open No. 4-264367, it has been proposed to produce an electrode using a mixed liquid of a carbon powder carrying a catalyst and a colloidal liquid of PTFE.
[19] In addition, J. Electronal. Chem. No. 197 (1986) and page 195 propose a method of forming a gas diffusion electrode for an acidic electrolyte by mixing a carbon powder subjected to water repellent treatment with PTFE and a carbon powder carrying a catalyst. On the other hand, US Patent No. 5211984 proposes a method for producing a catalyst layer of an electrode using only a polymer electrolyte, a catalyst and a carbon powder without using the above water repellent material.
[20] However, when a carbon powder carrying a catalyst and a water-repellent material such as a fluorine resin or a water-repellent carbon powder are simultaneously added to a dispersion liquid in which the polymer electrolyte is dispersed, a large amount of the polymer electrolyte is adsorbed to the water-repellent material or the water-repellent carbon powder. do. At this time, the more the polymer electrolyte adsorbs to the carbon powder, the more uneven and inadequate the contact between the polymer electrolyte and the catalyst is, and as a result, a sufficient reaction area cannot be obtained at the interface between the electrode and the ion exchange membrane. I had a problem.
[21] In addition, when the dispersion liquid using an alcohol solvent is applied onto a plate-like porous substrate, or when the ink dispersion is applied onto the porous substrate, the dispersion liquid penetrates or permeates into the substrate. Therefore, the dispersion liquid cannot be molded directly on the substrate surface portion, and complicated processing techniques such as transfer are required. In addition, as a method of directly applying the ink phase dispersion to the surface of the film, a complicated production technique for replacing the exchanger of the film many times is required. In addition, the method of adding the fluorine resin has a problem that the catalyst fine particles are excessively coated by the fluorine resin, the reaction area is reduced, and the polarization characteristics are lowered.
[22] Meanwhile, J. Electronal. Chem. As in the technique described in No. 197 (1986) and page 195, when the carbon powder repelled by PTFE was used, the phenomenon that the catalyst particles were covered with PTFE was surely suppressed. However, in this proposal, when the polymer electrolyte is used, the addition of the water repellent treated carbon powder and the effect of the addition amount have not been examined.
[23] In addition, when an electrode is manufactured using only carbon powder and a polymer electrolyte carrying a catalyst, so-called flooding occurs due to the generated water generated in the fuel cell. When the battery is driven at a high current density, the voltage of the battery becomes low and unstable. I had a problem.
[24] That is, in order to exhibit higher performance, it has been required to increase the reaction area inside the electrode by sufficiently and uniformly contacting the polymer electrolyte and the catalyst.
[25] In addition, the polymer electrolyte type exhibits high performance even when the battery is driven at a high current density by increasing the gas permeability of the electrode by forming hydrogen ion channels and gas channels without excessively covering the catalyst by adding fluorine resin. Fuel cells were also required.
[26] (4) Improvement of reaction catalyst layer
[27] Currently, the polymer electrolyte used in the polymer electrolyte fuel cell exhibits the required ion conductivity when sufficiently wet with water. On the other hand, the electrode reaction as a battery is a production reaction of water generated at the three-phase interface of the catalyst, the polymer electrolyte, and the reaction gas, and if the produced water generated by the water vapor or the electrode reaction in the gas to be supplied is not discharged promptly and stays in the electrode or diffusion layer, Gas diffusion becomes worse and battery characteristics deteriorate on the contrary.
[28] In view of this, measures for promoting the moisturization of the polymer electrolyte and the discharge of water have been taken for the electrode used in the polymer electrolyte fuel cell. For example, as described above, as a general electrode, a carbon powder carrying a noble metal serving as a catalytic reaction layer is formed on a porous conductive electrode substrate serving as a gas diffusion layer. As the porous conductive substrate, carbon paper made of carbon fiber, carbon cloth, or the like is used. These porous conductive substrates are subjected to a water repellent treatment using a dispersion of PTFE-based material in advance, so that the generated water generated by the electrode reaction is promptly discharged, and the polymer electrolyte membrane or the polymer electrolyte in the electrode has a suitable wet state. It is common to make it possible. As another method, a method of mixing the water-repellent carbon powder in the catalytic reaction layer and discharging excess product water in the catalytic reaction layer is also employed.
[29] However, according to the above-described technique, although the dischargeability of water in the gas diffusion layer is improved, the dischargeability of water in the catalytic reaction layer and the gas diffusion property into the catalytic reaction layer are inferior, in particular, when the air utilization is high or during large current discharge. There was a problem that the battery characteristics were lowered.
[30] In addition, when the carbon subjected to the water repellent treatment using the PTFE dispersed particles of the submicron order is introduced into the catalytic reaction layer, as described above, the polymer electrolyte in the catalytic reaction layer adsorbs a lot to the water-repellent carbon particles, There was a problem that the contact ratio between the polymer electrolyte and the catalyst fine particles was insufficient and became uneven, or the catalyst particles were covered with PTFE, so that a sufficient three-phase interface could not be secured. In addition, when the carbon particles carrying the catalyst particles exhibit water repellency, there is a problem that the state of the polymer electrolyte in the polymer electrolyte membrane or the catalyst reaction layer is shifted from the wet state to the dry state, resulting in a decrease in battery characteristics.
[31] As such, there is a demand for a high-performance electrode having a design in which water does not stay in the catalytic reaction layer and the polymer electrolyte is kept in an appropriate wet state.
[32] That is, an object of the present invention is to solve the above problems by controlling the configuration of the electrode in the fuel cell and to improve the efficiency of the electrode reaction in the polymer electrolyte fuel cell.
[33] [Initiation of invention]
[34] The present invention is a fuel cell comprising a polymer electrolyte membrane, a pair of electrodes having a catalytic reaction layer and a gas diffusion layer, wherein the polymer electrolyte membrane is sandwiched by a pair of electrodes, and supports the catalyst particles in the catalytic reaction layer. A polymer electrolyte fuel cell, characterized in that a part of the carrier to penetrate the inside of the polymer electrolyte membrane.
[35] It is effective that the carrier is acicular carbon fiber.
[36] The present invention also provides a fuel cell comprising a polymer electrolyte membrane, a pair of electrodes having a catalytic reaction layer and a gas diffusion layer, wherein the polymer electrolyte membrane is sandwiched by a pair of electrodes, wherein the catalytic reaction layer and The present invention also relates to a polymer electrolyte fuel cell having a layer composed of conductive fine particles between gas diffusion layers.
[37] In this case, it is effective that a part of the layer made of the conductive fine particles penetrate into the gas diffusion layer.
[38] In addition, it is effective that the average primary particle diameter of the conductive fine particles is 10 to 100 nm.
[39] In addition, it is effective that the materials of the conductive fine particles constituting the layer composed of the conductive fine particles differ in both sides of the polymer electrolyte membrane.
[40] In addition, it is effective that the conductive fine particles are selected from the group consisting of conductive fine particles made of carbon, conductive fine particles made of metal, conductive fine particles made of carbon-polymer composite material, and conductive fine particles made of metal-polymer composite material.
[41] It is effective that the carbon-polymer composite material is a carbon powder having PTFE attached thereto.
[42] It is effective that PTFE content of the layer which consists of said electroconductive fine particles is 5-75 weight%.
[43] The present invention also provides a fuel cell including a polymer electrolyte membrane, a pair of electrodes having a catalytic reaction layer and a gas diffusion layer, wherein the polymer electrolyte membrane is sandwiched by a pair of electrodes, the catalyst in the catalytic reaction layer. The present invention relates to a polymer electrolyte fuel cell comprising a hydrogen ion diffusion layer on at least one surface of a carrier supporting particles and the catalyst particles.
[44] It is effective that the hydrogen ion diffusion layer is formed by chemically bonding a silane compound to at least one surface of the catalyst particles and the carrier supporting the catalyst particles.
[45] It is effective that the hydrogen ion diffusion layer is composed of an organic compound having a basic functional group and a hydrogen ion conductive solid electrolyte, and the organic compound modifies at least one surface of the catalyst particles and the carrier supporting the catalyst particles. .
[46] In this case, it is effective that the basic functional group has a nitrogen atom having a non-covalent electron pair.
[47] Moreover, it is effective that the organic compound which has the said basic functional group is a silane compound.
[48] In addition, it is effective that the silane compound has a functional group capable of dissociating hydrogen ions.
[49] It is also effective that the silane compound has at least one of a hydrocarbon chain and a fluorocarbon chain.
[50] Further, the silane compound is a carrier supporting the catalyst particles and the catalyst particles via at least one functional group selected from the group consisting of phenolic hydroxyl groups, carboxyl groups, lactone groups, carbonyl groups, quinone groups and carboxylic acid anhydride groups. It is effective to be chemically bound to at least one surface.
[51] The present invention also provides a fuel cell including a polymer electrolyte membrane, a pair of electrodes having a catalytic reaction layer and a gas diffusion layer, wherein the polymer electrolyte membrane is sandwiched by a pair of electrodes, wherein the catalytic reaction layer is at least A polymer electrolyte fuel cell comprising a catalyst body formed by supporting catalyst particles on a hydrophilic carbon material and a water repellent carbon material.
[52] In this case, it is effective that the hydrophilic layer is chemically bonded to at least part of the surface of the catalyst particles.
[53] In the catalytic reaction layer, it is effective that the catalyst body is selectively disposed on the polymer electrolyte membrane side, and the water-repellent carbon material is selectively disposed on the gas diffusion layer side.
[54] It is also effective that the water-repellent carbonaceous material has a monomolecular layer formed by chemically bonding a silane coupling agent having a hydrophobic portion to at least a portion of the surface of the carbonaceous material.
[55] It is also effective that the hydrophilic carbon material has a layer formed by chemically bonding a silane coupling agent having a hydrophilic portion to at least a portion of the surface of the carbon material.
[56] In addition, the silane coupling agent is chemically bonded to the surface of the carbon material through at least one functional group selected from the group consisting of phenolic hydroxyl group, carboxyl group, lactone group, carboxyl group, quinone group and carboxylic acid anhydride group. It is effective.
[1] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel cell using a polymer electrolyte used for a portable power source, an electric vehicle power source, a home cogeneration system, and the like, and a manufacturing method thereof. The present invention relates in particular to electrodes of fuel cells.
[57] 1 is a schematic longitudinal sectional view showing an electrode electrolyte membrane assembly in an embodiment of the present invention.
[58] FIG. 2 is a schematic cross-sectional view schematically showing a surface portion of an electrolyte membrane in the electrode electrolyte membrane assembly shown in FIG. 1.
[59] 3 is a schematic sectional view of an electrode used in Example 5 of the present invention.
[60] 4 is a diagram showing the relationship between the current and the voltage of the fuel cell single cell according to the fifth embodiment of the present invention.
[61] 5 is a diagram showing the relationship between the current and the voltage of the fuel cell single cell according to the sixth embodiment of the present invention.
[62] 6 is a diagram showing the relationship between the current and the voltage of the fuel cell single cell according to the seventh embodiment of the present invention.
[63] Fig. 7 is a schematic diagram conceptually showing the shape of the electrode part in the ninth embodiment of the present invention.
[64] Fig. 8 is a schematic diagram conceptually showing the shape of the electrode part in the tenth embodiment of the present invention.
[65] Fig. 9 is a schematic sectional view of a catalyst fine particle or catalyst carrier adsorbing a monomolecular film in Examples 9 and 10 of the present invention.
[66] Fig. 10 is a schematic diagram conceptually showing the shape of the adsorption monomolecular film in Examples 9 and 10 of the present invention.
[67] Fig. 11 is a schematic cross-sectional view of the fuel cell produced in Examples 9 to 11 and 14 to 16 of the present invention.
[68] 12 is a diagram showing the characteristics of a fuel cell constructed using the electrodes of Examples 9 to 11 of the present invention.
[69] Fig. 13 is a schematic diagram conceptually showing the shape of the surface of the catalyst carrier in Examples 9 and 10 of the present invention.
[70] Fig. 14 is a schematic cross-sectional view of a catalyst fine particle or catalyst carrier adsorbing a monomolecular film in Examples 9 and 10 of the present invention.
[71] FIG. 15 is a diagram showing the characteristics of a fuel cell constructed using the electrodes of Examples 9 and 10 of the present invention.
[72] Fig. 16 is a schematic diagram conceptually showing the shape of the surface of the carbon particles used in Example 14 of the present invention.
[73] FIG. 17 is a diagram showing a relationship between current and voltage of the fuel cell obtained in Example 14 of the present invention. FIG.
[74] 18 is a schematic sectional view of an electrode in a fifteenth embodiment of the present invention.
[75] Fig. 19 is a schematic diagram conceptually showing the shape of the surface of the catalyst-supported carbon particles used in Example 16 of the present invention.
[76] Best Mode for Carrying Out the Invention
[77] In order to solve the above-mentioned problems, the present invention can adopt various forms. EMBODIMENT OF THE INVENTION Below, for each said problem, embodiment and its Example are described.
[78] (1st embodiment)
[79] In a first embodiment of the present invention for solving the above problem (1), a plurality of laminates in which a pair of electrodes in which a polymer electrolyte membrane is sandwiched are sandwiched with conductive separators, and an oxidizing agent in one side of the electrode with fuel gas In a polymer electrolyte fuel cell having gas supply and discharge means for supplying and discharging gas, respectively, a portion of the carbon particles carrying the electrode reaction catalyst infiltrates into the polymer electrolyte membrane.
[80] In this case, it is effective that the carbon particles carrying the catalyst are acicular fibers.
[81] In addition, such a polymer electrolyte fuel cell may be manufactured using a process of incorporating a catalyst-carrying carbon particle into a carrier gas to impinge on the polymer electrolyte membrane to infiltrate a portion of the carbon particle into the polymer electrolyte membrane. Can be.
[82] In addition, the carbon particles carrying the catalyst can be produced by a step of injecting a part of the carbon particles into the polymer electrolyte membrane by charging the static electricity and simultaneously accelerating the electric electrolyte to the polymer electrolyte membrane.
[83] Since the first embodiment of the present invention has a configuration in which carbon particles carrying a catalyst are infiltrated or inserted into the polymer electrolyte membrane as described above, hydrogen ions generated in the electrode reaction can be easily moved into the polymer electrolyte membrane. have. At the same time, the movement of electrons can be made easy by welding an electrode such as carbon paper to one end of the carbon particles.
[84] EMBODIMENT OF THE INVENTION Below, the Example which concerns on the 1st Embodiment of this invention is described.
[85] Example 1
[86] In the black carbon powder or the granulated acetylene black powder, 25 wt% of platinum particles having an average particle diameter of about 30 angstroms were supported. This is referred to as catalyst supported carbon particles. The average particle diameter of the black carbon particles and the granulated acetylene black powder was 2 to 10 microns.
[87] With PTFE as the main chain, the catalyst-carrying carbon powder is sprinkled on a 50-micron-thick polymer electrolyte membrane 11 having a side chain having a sulfonic acid group at its end, and slowly pressed at a pressure of 2000 kgf / 10 cm by a roller press of 10 cm diameter. Pressurization was carried out so that carbon particles might be buried and infiltrated in the polymer film. At this time, as a result of pressurizing various temperatures and humidification conditions, the higher the humidity and the higher the temperature, the higher the degree of penetration of the carbon particles into the film. The amount of the catalyst-carrying carbon powder penetrated into the membrane was about 0.01 to 0.5 mg / cm ² per catalyst reaction layer in terms of platinum amount in any carbon powder.
[88] Next, both sides were sandwiched by a cathode 12 and an anode 13 made of polyacrylonitrile-based carbon fibers, and hot pressed at 110 kgf for 10 minutes at a pressure of 10 kgf / cm ^{2 to obtain} a polymer electrolyte membrane ( 1) and the anode 2 and the cathode 3 were integrally bonded. This electrode electrolyte membrane assembly is shown in FIG.
[89] A laminated battery was assembled by stacking 10 cells of a 5 cm x 5 cm electrode using a fluororesin sealing material and a carbon separator plate. As a result of a discharge test in which hydrogen was supplied to the anode and air to the cathode, the use of acetylene black granules in the carbon powder showed that the use rate of the fuel was 70% and the air use rate was 0.3 mg / cm ² . At 30%, an output of 0.6 V-0.5 A / cm ² was obtained. This is almost the same performance as a conventional battery having a platinum consumption of 0.5 mg / cm ² . The use of the glass carbon powder in the carbon powder has a lower performance than that of the acetylene black. Moreover, when platinum use amount was less than 0.2 mg / cm <^2> , performance fell rapidly.
[90] Example 2
[91] Next, various methods were examined in order to insert carbon particles into the polymer electrolyte membrane more efficiently. The carbon powder carrying the catalyst was collided with the polymer electrolyte membrane at high speed by using nitrogen as the carrier gas. The gas flow rate of the nitrogen gas was changed to 1 to 200 m / sec, and the nitrogen gas was humidified in order to prevent sudden drying of the electrolyte membrane. The average particle diameter of the carbon powder was 0.1-20 microns. In this example, the carbon particles in the polymer electrolyte membrane could be infiltrated even if the press-in of the particles by the roller press as in Example 1 was not used. As a result of the same discharge test as in Example 1, overall performance was obtained better than that in Example 1. Ultrafine powder with a particle diameter of less than 1 micron of glass carbon is used, and 0.62 V-0.5 A / cm ² (fuel utilization rate 70%, air utilization rate 30%) despite the low amount of platinum 0.2 mg / cm ² . As a result, high performance was achieved. When acetylene black was also used, higher performance was confirmed as compared with Example 1.
[92] Example 3
[93] In this example, acicular carbon was used instead of the spherical carbon powder of Example 2. As acicular carbon, a polyacrylonitrile-based carbon fiber (0.01 to 0.3 mg / cm ² ) having a large specific surface area (10 m ² / g or more) supported by platinum was used. The average length of acicular carbon was 15 microns. As a result of the discharge test, when the amount of platinum used was 0.1 mg / cm ² , very high performance was obtained at 0.64 V-0.5 A / cm ² (70% fuel utilization and 30% air utilization).
[94] According to the micrograph of the cross section of the polymer electrolyte membrane, as shown in the schematic diagram in FIG. 2, it was observed that a large number of needle-like carbons 4 serving as electrode reaction portions penetrated into the polymer electrolyte membrane 1. The exposed portion of the needle-like carbon 4 of FIG. 2 is buried in the anode or the cathode. Since acicular particles such as carbon fibers reach a deeper portion of the polymer electrolyte membrane, for example, a depth of about 10 microns, and the fibers are exposed on the surface, electrical bonding with the electrode is also good.
[95] Example 4
[96] In order to infiltrate the carbon particles into the polymer electrolyte membrane more efficiently, the electric acceleration method was examined as various methods. Various carbon powders carrying catalyst platinum were blown out of the nozzle and electrostatically charged by corona discharge. Then, an acceleration voltage was applied between the injector for injecting carbon and the metal fixing device to which the polymer electrolyte membrane was fixed. The voltage for acceleration was examined up to 100 V to 5000 V. The amount to chop the carbon powder was controlled by time. If it is chopped with high acceleration voltage for too long, the curvature of a polymer electrolyte membrane might become large or it may be damaged. The catalyst was supported on acetylene black, glass carbon and acicular carbon, and experimented under various conditions. As a result, the performance of immersing acicular carbon at 1000 V for 1 minute at an accelerating voltage was remarkably high, and the amount of platinum used was 0.07 mg / At cm ² , 0.66 V-0.5 A / cm ² (70% fuel utilization, 30% air utilization) was recorded. It was confirmed that it was more effective to chop the carbon powder in the vacuum chamber under reduced pressure or to apply a little polymer electrolyte to the carbon particles again.
[97] In a series of experiments, the carbon particles are pushed by a roller press or the like, so that the carrier gas, or the method of electrically accelerated and compacted carbon, has a better performance. The carbon surface and the polymer electrolyte when compacted at higher speed are better. It is presumed that this is because the bonding with the resin improves. As the electrode used as the current collector, in addition to the carbon paper used in the present embodiment, a carbon cloth or a conductive sheet in which carbon powder is mixed in the resin can be used. In addition, in order to improve the electrical bonding property with the chopped carbon particles and carbon needles, even if a method of coating conductive carbon paste on the surface to be bonded to the polymer electrolyte membrane of carbon paper, good results were obtained.
[98] (2nd Embodiment)
[99] A second embodiment of the present invention for solving the above problem (2) is a fuel cell provided with electrodes comprising a catalytic reaction layer and a gas diffusion layer on both sides of a polymer electrolyte membrane, wherein the catalyst reaction layer and the gas diffusion layer A polymer electrolyte fuel cell characterized by arranging a layer made of conductive fine particles in between.
[100] It is effective that the layer made of the above conductive fine particles intrude at least partially into the gas diffusion layer.
[101] Moreover, it is effective to comprise the layer which consists of electroconductive fine particles from electroconductive fine particles which have a 10-100 nm average primary particle diameter.
[102] The conductive fine particles may be made of different materials from both sides of the polymer electrolyte.
[103] The conductive fine particles may be composed of at least one of carbon, metal, carbon-polymer composite material and metal-polymer composite material. That is, the layer composed of conductive fine particles may be composed of one kind of conductive fine particles or may be composed of a plurality of conductive fine particles.
[104] As said carbon-polymer composite material, the carbon powder to which PTFE adhered, etc. are mentioned, for example.
[105] In this case, the layer made of conductive fine particles may contain 5 to 75 weight of PTFE.
[106] According to the second embodiment of the present invention, since the layer made of conductive fine particles is disposed between the catalyst reaction layer and the gas diffusion layer, the contact resistance between the electrode catalyst layer and the gas diffusion layer is reduced and the battery characteristics are improved.
[107] In addition, the effect can be further improved by injecting a layer made of conductive fine particles into a part of the gas diffusion layer. In addition, since the catalytic reaction layer cannot penetrate into the gas diffusion layer, the amount of the noble metal catalyst used in the catalytic reaction layer can be reduced than before, and a cost reduction effect can be expected.
[108] In general, a method such as hot place is used to join the polymer electrolyte membrane and the electrode. In this case, the use of a carbon material having PTFE adhered to the conductive fine particle layer also has the advantage that the physical binding property between the electrode catalyst layer and the gas diffusion layer is increased, and the handling becomes easy. In this case, since the PTFE is introduced, a secondary effect can be expected, in particular, that a part of the generated water generated in the air electrode is put into the electrolyte membrane and the remaining generated water can be discharged to the gas diffusion layer side. In this case, it is effective by changing the content of PTFE in the air electrode and the fuel electrode.
[109] That is, according to the second embodiment of the present invention, since the conductive fine particle layer is disposed between the electrode catalyst layer and the gas diffusion layer, a fuel cell having higher performance than before can be formed.
[110] EMBODIMENT OF THE INVENTION Below, the Example of 2nd Embodiment of this invention is described.
[111] Example 5
[112] First, the manufacturing method of the electrode used for the fuel cell of this invention is demonstrated. Screen printing method on carbon paper (TGP-H-120 manufactured by Toray Co., Ltd., made of Toray Corporation, thickness of 360 µm) to form an gas diffusion layer 1 by incorporating acetylene black having an average primary particle diameter of 50 nm into butyl acetate. Coating was carried out to form the screen printable particulate layer 2. Further, an electrode catalyst powder made of carbon powder carrying 25 wt% of platinum is mixed with a dispersion of a polymer electrolyte (Flemion, manufactured by Asahi Glass Co., Ltd.) and butyl acetate, and inkized. Coating was carried out using screen printing to form a catalytic reaction layer. The platinum amount per unit area was 0.2 mg / cm <^{2> here} .
[113] The electrode thus produced was placed on both sides of the polymer electrolyte membrane (Nafion 112, manufactured by Du Pont), and hot pressed to prepare an electrode-electrolyte assembly. 3 is a schematic cross-sectional view of the electrode portion of the joined body. As a result, it is found that a part of the conductive fine particle layer 6 penetrates into the carbon paper "gas diffusion layer 5". And 7 is a catalytic reaction layer. In addition, for comparison, an electrode of a catalytic reaction layer and a gas diffusion layer having no conductive fine particle layer was also prepared. These were set in the unit cell measuring apparatus to constitute a unit cell.
[114] These cells have hydrogen gas flowing through the anode and air through the cathode, with a battery temperature of 75 ° C, fuel utilization of 80%, air utilization of 30%, gas humidification of hydrogen gas of 75 ° C and air of 65 ° C dew point. Was adjusted to The battery current-voltage characteristics at this time are compared and shown in FIG. As a result, it was found that the battery having the conductive fine particle layer exhibited higher characteristics than the battery having no conductive fine particle layer. This is considered to be because the contact resistance between the catalyst of the electrode and the gas diffusion layer was reduced by providing the conductive fine particle layer, and the reaction area of the platinum catalyst which actually contributed to the reaction was increased. For this reason, it showed that Pt use amount can be reduced more.
[115] Example 6
[116] Next, the case where the average primary particle diameter of the carbon which comprises an electroconductive fine particle layer was changed was investigated. In addition to the 50 nm acetylene black used in Example 5, five kinds of carbons having different particle diameters were used, and the same cell as in Example 5 was fabricated to investigate the cell performance. The electrode production method and the battery operating conditions were the same as in Example 5. In Table 1, the battery voltages at the current densities of 700 mA / cm ² are compared with respect to these batteries.
[117] Table 1
[118] Average primary particle diameter (nm) Battery voltage (V) 5 0.59 10 0.63 50 0.64 100 0.63 500 0.58
[119] As a result, it was found that the battery performance was increased when the particle diameter was 10 to 100 nm. This is considered to be because when the particle diameter is too small, the carbon fine particles penetrate completely into the porous carbon paper and the gas diffusion worsens, resulting in deterioration of characteristics. In the case where the particle diameter is 500 nm, the particle diameter is so large that contact with the carbon paper is bad, and battery characteristics are deteriorated.
[120] Moreover, the case where the material which comprises an electroconductive fine particle layer was changed next was examined. In addition to carbon particles, electrodes were produced in the same manner as for titanium and nickel, and set in a unit cell measuring device to investigate battery performance. As a result, initial battery characteristics were equivalent even when any material was used.
[121] From these results, in the fuel cell of this embodiment, since the electrically conductive fine particle layer was disposed between the catalyst reaction layer and the gas diffusion layer, it was found that the contact resistance can be reduced and the battery characteristics are improved compared with the conventional one. It has also been found that battery characteristics are increased when a material having a particle diameter of 10 to 100 nm is used. As for the conductive material to be used, all of the materials investigated in this example showed good results.
[122] In the present invention, the conductive fine particle layer is formed using the screen printing method, but any other method may be used as long as it can be formed between the catalytic reaction layer and the gas diffusion layer. The polymer electrolyte membrane, the electrode catalyst and the gas diffusion layer to be used are also not limited to this embodiment.
[123] Example 7
[124] In the present Example, the case where the carbon powder which PTFE adhered was used for the electroconductive fine particle layer was investigated.
[125] PTFE-attached carbon powder (PTFE / C) is a colloid mill made of acetylene black, PTFE dispersion (made by Daikin Industries Co., Ltd., D-1), and surfactant "Triton X-100 made by ACROSORGA NICSCO. (USA)". After mixing by using a heat treatment was produced. The PTFE content of the produced PTFE / C was 30 weight%.
[126] The obtained PTFE / C was screen-printed on the carbon paper similarly to Example 5, and the electroconductive fine particle layer was formed. Subsequently, the catalyst reaction layer was formed in the same manner to prepare an electrode. The obtained electrodes were placed on both sides of the Nafion membrane to perform hot pressing to prepare an electrode-electrolyte assembly (MEA). This MEA has high bonding property over the whole surface, and it is considered that the reason why PTFE functioned as a binder in the MEA.
[127] Using this MEA, a unit cell was constructed in the same manner as in Example 5 to check the battery performance. In FIG. 5, the result is compared with the case where the acetylene black of Example 5 was used for the electroconductive fine particle layer. Accordingly, it can be seen that the battery characteristics are improved by using PTFE / C. This is considered to be because water repellency in the vicinity of the electrode is improved by introduction of PTFE.
[128] Next, the battery characteristics in the case of changing the amount of PTFE attached were examined. The amount of PTFE was changed by adjusting the density | concentration of PTFE dispersion liquid. In Table 2, when PTFE was changed, the battery voltage of the current density of 700 mA / cm ² is shown.
[129] TABLE 2
[130] PTFE amount (wt%) Battery voltage (V) One 0.63 5 0.66 10 0.67 25 0.68 50 0.68 75 0.67 80 0.57
[131] Accordingly, it can be seen that the battery performance is increased when the amount of PTFE is 5 to 75% by weight. This is considered to be because when the amount of PTFE is large, the conductivity is lowered, the battery performance is lowered, and the water repellency at the electrode portion is lowered at the lower portion. According to these results, it was found that the use of PTFE / C for the conductive fine particle layer improves the bonding performance of the MEA and the battery performance. This time, PTFE / C having a different loading amount was used to adjust the PTFE amount, but in addition to this, the PTFE amount may be adjusted by mixing PTFE / C and carbon powder, but the present invention is not limited to this embodiment.
[132] Example 8
[133] In this embodiment, the case where PTFE / C having a different composition from the anode and the cathode was used for the conductive particulate layer was investigated. Each electrode was produced in the same manner as in Example 2, using PTFE / C having a PTFE-supported amount of 60% by weight as the conductive particulate layer of the anode and PTFE / C having a PTFE-supported amount of 30% by weight as the conductive particulate layer of the cathode. The electrodes thus produced were placed on both sides of the Nafion membrane, and hot pressed to prepare an electrode-electrolyte assembly (MEA).
[134] The cell performance was examined by arranging the electrode using PTFE / C having a PTFE loading of 60% by weight in the unit cell test apparatus so as to be on the fuel gas flow path side. Here, the test conditions and the like of the unit cell were the same as in Example 6. 8 shows the current-voltage characteristics of this battery as compared with the case where PTFE / C having a PTFE loading of 30% by weight was used for the positive electrode of Example 6. FIG.
[135] As a result, it was found that the properties of the PTFE-supported amount were improved compared to the same case in the case of using a different composition from the anode and the cathode. This is considered to be because the humidification conditions of the polymer electrolyte membrane at the fuel electrode and the air electrode during battery operation are better than those using the same composition. Here, PTFE / C having a different PTFE loading in the conductive fine particle layer is used. However, other composite materials such as carbon materials, metal fine particles, mixtures of carbon materials and PTFE / C can also be used.
[136] (Third Embodiment)
[137] A third embodiment of the present invention for solving the above problem (3) is a fuel cell comprising a polymer electrolyte membrane and a pair of electrodes having a catalytic reaction layer sandwiching the polymer electrolyte membrane, wherein the electrode comprises a catalyst. A polymer electrolyte fuel cell comprising a diffusion layer of hydrogen ions on a carrier or surface of a catalyst particle.
[138] The diffusion layer of hydrogen ions can be formed by chemically bonding a silane compound to the surface of the catalyst particles or the carrier of the catalyst particles.
[139] The catalyst particles or the carrier surface of the catalyst particles may be modified with an organic compound having a basic functional group, and a diffusion layer of hydrogen ions may be formed from the organic compound and a hydrogen ion conductive solid electrolyte.
[140] It is effective that the basic functional group has a nitrogen atom having an unshared electron pair.
[141] In addition, the silane compound preferably has a functional group capable of dissociating hydrogen ions at its terminal, and preferably has at least one of a hydrocarbon chain or a fluorocarbon chain.
[142] The carbon particles or carbon fiber and the silane compound may be chemically bonded through at least one functional group selected from phenolic hydroxyl group, carboxyl group, lactone group, carbonyl group, quinone group or carboxylic anhydride group.
[143] In this polymer electrolyte fuel cell according to the third embodiment, the electrode can be manufactured as follows.
[144] That is, after immersing the silane compound on the surface of the to-be-bonded material by immersing at least one to-be-joined material selected from a catalyst particle, a catalyst carrier, carbon particle, or carbon fiber in the solvent containing a silane compound, What is necessary is just to form the diffusion layer of hydrogen ion by chemically bonding the surface of the said to-be-joined material with the silicon atom among the molecules of the said silane compound.
[145] According to the third embodiment, the hydrolyzable group of the silane compound is hydrolyzed on the surface of the catalyst metal or on the surface of the carbon material serving as the catalyst by moisture in the solution or in the air and adsorption water on the surface of the catalyst. At this time, the hydrolyzable group is changed into an active silanol group (≡SiOH), and reacts with an oxide on the surface of the catalytic metal or a functional group on the surface of the carbon material to form a strong bond. By having the silane compound have a hydrogen ion dissociable functional group such as a sulfonic acid group or a carboxyl group, the hydrogen ionization layer can be coated on the surface of the catalyst in the form of a single molecule. Then, by covering the catalyst metal and the carbon carrier, it becomes possible to form a monomolecular hydrogen ion channel. The thickness of the single molecule layer can be controlled to several nm to several tens of nm.
[146] Generally, the polymer electrolyte exhibits a sufficient gas supply capacity in the depth direction up to about several hundred nm for the electrode reaction of the fuel cell. Therefore, the polymer electrolyte layer according to the third embodiment of the present invention can maintain sufficient gas solubility and cover the surface of the catalyst as in the case of using PTFE disperse particles of a submicron order that has been conventionally used. There is nothing to disturb the supply of
[147] 7 shows a cross section of the fuel cell electrode according to the embodiment of the present invention. In FIG. 7, the polymer electrolyte layer is uniformly adsorbed to the catalyst powder as described above, so that the fine particles 13, the carbon fine powder 14, and the polymer electrolyte of the catalyst (11) inside the catalyst layer 12 of the electrode 11. It is possible to make 15) the state in which it adhered uniformly mutually.
[148] By the structure of the catalyst layer 12 as described above, the gas channel 17 and the polymer electrolyte layer formed by the empty holes between the carbon powders 14 serving as the supply paths of fuel gas such as hydrogen or oxygen gas such as oxygen are formed. The three channels of the hydrogen ion channel 18 formed by (15) and the electron channel 16 formed by the carbon fine powder interconnection are efficiently formed in the very vicinity of the same catalyst layer. In FIG. 7, 19 is a gas diffusion layer and 20 is a polymer electrolyte membrane.
[149] At this time, a reaction represented by the reaction formula: H ₂ → 2H ⁺ + 2e ⁻ occurs in the hydrogen electrode, and a reaction represented by the reaction formula: 1 / 2O ₂ + 2H ⁺ + 2e ⁻ → H ₂ O in the oxygen electrode. This happens. At this time, when the electrode shown in Fig. 7 is used, the supply of hydrogen and oxygen gas and the transfer of hydrogen ions and electrons are simultaneously and extensively lubricated, thereby increasing the reaction rate and the reaction area and exhibiting higher discharge performance. The polymer fuel cell can be realized.
[150] In addition, since the size of the single molecule is sufficiently small, a polymer electrolyte molecule of several hundred nm order conventionally used can coat the catalyst in the pore which could not be adsorbed. For this reason, a hydrogen ion channel can be formed also in the catalyst in a pore, and can contribute to reaction.
[151] At this time, by having the silane compound have a hydrocarbon chain, the water repellency of the polymer layer can be increased, and by having a fluorocarbon chain, the water repellency of the polymer layer can be further increased.
[152] In addition, when substituted into the ends of the silane compound, -SO ₃ H or -COOH group and the like, and the increased hydrophilicity is, to improve the water holding capacity of the electrode. As a result, for example, the fuel cell is operated at a low current density, and the electrode maintains a constant water holding force and high performance even when the number of generated water is low or the air is operated at low humidity. When the water repellency is increased, the fuel cell is operated at a high current density, for example, and the gas diffusion capability of the electrode can be improved and high performance can be obtained even when the generated water is large or the operation is performed in high humidified air.
[153] Further, as shown in FIG. 8, a hydrogen ion channel is formed on the surface of the catalyst by using a hydrogen ion dissociable functional group and a water-repellent silane compound having a hydrocarbon chain, and a stronger water-repellent silane compound having a fluorocarbon chain. It is also possible to form a gas channel on the surface of the catalyst using. By using this, a polymer fuel cell exhibiting higher polarization characteristics in a high current density range can be realized. By coating the water-repellent silane compound having a fluorocarbon chain on the carbon powder not carrying a catalyst, the water-repellent monomolecular layer 21 can be formed, and the gas channel 17 is formed without reducing the catalyst surface area. can do.
[154] In addition, by mixing a polymer electrolyte layer used in the above configuration and a polymer electrolyte such as "Nafion solution" manufactured by Aldrich Chemical Co., Ltd., which is conventionally used, continuous hydrogen ion channels are formed from the catalyst in the pore to the surface of the electrolyte membrane. It is possible to realize a high performance electrode having a large reaction area and small internal resistance.
[155] Further, the hydrolyzable group of the silane compound is hydrolyzed on the surface of the catalyst metal or on the surface of the carbon material serving as the catalyst by water in the solution or in the air and adsorption water on the surface of the catalyst. At this time, the hydrolyzable group is changed into an active silanol group (≡SiOH), reacts with an oxide on the surface of the catalytic metal or a functional group on the surface of the carbon material, and forms a strong bond. When the silane compound has a basic functional group having a nitrogen atom having a non-covalent electron pair such as an amide group or an amine group at its terminal, interaction with a polymer electrolyte having an acid group such as sulfonic acid can be caused. At this time, the polymer electrolyte layer can be formed by strongly pulling the polymer electrolyte on the monomolecular surface, that is, near the surface of the catalyst carrier. Accordingly, it is possible to form a hydrogen ion channel, which is a dense hydrogen ionization layer on the surface of the catalyst and the catalyst carrier.
[156] This effect is due to the interaction between the basicity of the monomolecular layer coated with the catalyst carrier and the acidic reaction of the polymer electrolyte, which enables the polymer electrolyte to be present closer to the catalyst metal.
[157] In addition, the presence of the polymer electrolyte in the vicinity of the catalyst and the increase in the ratio of covering the catalyst metal resulted in the formation of a hydrogen ion channel that effectively transports the hydrogen ions produced by the catalytic reaction and improved catalyst efficiency. .
[158] In the case where the main chain skeleton of the silane compound forming the monomolecular layer is a hydrocarbon chain, the water repellency of the hydrocarbon chain is relatively weak, so that the entire catalyst layer is wet. This indicates that the water holding power of the electrode is improved. In other words, the fuel cell is operated at a low current density, so that the electrode can maintain a constant water holding power and obtain high performance even when the number of generated products is low or in low-humidity air.
[159] On the other hand, the hydrogen fluoride chain is highly water repellent, and as shown in Fig. 13, a monolayer layer 81 is formed by using a silane compound having a hydrogen fluoride chain, and a hydrogen fluoride chain is used as the polymer electrolyte. Flemion], the water repellent layer 83 can be formed between the monomolecular layer 81 and the polymer electrolyte layer 82 by both water repellent effects. At this time, the water present in the water repellent layer 83 can be more easily drawn out of the reaction product water out of the system by the water repellent effect of both layers described above, and can maintain the effect of humidifying the inside of the electrode in an appropriate state.
[160] As described above, even when the polymer fuel cell is operated at a high current density, and a large number of generated water is used or when high humidified air is used, sufficient water diffusion capability can be exhibited in the electrode due to this water repellent effect, and the battery is sufficiently high. Performance can be obtained.
[161] In the case of using a silane compound having a hydrocarbon chain, a hydrogen ion channel can be formed on the surface of the catalyst, and when using a silane compound having a hydrogen fluoride chain, a gas channel can be formed on the surface of the catalyst. As described above, by changing the main chain skeleton of the silane compound, the characteristics of the catalyst layer in the electrode can be designed in accordance with a suitable operating environment, thereby realizing a polymer fuel cell exhibiting high discharge characteristics.
[162] Below, the Example of 3rd Embodiment of this invention is described.
[163] Example 9
[164] As shown in Fig. 9, the catalyst particles 3 made of platinum having a particle diameter of about 1 to 10 nm are directly combined in a nitrogen gas atmosphere on the surface of the carbon particles 14 carrying 20% by weight. The adsorption reaction of the silane compound was carried out by adsorption to form a protective film 22 of a single molecule made of the silane compound. As the silane compound, n-hexane dissolved at a concentration of 1% by weight was adjusted using CH _3- (CH ₂ ) n-SiCl ₃ (n is an integer of 10 or more and 25 or less) having a linear hydrocarbon chain. Then, the carbon powder carrying the platinum particles described above was immersed.
[165] At this time, a natural oxide film is formed on the surface of the catalyst particles 13, which contains an -OH group or an oxide. As the carbon powder 14, those having surface functional groups such as phenolic hydroxyl group, carboxyl group, lactone group, carbonyl group, quinone group, and carboxylic acid anhydride were used on the surface thereof. The monomolecular adsorption membrane 22 made of the silane compound is then subjected to the surface of the catalytic metal 13 and the surface of the carbon carrier 14 by reacting with -SiCl ₃ , -OH or other functional groups or oxides. To a thickness of about 2 to 10 nm. Moreover, by changing the molecular weight of a single molecule, it was possible to shape | mold to thickness of about 1-100 nm.
[166] The chemical adsorption material is not limited to the silane compound used above as long as it contains a group having a bond to an -OH group or an oxide, such as a 'SiCl group'.
[167] As shown in Fig. 10, as the hydrogen ion dissociable functional group shown below, for example, a silane compound containing a sulfonic acid group, a carboxyl group, or the like could be hydrolyzed and used. That is, SiCl _3- (CH ₂ ) n-SO ₂ Cl (n is an integer), SiCl _3- (CH ₂ ) n-COCH ₃ (n is an integer), SiCl _3- (CH ₂ ) n- (C ₆ H ₄ ) -SO ₂ Cl (n is an integer), SiCl _3- (CH ₂ ) n-(C ₆ H ₄ ) -COOCH ₃ (n is an integer), and the like. By this method, a hydrogen ionizable monolayer 23 was formed on the surface of the catalytic metal 13 and the carbon carrier 14.
[168] Example 10
[169] In this embodiment, a silane compound containing fluorine, SiCl _3- (CH ₂ ) ₂ -CF ₃ , in a portion of the linear hydrocarbon chain is dissolved in cyclic silicone oil "KF994" manufactured by Shin-Etsu Chemical Co., Ltd. In the same manner as in the above-described Example 9, a water-repellent monomolecular layer 21 was formed on the surface of the carbon carrier. By using such a silane compound, the water repellency in the electrode can be improved and a gas channel for supplying the reaction gas can be formed.
[170] As the silane compound containing fluorine in a part of the linear hydrocarbon chain, SiC 1 _3- (CH ₂ ) _2- (CF ₂ ) m-CF ₃ (m is an integer of 0 to 9 or less) could also be used. .
[171] Example 11
[172] In this embodiment, SiCl _3- (CH ₂ ) n-(CF ₂ ) m -SO, which is a silane compound containing a sulfonic acid group as a hydrogen ion dissociable functional group and containing fluorine in a part of a linear hydrocarbon chain. ₃ H was formed by using the (n, m is an integer of 2 to 10), the monomolecular layer 23 of the proton conductivity to the surface of the catalyst metal 13 and the carbon carrier 14.
[173] As the hydrogen ion dissociable functional group, for example, a silane compound containing fluorine may be used as part of the linear hydrocarbon chain, including the sulfonic acid group, the carboxyl group, and the like described below. That is, SiC1 _3- (CH ₂ ) _2- (CF ₂ ) m-SO ₂ Cl (n, m is an integer), SiC1 _3- (CH ₂ ) _2- (CF ₂ ) m-COOCH ₃ (n, m is Integer), SiC1 _3- (CH ₂ ) _2- (CF ₂ ) m- (C ₆ H ₄ ) -SO ₂ Cl (n, m is an integer), SiCl _3- (CH ₂ ) _2- (CF ₂ ) m When-(C ₆ H ₄ ) -COOCH ₃ (m is an integer) was used, the effect was obtained by hydrolysis.
[174] (Comparative Example 1)
[175] For comparison, a carbon fine powder containing 20 wt% of platinum catalyst ultrafine particles 13 having a particle diameter of about 1 nm to 10 nm and a "5 wt% -Nafion solution" manufactured by Aldrich Chemical Co., Ltd. (USA) 14) was produced. The carbon fine powder 14 and butanol were mixed, dispersed in a ball mill, and then coated on carbon paper (Torre, TGP-H-120, film thickness of 360 µm) to form an electrode layer having a catalyst layer 12 ( 11) was produced.
[176] [Evaluation 1]
[177] As described above, the electrode catalyst powders described in Examples 9 to 11 and Comparative Example 1 were used to form the carbon diffusion film 19 manufactured by Toray Co., Ltd., TGP-H-120, and a film thickness of 360 µm. ), The catalyst layer 12 was formed, and this was used as the electrode 11.
[178] The electrode thus prepared was placed on both sides of the polymer electrolyte membrane (Nafion 112, manufactured by Du Pont) (10), subjected to hot press to fabricate an electrode-electrolyte assembly, and the resulting cell was measured in the fuel cell measurement cell shown in FIG. It was made and tested.
[179] In FIG. 11, 20 is a polymer electrolyte membrane. In FIG. 11, 24 and 25 are a cathode and an anode, respectively. The amount of the polymer electrolyte added was also referred to as the positive electrode and was 1.0 mg / cm ² per electrode area, but equivalent characteristics were obtained in the range of 0.1 to 3.0 mg / cm ² . In addition, the addition amount of platinum was 0.5 mg / cm <^2> by weight per electrode area similarly.
[180] Hydrogen gas was made to flow in the negative electrode 24 of these unit cells, and air was made to flow in the positive electrode 25. The battery was discharged by adjusting the battery temperature to 75 ° C, the fuel utilization rate to 80%, the air utilization rate to 30%, and the gas humidification so that the hydrogen gas was 75 ° C and the air to a dew point of 65 ° C.
[181] The unit cells produced using the method of Example 9, 11 and the comparative example 1 were set to A, B, and X, respectively. In addition, the unit cell in which the catalyst reaction layer was prepared was mixed by mixing the catalyst powder treated in Example 9 and the carbon carrier treated in Example 10 to obtain C.
[182] 12 shows current-voltage characteristics of batteries A, B, C, and X of Examples and Comparative Example 1 of the present invention. Table 3 shows the current density characteristics when the battery voltage is 850 mV, which is the reaction rate region, and the battery and voltage when the current density of the battery is 1000 mA / cm ² .
[183] TABLE 3
[184] Battery name Current density (mA / cm ² ) Voltage (V) A 48 0.55 B 50 0.64 C 50 0.66 X 9 0.29
[185] In Table 3, when the current density when the battery voltage is 850 mV, the battery C of Comparative Example 1 is 9 mA / cm ² , whereas the batteries A, B, and C using the electrode of the present example are The current density of 48, 50, 50 mA / cm ² was maintained, and this was about 5 times or more superior to the comparative example. This reason is considered that the electrode of this invention has a reaction area 5 times or more compared with the electrode of a comparative example.
[186] In addition, as the electrode of the present invention, a single molecule of a polymer having a film thickness of about 1 to l00 nm could be formed. Since the size of a single molecule is small enough, it is possible to coat a catalyst in a pore in which a polymer electrolyte molecule of several hundred nm order such as a conventional "Nafion solution" or the like cannot be adsorbed, and also form a hydrogen ion channel in the catalyst in the pore. It is considered that the high current density can be obtained by contributing to the reaction.
[187] The battery voltage when the current density was 1000 mA / cm ² was 0.55, 0.64, 0.66 V, while the batteries A, B, and C of the comparative example were 0.29 V, respectively. I could keep it. As described above, since the electrode of the present invention has a large reaction area, it is considered that a high characteristic can be obtained in comparison with the comparative example even when driven at a high current density. In addition, in the battery B, in order that the hydrogen-ion conductive monomolecule layer itself contains fluorine in a part of the hydrocarbon chain, gas solubility can be improved, the gas supply ability to the catalyst is improved, and We think that characteristic improved. Further, in the battery (C), a catalyst powder in which the hydrogen thermophilic monomolecular layer treated in Example 9 was adsorbed, and a carbon carrier in which a monomolecular layer containing fluorine was adsorbed to a portion of the linear hydrocarbon chain of Example 10 were used. Since it was mixed and the catalyst reaction layer was formed, it is considered that the gas supply capacity in the catalyst layer was increased, and the characteristics in the high current density region were improved.
[188] Example 12
[189] As shown in Fig. 14, the catalyst particles 91 made of platinum in the form of particles having a particle diameter of about 1 to 10 nm are chemically directly in the nitrogen gas atmosphere on the surface of the carbon particles 92 carrying 20 wt%. The adsorption reaction of the silane compound was carried out by adsorption to form a protective film of a single molecule composed of the silane compound. As the silane compound, an ethanol solution dissolved at a concentration of 1% by weight using CH _3- (CH ₂ ) n -Si (OCH ₃ ) ₃ (n is an integer of 2 to 10) having a linear hydrocarbon chain is used. The carbon powder carrying the platinum particles described above was immersed therein and heated at 60 ° C. for 1 hour.
[190] At this time, a natural oxide film is formed on the surface of the catalyst particles 91, which contains an -OH group or an oxide. Moreover, the carbon powder 92 used what has surface functional groups, such as a phenolic hydroxyl group, a carboxyl group, a lactone group, a carbonyl group, a quinone group, and a carboxylic anhydride group, exists in the surface. Therefore, by de-alcoholization with -Si (OCH ₃ ) ₃ group, -OH group, other functional group or oxide, the monomolecular adsorption membrane 93 by the silane compound is formed on the surface of the catalytic metal 91 and carbon. The surface of the carrier 92 was molded to a thickness of about 2 to 10 nm. Moreover, by changing the molecular weight of a single molecule, it was possible to shape | mold to thickness of about 1-100 nm.
[191] In addition, as a material for chemisorption, if it contains a group having a bond to -OH group or an oxide, such as Si (OCH ₃ ), Si (OC ₂ H ₅ ) group, etc., it is limited to the silane compound used above. It doesn't happen.
[192] As shown in FIG. 13, Si (OCH ₃ ) _3- (CH ₂ ) n-NH ₂ (n is 2 to 10, which is a silane compound containing an amine group as a basic functional group having a nitrogen atom having a non-covalent electron pair). Integer)) was used. By this method, the monomolecular layer 93 was formed on the surface of the carbon powder 92. In addition, by the action of the terminal base group, the polymer electrolyte layer 94 is densely formed in the vicinity of the surface of the catalyst metal and the carbon carrier to cover the monolayer 93, thereby forming a hydrogen ion channel for efficient hydrogen ion transport. It was.
[193] In this embodiment, Si (OCH ₃ ) _3- (CH ₂ ) n -NH ₂ (n is a silane compound containing an amide group or an amine group, for example, as a basic functional group having a nitrogen atom having a non-covalent electron pair). Integer), Si (OCH ₃ ) _3- (CH ₂ ) m-NH- (CH ₂ ) n-NH ₂ (m, n is an integer from 2 to 10), Si (OCH ₃ ) _3- (CH ₂ ) n- (C ₆ H ₄ ) -NH ₂ (n is an integer from 2 to 10), Si (OCH ₃ ) _3- (CH ₂ ) mN (CH ₃ ) ₂ (m is an integer from 2 to 10), Si (OCH ₃ ) _3- (CH ₂ ) n-(C ₆ H ₄ ) -N (CH ₃ ) ₂ (n is an integer from 2 to 10), Si (OC ₂ H ₅ ) _3- (CH ₂ ) nN (CH ₂ CH ₂ OH) ₂ (CH ₂ ) n (n is an integer of 2 to 10) could also be used.
[194] (Example 13)
[195] In this embodiment, as a basic functional group, a part of the linear hydrocarbon chain of the silane compound containing an amine group contains fluorine, and Si (OCH ₃ ) _3- (CH ₂ ) n-(CF ₂ ) m-NH ₂ (n, m is an integer of 2 to 10), and the monomolecular layer 22 was formed on the surface of the catalyst metal 13 and the carbon carrier 14 in the same manner as that of the straight chain hydrocarbon.
[196] In addition, as a silane compound to be used, fluorine is included in a part of a straight chain hydrocarbon chain including an amine group and an amide group, and Si (OCH ₃ ) _3- (CH ₂ ) n-(CF ₂ ) m -NH ₂ (n , m is an integer of 2 to 10), Si (OCH ₃ ) _3- (CH ₂ ) m-NH- (CH ₂ ) n- (CF ₂ ) 1 -NH ₂ (n, m, l is 2 to 7 Integer), Si (OCH ₃ ) _3- (CH ₂ ) n-(CF ₂ ) mN (CH ₃ ) ₂ (n, m is an integer of 2 to 8), Si (OCH ₃ ) _3- (CH ₂ ) n -(CF ₂ ) m- (C ₆ H ₄ ) -NH ₂ (n, m is an integer from 2 to 7), Si (OCH ₃ ) _3- (CH ₂ ) n- (CF ₂ ) m- (C ₆ H ₄ ) -N (CH ₃ ) ₂ (n, m is an integer from 2 to 7), Si (OC ₂ H ₅ ) _3- (CH ₂ ) n (CF ₂ ) mN (CH ₂ CH ₂ OH) ₂ ( n, m is an integer of 2-7), it was also possible to use.
[197] (Comparative Example 2)
[198] For comparison, a carbon fine powder containing 20 wt% of platinum catalyst ultrafine particles 13 having a particle diameter of about 1 to 10 nm and a "5 wt% -Nafion solution" manufactured by Aldrich Chemical Company (USA) ( 14) was produced. The carbon fine powder 14 and butanol were mixed, dispersed in a ball mill, and then coated on the carbon paper "Toray Co., Ltd. product, TGP-H-120, film thickness of 360 micrometers", and catalyzed by the catalytic reaction layer 12. The electrode 11 in which the was formed was produced.
[199] [Evaluation 2]
[200] As described above, using the electrode catalyst powders described in Examples 12, 13, and Comparative Example 2, this was used as the carbon diffusion film "Toray Co., Ltd. TGP-H-120, film thickness 360 micrometers" which is a gas diffusion layer. Coating was carried out on the catalyst reaction layer to obtain an electrode.
[201] The electrode thus produced was placed on both sides of the polymer electrolyte membrane (Nafion 112, manufactured by Du Pont) 20, and hot pressed to prepare an electrode-electrolyte assembly. Using the obtained single cell, the measurement cell of the fuel cell shown in FIG. 10 was produced and tested.
[202] Hydrogen gas flows through the anode 25 in the cathode 24 of these cells, the current temperature is 75 ° C, the fuel utilization rate is 80%, the air utilization rate is 30%, and the gas humidification is hydrogen gas at 75 ° C and air. Was adjusted to a dew point of 65 ° C., and the discharge test of the battery was carried out.
[203] The batteries produced using the electrodes produced in Examples 12, 13 and Comparative Example 2 were D (hydrocarbon chain type), E (hydrogen fluoride chain type) and Y (non-surface treatment type), respectively.
[204] 15 shows the current-voltage characteristics of the batteries D, E and Y of Examples and Comparative Examples of the present invention. In addition, Table 4 shows the battery and voltage when the drive current density of the battery is 300 mA / cm ² , which is a low current density, and 700 mA / cm ² , which is a high current density.
[205] Table 4
[206] Battery name Battery voltage (mV) i = 300 mA / cm ² i = 700 mA / cm ²D 770 670 E 750 690 Y 700 600
[207] In Table 4, it can be seen that the batteries D and E using the electrode of the present invention have higher battery characteristics compared with Comparative Example Y.
[208] Comparing the electrode of the present invention with a conventionally proposed electrode as a comparative example, despite the fact that the polymer electrolyte mass and platinum catalyst amount contained in the electrode are about the same, it is basic that the batteries D and E have improved characteristics over the battery Y. It is considered that the silane compound having a group covers the surface of the catalyst carrier and forms a monomolecular layer, and the monomolecular layer forms a more dense polymer electrolyte layer near the catalyst carrier, thereby enabling more efficient hydrogen ion exchange.
[209] In addition, in Table 4, it was confirmed that the difference in the main chain skeleton of the silane compound affects the battery characteristics. That is, a battery using an electrode made of a silane compound having a relatively weak hydrophobic hydrocarbon chain has a particularly high effect when the driving current of the battery is low, and an electrode made of an silane compound having a hydrogen fluoride chain having a high hydrophobicity. The battery was particularly effective when the driving current of the battery was high.
[210] In the above embodiment, the surface of the carbon powder, which is the catalyst carrier, was subjected to surface treatment. However, as long as the catalyst metal has -OH group or oxide on its surface, the structure of the present invention can be used for the catalyst metal itself.
[211] (4th Embodiment)
[212] In the fourth embodiment of the present invention for solving the above problem (4), the electrode in the fuel cell is characterized. That is, the fourth embodiment is a fuel cell including a hydrogen ion conductive polymer electrolyte membrane, a pair of electrodes sandwiched with the hydrogen ion conductive polymer electrolyte membrane, and an electrode electrolyte assembly including a pair of diffusion layers sandwiching the electrodes. The fuel cell is characterized in that the electrode has at least a catalyst body carrying catalyst particles on a hydrophilic carbon material, a hydrogen ion conductive polymer electrolyte, and a water repellent carbon material.
[213] It is preferable that a hydrophilic layer is chemically bonded to at least a part of the surface of the catalyst particles.
[214] In addition, it is preferable to selectively arrange the catalyst body in which the catalyst particles are supported on the hydrophilic carbon material on the hydrogen ion conductive polymer electrolyte membrane side, and selectively arrange the water repellent carbon material on the gas diffusion layer side.
[215] The water-repellent carbonaceous material preferably has a monomolecular layer formed by chemically bonding a silane coupling agent having a hydrophobic portion to a part or the entire surface of the carbonaceous material.
[216] It is preferable that the hydrophilic carbon material also has a layer formed by chemically bonding a part or the entire surface of the carbon material surface with a silane coupling agent having a hydrophilic portion.
[217] It is preferable that the said carbon material is chemically couple | bonded with a silane coupling agent through at least 1 functional group chosen from a phenolic hydroxyl group, a carboxyl group, a lactone group, a carbonyl group, a quinone group, or a carboxylic anhydride group.
[218] Next, the present invention also relates to a method for producing the electrode. That is, the electrode is chemically adsorbed on the surface of the catalyst particle or at least part of the surface of the carbon material by immersing at least one kind of catalyst particles or carbon material in a solvent containing a silane coupling agent, and then It can be produced by chemically bonding a silicon atom in the surface of the catalyst particle or the surface of the carbon material with the molecule of the silane coupling agent.
[219] As described above, in the fuel cell electrode according to the fourth embodiment of the present invention, since the catalytic reaction layer is composed of a polymer electrolyte, a hydrophilic carbon material, and a water-repellent carbon material, the vicinity of the three-phase interface near the electrode reaction occurs. The moisture is properly maintained by the hydrophilic carbon material, and the excess water is quickly discharged by the adjacent water-repellent carbon material.
[220] As a result, even when the fuel cell is operated at a relatively low current density, the electrode can maintain a constant water holding force by the hydrophilic carbon material and high characteristics can be expected. In addition, in the case of operating at a relatively high current density, the excess water is quickly discharged by the water-repellent carbon material disposed in the very vicinity of the hydrophilic carbon material, so that flooding does not easily occur, thereby improving battery performance.
[221] In addition, when the hydrophilic carbon material is disposed on the polymer electrolyte membrane side and the water-repellent carbon material on the gas diffusion layer side, the polymer electrolyte membrane side becomes a high humidification atmosphere, and the ion conductivity of the polymer electrolyte membrane is improved, thereby improving battery characteristics.
[222] In the fuel cell electrode according to the present embodiment, on the surface of the carbon particles, the hydrolyzable group of the silane coupling agent having a hydrophobic portion is hydrolyzed by the moisture in the solution or in the air and the adsorbed moisture on the carbon surface. . Then, it changes to an active silanol group () SiOH) and reacts with a functional group on the carbon surface to form a strong bond. As a result, very small monomolecular repellent layers of several nm to several tens of nm are formed on the surface of the carbon particles. When the water-repellent carbon particles are used, even when the electrode is formed by mixing with the hydrophilic catalyst-carrying carbon particles, the catalyst particles in the electrode are covered, as in the case of using the PTFE dispersion particles, which are submicron orders, to prevent the supply of the reaction gas. There is nothing to do.
[223] In the fuel cell of the present invention, on the surface of the catalyst particles or on the surface of the carbon particles supported by the catalyst, the hydrolyzable group of the silane coupling agent is formed in the same manner as before by the moisture in the solution or in the air and the adsorption moisture on the carbon surface. Hydrolysis. Then, it changes to an active silanol group () SiOH) and reacts with a functional group on the carbon surface to form a strong bond. By providing the silane coupling agent with a hydrophilic group such as a sulfonic acid group or a carboxyl group, the catalyst surface becomes hydrophilic and the wet state near the three-phase interface is maintained.
[224] As described above, when the electrode of the present embodiment is used, in the vicinity of the three-phase interface where the electrode reaction occurs, the wet state is properly maintained by the hydrophilic catalyst-carrying carbon particles, and the excess water is quickly discharged by the adjacent water-repellent carbon. Since it is discharged, a high performance polymer electrolyte fuel cell can be constructed conventionally.
[225] Hereinafter, the Example of 4th Embodiment of this invention is described.
[226] Example 14
[227] First, the manufacturing method of a water repellent carbon material is described. The front surface silane coupling agent was adsorbed on the surface of the carbon powder by a chemical adsorption method in a nitrogen gas atmosphere to form a monomolecular film made of the silane coupling agent. As the silane coupling agent, a hexane solution dissolved at a concentration of 1% by weight was adjusted using CH _3- (CH ₂ ) n -SiCl ₃ (n is an integer of 10 to 25) having a linear hydrocarbon chain, The carbon particles were immersed. The carbon particles used at this time were subjected to dehydrochlorination reaction of the functional group and -SiCl ₃ of the silane coupling agent described above using a digraphite carbon leaving a phenol hydroxyl group and a carboxyl group on the surface. To form a monomolecular repellent membrane. This shape is shown in FIG.
[228] In FIG. 16, 101 is a carbon particle, 102 is a monomolecular water repellent membrane. The thickness of the monomolecular water repellent film 102 was about 2-10 nm. Here, this film thickness could be 1-100 nm by changing the molecular weight of a single molecule. In addition, as a material of chemisorption, if it contains the group which has a bond with respect to -OH group, for example, a -SiCl group, it is not limited to the silane type surfactant used in this Example.
[229] Next, a hydrophilic carbon powder carrying 25 wt% of platinum serving as an electrode catalyst and the water-repellent carbon material were mixed, and a solution in which the -SO ₃ H group pendant polyfluorocarbon polymer electrolyte was dispersed therein. -1, manufactured by Asahi Glass Co., Ltd. "and butanol, and ink was added. This ink was coated on the carbon paper &quot; Toray Co., Ltd. product, Tn-H-120, film thickness 360 mu m) serving as a gas diffusion layer by screen printing, and thereafter, butanol was removed by heating and drying. It was set as the electrode A 'of a present Example.
[230] In the above process, the carbon powder which carried platinum was used the thing which has many functional groups on the surface, and has hydrophilicity (VulcanXC 72R by Cabot Corporation). In addition, the platinum amount per unit area was 0.5 mg / cm <^2> . In addition, the mixed weight ratio of the platinum-supported hydrophilic carbon powder, the water-repellent carbon material, and the polyfluorocarbon polymer electrolyte was 100: 20: 3 after finishing.
[231] Next, a comparative electrode B 'was produced. The comparative electrode B 'has been conventionally proposed in that a carbon powder carrying a precious metal serving as a catalyst and a water repellent are formed on a porous conductive electrode substrate serving as a gas diffusion layer. The porous conductive substrate is made of the same carbon paper (Torre, TGP-H-120, film thickness of 360 µm) as used for the above-mentioned electrode (A '), and the polyfluoro pre-SO ₃ H group pendant. Water-repellent treatment was performed using the solution which disperse | distributed the carbon type polymer electrolyte [FSS-1, Asahi Glass Co., Ltd. product]. In the above structure, the carbon powder used "Denka Black and Denki Chemical Co., Ltd." which are small in surface functional groups and show water repellency. In addition, the water-repellent agent is, -SO ₃ H group pendent a polyfluoroalkyl solution a dispersion of carbon-based polymer electrolytes used in the "FSS-1, Asahi Glass Co., Ltd. The". The other configuration was the same as that of the electrode A 'described above.
[232] The electrode A 'of the present Example thus prepared and the electrode B' of the comparative example were placed on both sides of the polymer electrolyte membrane (Nafion112, manufactured by Du Pont) to be hot pressed to prepare an electrode-electrolyte assembly. This was set in the unit cell measuring apparatus shown in FIG. 11 to constitute a unit cell. In Fig. 11, 20, 24 and 25 are electric electrode-electrolyte conjugates.
[233] These cells have hydrogen gas flowing through the anode and air flowing through the cathode, with a current temperature of 75 ° C, fuel utilization of 80%, air utilization of 30%, gas humidification of hydrogen gas of 75 ° C and air of 65 ° C. Adjusted to 17 shows current-voltage characteristics of the battery at this time.
[234] In FIG. 17, it was confirmed that the use of the electrode A 'of the present embodiment showed superior characteristics as compared with the electrode B' of the conventionally proposed configuration. The reason for this is that when the water-repellent carbon powder treated with the silane coupling agent is used, as in the case of the PTFE supported carbon powder using the PTFE dispersion particles of the submicron order, the catalyst fine particles in the electrode are coated to supply the reaction gas. We think that it is by not disturbing.
[235] Example 15
[236] In the present Example, the electrode which arrange | positioned the catalyst reaction layer to the polymer electrolyte membrane side, and the water-repellent carbon particle on the gas diffusion layer side was produced, and the characteristic was evaluated. First, the catalyst-carrying carbon powder shown in Example 14 and the water-repellent carbon powder treated with the silane coupling agent were coated with another ink to form an electrode. This is shown in FIG. 18. First, the water repellent carbon powder "Denka Black, made by Denki Chemical Industries, Ltd." is inkized using butanol, and screened on carbon paper "Toray Co., Ltd., TGP-H-120, film thickness of 360 micrometers". Printed. After drying, the catalyst-supported carbon powder 106 was prepared by dispersing the solution "FSS-1, manufactured by Asahi Glass Co., Ltd." and butanol in which the polyfluorocarbon polymer electrolyte in which the -SO ₃ H group of the polymer electrolyte solution was pendant was dispersed. It was made into an ink and coated on the carbon paper 108 on which the water-repellent carbon powder 107 was coated by screen printing to prepare an electrode.
[237] Using the electrode thus produced, an electrode-electrolyte assembly was produced, and the unit cell shown in FIG. 11 was constructed as in Example 14. Table 5 shows the battery voltages when a current of 700 mA / cm ² flows through this unit cell. In Table 5, the characteristic of the battery by the electrode A 'and the electrode B' produced in the said Example 14 was also described.
[238] Table 5
[239] Battery voltage (mV) Example 15 710 Electrode A ' 690 Electrode B ' 620
[240] In Table 5, a carbon powder treated with the silane coupling agent of Example 14 was used by mixing the electrode catalyst layer employed in Example 15 with the electrode having the water repellent carbon particles disposed on the polymer electrolyte membrane side and the diffusion layer side. It can be seen that the performance equivalent to that. Accordingly, it has been found that a battery having more excellent characteristics can be constructed by using an electrode having the electrode catalyst layer disposed on the polymer electrolyte membrane side and the water repellent carbon particles placed on the diffusion layer side.
[241] Example 16
[242] Next, a case where the catalyst-carrying carbon powder is treated with a silane coupling agent is shown using FIG. 19. ClSO _2- (CH ₂ ) having a hydrocarbon chain and a fluorocarbon chain as the main chain and having a sulfonic acid group at the end thereof, by using the platinum-supported carbon powder used in Example 14 and replacing it with the silane coupling agent used in Example 14. n- (CF ₂ ) m-SiCl ₃ (n, m is an integer of 10 to 25), and reacts with water vapor to form the surface of the platinum particles 109 and the surface of the carbon particles 101. , The monomolecular film 110 having a sulfonic acid group was formed. This monomolecular film exhibits hydrophilicity because of its sulfonic acid group at its terminal. In addition, as long as the silane coupling agent contains the site | part which shows hydrophilicity, it is not limited to the silane type surfactant shown in the Example.
[243] The hydrophilic platinum-supported carbon powder thus treated and the water-repellent carbon powder treated with the silane coupling agent used in Example 14 were mixed to prepare an electrode as in Example 14, and the unit cell shown in FIG. 11 was produced using the same.
[244] When the characteristics of this battery were evaluated under the same conditions as in Example 14, the voltage at a current density of 700 mA / cm ² was 720 mV. This is a higher characteristic than the battery produced in Example 14, which is thought to be due to the improved wettability near the three-phase interface by hydrophilic treatment of carbon powder carrying catalyst particles with a silane coupling agent.
[245] In the present invention, a chlorosilane-based surfactant having a sulfonic acid group is used as the silane coupling agent, but any one may be used as long as it has a site such as a carboxyl group or the like as long as it has a hydrophilic site. In addition, this time, although both a catalyst fine particle and a carbon particle were processed, if it can adapt this invention, it can also process only one side. In addition, as long as the present invention can be applied to the used carbon powder and the catalyst-supported carbon powder, the present invention is not limited to this embodiment.
[246] As apparent from the first embodiment of the present invention, the fuel cell of the present invention can obtain higher battery performance even with the same amount of platinum, and can significantly reduce the amount of platinum used when attempting to obtain equivalent battery performance. have.
[247] According to the second embodiment of the present invention, since the fuel cell according to the present invention has a layer made of conductive fine particles disposed between the catalyst reaction layer and the gas diffusion layer, the contact resistance between the catalyst reaction layer and the gas diffusion layer is reduced. Battery characteristics are improved. Moreover, when the layer which consists of electroconductive fine particles penetrates into some gas diffusion layer, the effect improves more. In addition, since the catalytic reaction layer does not penetrate into the gas diffusion layer, the amount of the noble metal catalyst used in the catalytic reaction layer can be reduced than before, and a cost reduction effect can be expected. In addition, the use of a carbon material having PTFE adhering to the conductive fine particle layer also has the advantage of increasing the physical binding properties of the catalytic reaction layer and the gas diffusion layer, thereby facilitating handling. In this case, since the PTFE is introduced, a secondary effect can be expected, in particular, that some of the generated water generated in the air electrode is knitted in the electrolyte membrane, and the excess generated water is discharged to the gas diffusion layer side. Thus, in the fuel cell according to the present invention, since the conductive fine particle layer is disposed between the catalyst reaction layer and the gas diffusion layer, it is possible to construct a fuel cell having a higher performance than the conventional one.
[248] In the electrode for fuel cell according to the third embodiment of the present invention, the surface of the catalyst particles or the catalyst carrier has a surface diffusion function of hydrogen ions, and the functional polymer is adsorbed. As a result, the monomolecular polymer electrolyte layer is uniformly adsorbed on the catalyst metal surface or the carbon surface supported by the catalyst, so that hydrogen ion channels can be formed in the catalyst in the pores. In addition, the reaction area is increased, and it is possible to realize a polymer fuel cell exhibiting higher discharge performance.
[249] In addition, by having a hydrocarbon chain in the silane compound, the hydrophilicity of the polymer layer can be increased. For example, the fuel cell is operated at a low current density, so that the electrode remains constant even when operating in low water or low-humidity air. Maintaining the water holding power, high performance can be obtained.
[250] In addition, by providing a fluorocarbon chain, the water repellency of the polymer layer can be increased. For example, the fuel cell is operated at a high current density, so that the electrode has a gas diffusion capacity even when operating with a large number of generated water or in a high humidified air. This improves and high performance can be obtained.
[251] In addition, since the reaction area is increased, the amount of the noble metal catalyst used in the electrode catalyst layer can be reduced compared to the prior art, and there is an advantage that cost reduction can be expected.
[252] In addition, the electrode of the present invention is characterized by adsorbing functional polymers having a surface diffusion function of hydrogen ions on the surface of the catalyst particles or the catalyst carrier. This functional polymer functions as a polymer electrolyte layer. In this formation, a monolayer as a functional polymer was formed by using a silane compound having a basic functional group. As described above, the functional polymer has a surface diffusion function of hydrogen ions. By modifying the surface of the catalyst carrier, a dense polymer electrolyte layer is formed in the vicinity of the catalyst, thereby forming an efficient hydrogen ion channel and a gas channel. As a result, a polymer fuel cell exhibiting high discharge performance can be realized.
[253] In addition, the use of highly efficient hydrogen ion exchange capability enables reduction of the amount of the noble metal catalyst used in the catalytic reaction layer without deterioration of the discharge characteristics, thereby reducing the cost.
[254] In addition, the wettability of the electrode can be controlled by selecting the skeleton structure of the silane compound that modifies the surface. This makes it possible to produce an electrode catalyst that is optimal for the driving conditions of the fuel cell.
[255] As apparent from the fourth embodiment of the present invention, in the fuel cell according to the present invention, since the catalytic reaction layer is composed of a polymer electrolyte, a water-repellent catalyst-carrying carbon particle, and a water-repellent carbon particle, a three-phase electrode reaction occurs. In the vicinity of the interface, the wet state is properly maintained by the hydrophilic catalyst supported carbon particles, and the excess water is discharged quickly by the adjacent water-repellent carbon.
[256] In addition, when the hydrophilic catalyst-carrying carbon particles are arranged on the polymer electrolyte membrane side and the water-repellent carbon particles are on the gas diffusion layer side, the polymer electrolyte membrane side becomes a high humidification atmosphere, and the ion conductivity of the polymer electrolyte membrane is improved, thereby improving battery characteristics.
[257] In the fuel cell of the present invention, the hydrolyzable group of the silane coupling agent having a hydrophobic portion is hydrolyzed in the solution or in the air by the adsorption moisture of the carbon surface and the active silanol group ( ≡SiOH), and react with the functional groups on the carbon surface to form a strong bond. As a result, very small monomolecular repellent layers of several nm to several tens of nm are formed on the surface of the carbon particles. When the water-repellent carbon particles are used, even if the electrode is formed by mixing with the hydrophilic catalyst-supported carbon particles, as in the case of using PTFE dispersion particles of the submicron order, the catalyst particles in the electrodes are prevented from interfering with the supply of the reaction gas. There is no work.
[258] In the fuel cell of the present invention, the hydrolyzable group of the silane coupling agent is adsorbed on the surface of the catalyst particles or on the surface of the carbon particles supported by the catalyst by adsorbing moisture in the solution or in the air and carbon surface as before. It is decomposed to change into an active silanol group (≡SiOH), which reacts with a functional group on the carbon surface to form a strong bond. By providing a hydrophilic group, such as a sulfonic acid group and a carboxyl group, to this silane coupling agent, a catalyst surface becomes hydrophilic and the wet state of three phase interface vicinity is maintained.
[259] As described above, when the electrode according to the fourth embodiment of the present invention is used, in the vicinity of the three-phase interface in which the electrode reaction occurs, the wet state is properly maintained by the hydrophilic catalyst-supported carbon particles, and the excess water is generated by adjacent water repellent. Since carbon is quickly discharged, a polymer electrolyte fuel cell having higher performance than before can be configured.

权利要求:
Claims (20)
[1" claim-type="Currently amended] A fuel cell comprising a polymer electrolyte membrane, a pair of electrodes having a catalytic reaction layer and a gas diffusion layer, wherein the polymer electrolyte membrane is sandwiched by a pair of electrodes, and part of a carrier supporting the catalyst particles in the catalytic reaction layer. A polymer electrolyte fuel cell, wherein the polymer electrolyte membrane penetrates into the inside of the polymer electrolyte membrane.
[2" claim-type="Currently amended] The polymer electrolyte fuel cell according to claim 1, wherein the carrier is acicular carbon fiber.
[3" claim-type="Currently amended] A fuel cell comprising a polymer electrolyte membrane, a pair of electrodes having a catalytic reaction layer, and a gas diffusion layer, wherein the polymer electrolyte membrane is sandwiched by a pair of electrodes, wherein a conductive fine particle is formed between the catalytic reaction layer and the gas diffusion layer. Polymer electrolyte fuel cell having a layer made of.
[4" claim-type="Currently amended] 4. The polymer electrolyte fuel cell according to claim 3, wherein a part of the layer made of the conductive fine particles invades the gas diffusion layer.
[5" claim-type="Currently amended] The polymer electrolyte fuel cell according to claim 3 or 4, wherein materials of the conductive fine particles constituting the layer composed of the conductive fine particles are different on both sides of the polymer electrolyte membrane.
[6" claim-type="Currently amended] 4. The polymer electrolyte fuel cell according to claim 3, wherein the conductive fine particles are carbon powder having PTFE attached thereto.
[7" claim-type="Currently amended] A fuel cell comprising a polymer electrolyte membrane, a pair of electrodes having a catalytic reaction layer and a gas diffusion layer, wherein the polymer electrolyte membrane is sandwiched by a pair of electrodes, the catalyst particles in the catalytic reaction layer and the catalyst A polymer electrolyte fuel cell comprising a hydrogen ion diffusion layer on at least one surface of a carrier supporting particles.
[8" claim-type="Currently amended] 8. The polymer electrolyte fuel cell according to claim 7, wherein the hydrogen ion diffusion layer is formed by chemically bonding a silane compound to at least one surface of the catalyst particles and the carrier supporting the catalyst particles.
[9" claim-type="Currently amended] 8. The method of claim 7, wherein the hydrogen ion diffusion layer is composed of an organic compound having a basic functional group and a hydrogen ion conductive electrolyte, wherein the organic compound modifies at least one surface of the carrier supporting the catalyst particles and the catalyst particles. A polymer electrolyte fuel cell, characterized in that.
[10" claim-type="Currently amended] 8. The polymer electrolyte fuel cell according to claim 7, wherein the basic functional group has a nitrogen atom having a non-covalent electron pair.
[11" claim-type="Currently amended] 10. The polymer electrolyte fuel cell according to claim 9, wherein the organic compound having a basic functional group is a silane compound.
[12" claim-type="Currently amended] The polymer electrolyte fuel cell according to claim 8 or 11, wherein the silane compound has a functional group capable of dissociating hydrogen ions.
[13" claim-type="Currently amended] The polymer electrolyte fuel cell according to claim 8, 11 or 12, wherein the silane compound has at least one of a hydrocarbon chain and a fluorocarbon chain.
[14" claim-type="Currently amended] The said silane compound is at least 1 sort (s) as described in any one of Claims 11 and 11-14 selected from the group which consists of a phenolic hydroxyl group, a carboxyl group, a lactone group, a carbonyl group, a quinone group, and a carboxylic anhydride group. A polymer electrolyte fuel cell, which is chemically bonded to at least one surface of the catalyst particles and the carrier supporting the catalyst particles through a functional group.
[15" claim-type="Currently amended] A fuel cell comprising a polymer electrolyte membrane, a pair of electrodes having a catalytic reaction layer and a gas diffusion layer, wherein the polymer electrolyte membrane is sandwiched by a pair of electrodes, wherein the catalytic reaction layer catalyzes at least a hydrophilic carbon material. A polymer electrolyte fuel cell comprising a catalyst body formed by supporting particles, and a water repellent carbon material.
[16" claim-type="Currently amended] The polymer electrolyte fuel cell according to claim 15, wherein a hydrophilic layer is chemically bonded to at least a portion of the surface of the catalyst particles.
[17" claim-type="Currently amended] 17. The polymer electrolyte fuel cell according to claim 15 or 16, wherein in the catalytic reaction layer, the catalyst body is selectively disposed on the polymer electrolyte membrane side, and the water-repellent carbon material is selectively disposed on the gas diffusion layer side. .
[18" claim-type="Currently amended] 17. The polymer electrolyte fuel cell according to claim 15 or 16, wherein the water-repellent carbonaceous material has a monomolecular layer formed by chemically bonding a silane compound having a hydrophobic portion to at least a portion of the surface of the carbonaceous material.
[19" claim-type="Currently amended] 17. The polymer electrolyte fuel cell according to claim 15 or 16, wherein the hydrophilic carbon material has a layer formed by chemically bonding a silane compound having a hydrophilic portion to at least a portion of a surface of the carbon material.
[20" claim-type="Currently amended] 20. The carbonaceous material according to claim 18 or 19, wherein the silane compound is formed of at least one functional group selected from the group consisting of phenolic hydroxyl group, carboxyl group, lactone group, carbonyl group, quinone group and carboxylic acid anhydride group. A polymer electrolyte fuel cell, which is chemically bonded to a surface.

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KR100413645B1|2003-12-31|

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CN1159788C|2004-07-28|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1983-03-11|Priority to JP41184

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1998-06-16|Priority to JP168174

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1998-06-16|Priority to JP10168174A

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1998-10-13|Priority to JP290340

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1998-10-13|Priority to JP29034098A

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1999-02-05|Priority to JP02824599A

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1999-02-19|Priority to JP04118499A

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1999-06-10|Application filed by 모리시타 요이찌, 마쯔시다덴기산교 가부시키가이샤

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2000-02-04|Priority to JP28245

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2001-08-04|Publication of KR20010074511A

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2003-12-31|Application granted

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2003-12-31|Publication of KR100413645B1

优先权:

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申请号 | 申请日 | 专利标题

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JP41184|1983-03-11|

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JP168174|1998-06-16|

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JP10168174A|JP2000003714A|1998-06-16|1998-06-16|Solid high molecular fuel cell and manufacture thereof|

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JP29034098A|JP3444530B2|1998-10-13|1998-10-13|Fuel cell|

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JP290340|1998-10-13|

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JP02824599A|JP3992866B2|1999-02-05|1999-02-05|Fuel cell electrode and method for producing the same|

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JP04118499A|JP3565077B2|1999-02-19|1999-02-19|Electrode for fuel cell and method for producing the same|

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JP28245|2000-02-04|