JP5034172B2 - Gas diffusion layer for fuel cell and fuel cell using the same - Google Patents

Description

  The present invention relates to a fuel cell gas diffusion layer, and more particularly to a fuel cell gas diffusion layer having drainage and moisture retention.

  In recent years, in response to social demands and trends against the background of energy and environmental problems, fuel cells that can operate at room temperature and obtain high output density have attracted attention as power sources for electric vehicles and stationary power sources. A fuel cell is a clean power generation system in which the product of an electrode reaction is water in principle and has almost no adverse effect on the global environment. Fuel cells include solid polymer electrolyte fuel cells (PEFC), phosphoric acid fuel cells (PAFC), alkaline fuel cells (AFC), solid oxide fuel cells (SOFC), molten carbonate fuel cells ( MCFC). Among them, the polymer electrolyte fuel cell is expected as a power source for electric vehicles because it operates at a relatively low temperature and obtains a high output density.

  The polymer electrolyte fuel cell generally has a structure in which a membrane-electrode assembly (hereinafter also referred to as “MEA”) is sandwiched between separators. The MEA has a structure in which two electrodes are disposed on both sides of a solid polymer electrolyte membrane and this is sandwiched between gas diffusion layers. The electrode is a porous material formed of a mixture of an electrode catalyst and a solid polymer electrolyte, and is also called an electrode catalyst layer.

  In the polymer electrolyte fuel cell, electricity can be taken out through the following electrochemical reaction. First, hydrogen contained in the fuel gas supplied to the anode (fuel electrode) side is oxidized by the catalyst particles to become protons and electrons. Next, the generated protons pass through the solid polymer electrolyte contained in the anode-side electrode catalyst layer and the solid polymer electrolyte membrane in contact with the anode-side electrode catalyst layer, and enter the cathode (oxygen electrode) -side electrode catalyst layer. Reach. The electrons generated in the anode-side electrode catalyst layer include a conductive carrier constituting the anode-side electrode catalyst layer, and a gas diffusion layer in contact with a different side of the anode-side electrode catalyst layer from the solid polymer electrolyte membrane The cathode side electrode catalyst layer is reached through the separator and the external circuit. The protons and electrons that have reached the cathode-side electrode catalyst layer react with oxygen contained in the oxidant gas supplied to the cathode side to generate water. Such an electrochemical reaction mainly proceeds at a three-phase interface where catalyst particles, a solid polymer electrolyte, and a reaction gas such as a fuel gas or an oxidant gas are in contact with each other. Therefore, the gas diffusion layer is required to uniformly supply the supplied reaction gas to the electrode catalyst layer.

  In addition, a solid polymer electrolyte membrane in a fuel cell does not exhibit high proton conductivity unless it is wet. Therefore, it is necessary to make the humidity distribution of the solid polymer electrolyte membrane uniform by humidifying the reaction gas supplied to the solid polymer fuel cell using a gas humidifier or the like.

  Under operating conditions such as high humidification and high current density, the amount of water that moves with protons that move through the polymer electrolyte membrane from the anode to the cathode, and agglomerates in the cathode-side electrode catalyst layer The amount of product water increases. At this time, the generated water stays in the cathode-side electrode catalyst layer, and causes a flooding phenomenon that closes the pores that have become the reaction gas supply path. As a result, the diffusion of the reaction gas is inhibited, the electrochemical reaction is hindered, and as a result, the battery performance is lowered.

Therefore, conventionally, a gas diffusion layer having a carbon layer made of carbon black and a hydrophobic agent on the surface of the conductive porous base material layer is used for MEA (see, for example, Patent Document 1). In the carbon layer, carbon black coated with a hydrophobic agent is aggregated to form a porous structure. Therefore, not only can the reaction gas supplied by humidification be diffused more uniformly, but also excess water can be sucked up by capillary force and quickly discharged. Patent Document 2 discloses a gas diffusion layer having a carbon layer in which pores having different pore diameter distribution centers are mixed. Thereby, the gas passage and the water passage are separated, and the flooding phenomenon is prevented. Patent Document 3 discloses a gas diffusion layer having a carbon layer in which a water repellent material and a pore size distribution are inclined in the plane direction of the carbon layer.
JP 2003-89968 A JP 2001-57215 A Japanese Patent Laid-Open No. 2003-092112

  Conventionally, it has been desired for a fuel cell to maintain high power generation performance over a wide range of operating conditions.

  However, according to the gas diffusion layer in which the carbon layer is formed on the conductive porous substrate layer according to Patent Document 1, the drainage performance is improved to some extent, but under operating conditions such as low humidification and low current density. Further, there is a problem that the amount of generated water is small and the solid polymer electrolyte membrane is easily dried, and the battery output is lowered.

  Further, the gas diffusion layers of Patent Document 2 and Patent Document 3 can also improve drainage performance during high humidification operation, but sufficient moisture retention cannot be obtained, and solid high performance during low humidification operation can be obtained. There has been a problem that drying of the molecular electrolyte membrane cannot be sufficiently suppressed.

  Therefore, an object of the present invention is to provide a gas diffusion layer having both drainage and moisture retention.

The present invention provides a fuel cell gas diffusion layer having a carbon layer on a conductive porous substrate layer,
The above-mentioned problem is solved by the gas diffusion layer for a fuel cell in which the carbon layer contains at least two kinds of conductive carbons having different water vapor adsorption performance.

  According to this invention which has the said structure, it becomes possible to provide the gas diffusion layer which has both drainage property and moisture retention. Therefore, the gas diffusion layer can provide a fuel cell that can stably exhibit high power generation performance under a wide range of operating conditions.

  The first aspect of the present invention is that, as described above, in the gas diffusion layer for a fuel cell having a carbon layer on the conductive porous substrate layer, the carbon layer contains at least two types of conductive carbon having different water vapor adsorption performance. It is a gas diffusion layer for fuel cells.

  The water vapor adsorption performance of conductive carbon means the amount of water vapor that can be adsorbed on the surface of conductive carbon. Specifically, the volume (ml) of water vapor that can be adsorbed on the surface of the conductive carbon relative to the weight (g) of the conductive carbon is defined as the water vapor adsorption performance (ml / g) of the conductive carbon. The water vapor adsorption performance of the conductive carbon is assumed to be a relative pressure (water vapor pressure with respect to saturated water vapor pressure) 0 to 1 obtained by water vapor adsorption isotherm measurement at 70 ° C., which is a commercially available water vapor adsorption isotherm measuring device (Japan). It can be measured by Bell Co., Ltd. BELSORP 18).

  In the present invention, as a result of conducting various studies on imparting drainage and moisture retention to the gas diffusion layer, carbon can be obtained by using at least two types of conductive carbon having different water vapor adsorption performance for the carbon layer in the gas diffusion layer. It turned out to be easy to adjust the moisture retention in the layer. That is, in the carbon layer, a portion using conductive carbon having high water vapor adsorption performance can adsorb more water vapor, and it is possible to impart drainage and gas diffusibility to the gas diffusion layer. The portion using conductive carbon having a low water content has a small amount of water vapor adsorbed, and can keep the moisture retention in the gas diffusion layer moderate. Therefore, the gas diffusion layer of the present invention can have both drainage and moisture retention properties, and prevents drying of the solid polymer electrolyte membrane in the fuel cell even under operating conditions such as low humidification operation and low current density. Even under operating conditions such as high humidification operation and high current density, the flooding phenomenon caused by the generated water can be suppressed.

  In addition, by using at least two kinds of conductive carbon having different water vapor adsorption performances in the carbon layer, it is possible to easily adjust the portion of the carbon layer where moisture retention is to be improved and the portion where drainage is to be improved.

  Specifically, from the viewpoint of imparting moisture retention to the gas diffusion layer, the relative pressure (water vapor pressure with respect to the saturated water vapor pressure) 0 to 70 ° C. obtained from the water vapor adsorption isotherm measurement from the viewpoint of imparting moisture retention to the gas diffusion layer. A conductive carbon having a water vapor adsorption performance of 1 is preferably 0 to 0.5 ml / g, more preferably 0 to 0.3 ml / g, and particularly preferably 0 to 0.1 ml / g. It should be included in the layer.

  Further, from the viewpoint of imparting drainage to the gas diffusion layer, the water vapor adsorption performance at a relative pressure (water vapor pressure with respect to saturated water vapor pressure) 0 to 1 obtained by water vapor adsorption isotherm measurement at 70 ° C. is preferably 0.5 ml. The carbon layer may contain conductive carbon having a water vapor adsorption performance of more than / g and less than 1 ml / g, more preferably 0.7 to 1 ml / g, particularly preferably 0.8 to 1 ml / g.

  In the carbon layer of the present invention, it is preferable to use conductive carbon having at least two kinds of water vapor adsorption performance described above.

  In the carbon layer, the water vapor adsorption performance of the conductive carbon is preferably increased in the thickness direction. Thereby, moisture retention can be changed in the cross-sectional direction of the carbon layer.

  When the water vapor adsorption performance of the conductive carbon in the carbon layer decreases from the surface of the carbon layer toward the surface in contact with the conductive porous base material layer, the conductive carbon contained in the portion having a thickness of 0 to 50 μm from the carbon layer surface. The water vapor adsorption performance is preferably 0.5 to 1 ml / g, more preferably 0.7 to 1 ml / g, and particularly preferably 0.8 to 1 ml / g. The water vapor adsorption performance of the conductive carbon contained in the portion having a thickness of 0 to 50 μm from the surface in contact with the base material layer is preferably 0 to 0.5 ml / g, more preferably 0 to 0.3 ml / g, particularly preferably. The water vapor adsorption performance of the conductive carbon is preferably decreased from the surface of the carbon layer toward the surface in contact with the conductive porous substrate layer.

  In addition, when the water vapor adsorption performance of conductive carbon in the carbon layer is reduced from the surface of the carbon layer in contact with the conductive porous substrate layer toward the surface of the carbon layer, the carbon layer is included in a portion having a thickness of 0 to 50 μm. The water vapor adsorption performance of the conductive carbon is preferably 0 to 0.5 ml / g, more preferably 0 to 0.3 ml / g, and particularly preferably 0 to 0.1 ml / g. The water vapor adsorption performance of conductive carbon contained in a portion having a thickness of 0 to 50 μm from the surface in contact with the conductive porous substrate layer is preferably 0.5 to 1 ml / g, more preferably 0.7 to 1 ml / g, particularly preferably 0.8 to 1 ml / g, so that the water vapor adsorption performance of the conductive carbon decreases from the surface of the carbon layer in contact with the conductive porous substrate layer toward the surface of the carbon layer. It is good to do.

  In the carbon layer having a structure in which the water vapor adsorption performance of the conductive carbon increases in the thickness direction, the water vapor adsorption performance of the conductive carbon may increase stepwise in the thickness direction and gradually increase. It may be bigger. However, since it is easy to manufacture and the effect of moisturizing the electrolyte membrane is obtained, it is desirable that the water vapor adsorption performance of the conductive carbon increases stepwise in the thickness direction.

  As a preferred form of the carbon layer having such a structure, at least two layers of a carbon layer (1) and a carbon layer (2) are laminated, and water vapor of conductive carbon contained in the carbon layer (1). A form in which the adsorption performance is greater than the water vapor adsorption performance of the conductive carbon contained in the carbon layer (2) can be mentioned.

  In the gas diffusion layer of the present invention, the carbon layer (1) is preferably disposed in contact with the conductive porous substrate layer. The gas diffusion layer having such a configuration will be described with reference to the schematic cross-sectional view of FIG. In FIG. 1, the gas diffusion layer of the present invention has a configuration in which a carbon layer (1) 122 and a carbon layer (2) 123 are laminated in this order on a conductive porous substrate layer 121. By increasing the water vapor adsorption performance of the conductive carbon contained in the carbon layer (1) 122 over the carbon layer (2) 123, the water vapor adsorption of the conductive carbon in the carbon layer toward the thickness direction (arrow a direction). The performance can be increased in stages.

  Thus, by arrange | positioning a conductive porous base material layer and a carbon layer (1) in contact, water vapor adsorption | suction is accelerated | stimulated in a carbon layer (1), and humidity falls, A carbon layer and electroconductivity are reduced. It becomes possible to promote the movement of the gas between the porous base material layer and the gas diffusibility of the gas diffusion layer can be improved. Furthermore, when the gas diffusion layer is used as an MEA, the carbon layer (2) and the electrode catalyst layer can be disposed in contact with each other, and water vapor adsorption near the electrode catalyst layer is suppressed and generated by a power generation reaction. Thus, the humidity can be kept high by the water, and drying of the electrode catalyst layer and the solid polymer electrolyte membrane can be suppressed. Therefore, according to the gas diffusion layer having the carbon layer, drainage and moisture retention can be efficiently imparted to the carbon layer.

  The water vapor adsorption performance of the conductive carbon contained in the carbon layer (2) is preferably 0 to 0.5 ml / g, more preferably 0 to 0.3 ml / g, particularly preferably 0 to 0.1 ml / g. It should be in range. If the water vapor adsorption amount of the conductive carbon contained in the carbon layer (2) is within the above range, drying of the solid polymer electrolyte membrane in the membrane electrode assembly can be suppressed.

  The water vapor adsorption performance of the conductive carbon contained in the carbon layer (1) is preferably 0.5 to 1 ml / g, more preferably 0.7 to 1 ml / g, and particularly preferably 0.8 to 1 ml / g. It should be in range. If the water vapor adsorption amount of the conductive carbon contained in the carbon layer (1) is within the above range, flooding in the membrane electrode assembly can be suppressed.

  The water vapor adsorption performance of the conductive carbon contained in the carbon layers (1) and (2) in the gas diffusion layer of the present invention can be measured by measuring the water vapor adsorption isotherm of the gas diffusion layer.

  As the conductive carbon used for the carbon layer, the main component is preferably carbon. Thereby, high electron conductivity is obtained. More specific examples of the conductive carbon include carbon blacks such as oil furnace black, channel black, lamp black, thermal black, and acetylene black.

  Commercially available carbon can be used as the conductive carbon, such as Cabot Vulcan XC-72, Vulcan P, Black Pearls 880, Black Pearls 1100, Black Pearls 1300, Black Pearls 2000, Legal 400, Ketjen Black manufactured by Lion. EC, oil furnace black such as # 3150 and # 3250 manufactured by Mitsubishi Chemical Corporation; acetylene black such as Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd. and the like. In addition to carbon black, artificial graphite or carbon obtained from organic compounds such as natural graphite, pitch, coke, polyacrylonitrile, phenol resin, and furan resin may be used. Moreover, in order to improve corrosion resistance etc., you may process the said carbon particle, such as a graphitization process.

  In the carbon layer of the present invention, one having a desired water vapor adsorption performance from the above-described conductive carbon may be appropriately selected and used.

  The shape of the conductive carbon is not particularly limited, and may have any shape such as a particle shape, an elliptical shape, and a cubic shape. It is preferable to have it. In this case, the conductive carbon is not particularly limited, but those having an average particle diameter of preferably 1 to 10 μm, more preferably about 1 to 5 μm may be used.

  The carbon layer preferably contains conductive carbon and a hydrophobic agent. Thereby, the conductive carbon coated with the hydrophobic agent becomes an aggregate, and a carbon layer having a stable porous structure is obtained.

  When the carbon layer has a configuration in which at least two layers of the carbon layer (1) and the carbon layer (2) are laminated, the carbon layer (2) has a mass ratio of the conductive carbon and the hydrophobic agent. , Preferably 80:20 to 60:40, more preferably 80:20 to 63:37, and particularly preferably 80:20 to 65:35. As a result, the water vapor adsorption performance of the surface of the conductive carbon contained in the carbon layer (2) can be lowered, and the pore diameter can be appropriately adjusted, thereby improving the gas diffusibility in the carbon layer. It becomes possible.

  In the carbon layer (1), the mass ratio of the conductive carbon and the hydrophobic agent is preferably 90:10 or more and less than 80:20, more preferably 88:12 or more and less than 80:20, and particularly preferably 85:15. More than 80:20 is preferable. Thereby, the water vapor adsorption performance of the surface of the conductive carbon contained in the carbon layer (1) can be increased, and the pore diameter can be adjusted appropriately, and flooding in the carbon layer can be prevented.

  When the carbon layer has a structure of three or more layers, another carbon layer may be disposed between the carbon layer (1) and the carbon layer (2). At this time, another carbon further disposed between the carbon layer (1) and the carbon layer (2) so that the adsorption performance of the conductive carbon increases in the thickness direction in the entire carbon layer. What is necessary is just to adjust the mass ratio of the conductive carbon and the hydrophobic agent in the layer. Specifically, an intermediate value may be taken with respect to the mass ratio of the conductive carbon and the hydrophobic agent in the carbon layer (2) and the carbon layer (1).

  Since the specific description of the conductive carbon used in the carbon layer is as described above, detailed description thereof is omitted here.

  The hydrophobic agent used in the carbon layer is not particularly limited, but polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyhexafluoropropylene, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), etc. Fluorine-based polymer materials, polypropylene, polyethylene and the like.

  When the carbon layer has a configuration in which at least two layers of the carbon layer (1) and the carbon layer (2) are laminated, the carbon layer (1) in addition to the configuration in which the hydrophobic agent and the conductive carbon have a predetermined ratio. And the specific surface area of the conductive carbon contained in the carbon layer (2) is also preferred.

Specifically, the specific surface area of the conductive carbon contained in the carbon layer (2) is preferably less than 200 m ² / g, more preferably 50 to 150 m ² / g, particularly preferably 50 to 100 m ² / g. It is good to do. Thereby, not only can the water vapor adsorption performance of the conductive carbon contained in the carbon layer (2) be lowered, but also the durability of the carbon layer can be improved. The carbon layer (2) is disposed in contact with the electrode catalyst layer when the membrane electrode assembly is assembled. Since the solid polymer electrolyte such as Nafion (registered trademark), which is a constituent material of the electrode catalyst layer, is generally strongly acidic, there is a possibility of corroding the conductive carbon contained in the carbon layer (2). However, conductive carbon having a specific surface area of less than 200 m ² / g is also excellent in corrosion resistance. Therefore, by disposing the conductive carbon in the carbon layer (2), corrosion of the conductive carbon is suppressed and durability of the carbon layer is increased. It is possible to improve the performance.

Further, the specific surface area of conductive carbon contained in the carbon layer (1), preferably 200 meters ² / g or more, more preferably 500 to 1000 m ² / g, particularly preferably in a 750~1000m ² / g Good. As a result, not only can the water vapor adsorption performance of the conductive carbon contained in the carbon layer (1) be increased, but the water condensed from the water vapor spreads so as to cover the surface of the conductive carbon. It is possible to prevent flooding by suppressing the air holes in 1) from being blocked.

  When the carbon layer has a structure of three or more layers, another carbon layer may be disposed between the carbon layer (1) and the carbon layer (2). At this time, another carbon further disposed between the carbon layer (1) and the carbon layer (2) so that the adsorption performance of the conductive carbon increases in the thickness direction in the entire carbon layer. The specific surface area of the conductive carbon in the layer may be adjusted. Specifically, an intermediate value may be taken with respect to the specific surface area of the conductive carbon in the carbon layer (2) and the carbon layer (1).

  As the conductive carbon used for the carbon layer, the main component is preferably carbon. In addition, since the specific kind, shape, etc. of the said conductive carbon are the same as that mentioned above, detailed description is abbreviate | omitted here. The specific surface area of the conductive carbon in the carbon layer can be measured by a BET nitrogen adsorption method.

It is more preferable to use graphitized carbon as the conductive carbon having a specific surface area of less than 200 m ² / g. The graphitized carbon is obtained by graphitizing conductive carbon such as carbon black described above by heat treatment or the like. As graphitization proceeds, the conductive carbon has a reduced specific surface area and reduced water vapor adsorption performance, and improved corrosion resistance. Although it does not restrict | limit especially as said heat processing, The method etc. which heat-process the carbon black mentioned above at about 1500-3000 degreeC by inert gas atmosphere, etc. are mentioned.

As the conductive carbon having a specific surface area of less than 200 m ² / g, acetylene black is preferably used in addition to graphitized carbon. Acetylene black is preferably used because of its high purity of acetylene as a raw material and high temperature at the time of decomposition, it has a small specific surface area and low water vapor adsorption performance.

  The carbon layer in which the specific surface area of the conductive carbon is adjusted preferably further contains a hydrophobic agent as a binder in addition to the conductive carbon. As the hydrophobic agent, the same ones as described above are used, and detailed description thereof is omitted here.

  Regarding the carbon layer in which the specific surface area of the conductive carbon is adjusted, the mass ratio of the conductive carbon to the hydrophobic agent is preferably 90:10 to 60:40, more preferably 80:20 to 70:30. . Therefore, in the carbon layer (1) and the carbon layer (2), the mass ratio of the conductive carbon and the hydrophobic agent is set so that the water vapor adsorption performance of the obtained carbon layer has a desired value. It is better to adjust within the range.

More preferably, the weight ratio of the conductive carbon and the hydrophobic agent in the carbon layer (1), 90: 10-80: 20, in particular 90: 10 to 85: preferably set to 15. Thereby, not only can the water vapor adsorption performance of the surface of the conductive carbon contained in the carbon layer (1) be increased, but also flooding can be prevented. The mass ratio of the conductive carbon and the hydrophobic agent in the carbon layer (2) is preferably 80:20 to 60:40, more preferably 70:30 to 60:40. Thereby, not only can the water vapor adsorption performance of the surface of the conductive carbon contained in the carbon layer (2) be lowered, but a carbon layer having excellent gas diffusibility can be obtained.

  In the carbon layer containing conductive carbon and a hydrophilic agent, water vapor adsorption is promoted and gas diffusibility is high. Therefore, conductive carbon and a hydrophilic agent may be included in a portion where it is desired to increase the gas diffusibility of the carbon layer in the gas diffusion layer of the present invention.

  Preferably, in the carbon layer having a configuration in which at least two layers of the carbon layer (1) and the carbon layer (2) are laminated, the carbon layer (1) includes conductive carbon and a hydrophilic agent. As a result, water vapor adsorption is further promoted, gas movement between the carbon layer and the conductive porous substrate layer can be further promoted, and the gas diffusibility of the gas diffusion layer can be further improved. it can.

  As the conductive carbon in the carbon layer (1), the main component is preferably carbon. In addition, since the specific kind, shape, etc. of the said conductive carbon are the same as that mentioned above, detailed description is abbreviate | omitted here.

  The hydrophilic agent contains a hydrophilic group such as a sulfonic acid group such as a perfluorocarbon sulfonic acid polymer represented by Nafion (registered trademark manufactured by DuPont) and Flemion (registered trademark manufactured by Asahi Kasei Corporation). Polymers are preferred. These hydrophilic agents not only improve the water vapor adsorption performance of conductive carbon, but can also function as a binder, so that the conductive carbon coated with the hydrophilic agent becomes an aggregate and has a stable porosity. A carbon layer (1) having a textured structure is obtained.

  In the carbon layer (1), the mass ratio between the conductive carbon and the hydrophilic agent is preferably 90:10 to 60:40, more preferably 80:20 to 70:30. When the mass ratio of the conductive carbon and the hydrophilic agent is within the above range, the water vapor adsorption performance of the conductive carbon contained in the carbon layer (1) can be sufficiently enhanced.

  In the carbon layer having a configuration in which at least two layers of the carbon layer (1) and the carbon layer (2) are laminated, when the carbon layer (1) has a configuration including conductive carbon and a hydrophilic agent, As the carbon layer (2), a layer containing a hydrophobic agent and conductive carbon may be used. Since the carbon layer (2) containing the hydrophobic agent and conductive carbon is the same as described above, detailed description thereof is omitted.

  When the carbon layer has a structure of three or more layers, another carbon layer may be disposed between the carbon layer (1) and the carbon layer (2). At this time, another carbon further disposed between the carbon layer (1) and the carbon layer (2) so that the adsorption performance of the conductive carbon increases in the thickness direction in the entire carbon layer. The specific surface area of the conductive carbon in the layer may be adjusted. Specifically, an intermediate value may be taken with respect to the specific surface area of the conductive carbon in the carbon layer (2) and the carbon layer (1).

  In addition, conductive carbon that has been subjected to hydrophilic treatment in advance also has higher water vapor adsorption performance. Further, such conductive carbon can adsorb moisture condensed from water vapor so as to cover the surface of the conductive carbon. Therefore, excellent drainage and gas diffusibility can be imparted to the carbon layer by including hydrophilic conductive carbon in the portion of the gas diffusion layer of the present invention where the drainage of the carbon layer is desired to be enhanced.

  Preferably, in the carbon layer having a configuration in which at least two layers of the carbon layer (1) and the carbon layer (2) are laminated, the carbon layer (1) includes conductive carbon subjected to a hydrophilic treatment. As a result, water vapor adsorption is further promoted, gas movement between the carbon layer and the conductive porous substrate layer can be further promoted, and the gas diffusibility of the gas diffusion layer can be further improved. it can.

  As the conductive carbon used for the conductive carbon subjected to hydrophilic treatment, the main component is preferably carbon. In addition, since the specific kind, shape, etc. of the said conductive carbon are the same as that mentioned above, detailed description is abbreviate | omitted here.

  Examples of the conductive carbon subjected to the hydrophilic treatment include those whose surface has been modified to be hydrophilic by introducing a hydrophilic group such as a carboxyl group or a phenol group into the conductive carbon described above. The hydrophilic group acts as an active site that promotes the adsorption of water molecules from water vapor, and can promote the condensation of water through hydrogen bonds between the adsorbed water molecules. The water vapor adsorption performance can be further improved.

  The conductive carbon introduced with the hydrophilic group is a conductive carbon in a strong oxidizing aqueous solution containing potassium permanganate, nitric acid, chlorate, persulfate, perborate, percarbonate, hydrogen peroxide, and the like. It can be obtained by using a known method such as a liquid phase method for immersing.

  As the conductive carbon subjected to the hydrophilic treatment, in addition to the above, conductive carbon on which an oxide film is formed is also preferable. The oxide film formed on the conductive carbon surface by heat treatment in an air atmosphere has hydrophilicity.

  The thickness of the oxide film is preferably 50 to 200 nm, more preferably about 100 to 150 nm. If the thickness of the oxide film is less than 50 nm, sufficient water vapor adsorption performance may not be obtained, and if it exceeds 200 nm, the thermal conductivity may decrease. In addition, the thickness of the oxide film of the carbon particles can be measured by elemental analysis.

  The conductive carbon on which the oxide film is formed can be obtained by heat-treating the conductive carbon in an air atmosphere. The heat treatment is preferably performed at 500 to 1500 ° C., more preferably 700 to 1000 ° C., for about 0.5 to 1 hour.

  In order to further improve the hydrophilicity of the oxide film, an element that forms a substance that exhibits hydrophilicity by oxidation treatment may be added in advance to the conductive carbon surface before the heat treatment.

Examples of substances that exhibit hydrophilicity by oxidation treatment include oxides containing alkali and sodium such as sodium phosphate such as sodium phosphate (NaPO ₃ ), oxides of alkali metals such as potassium and lithium, magnesium, calcium, etc. And at least one metal oxide selected from the group consisting of oxides of alkaline earth metals.

Therefore, elements added in advance to the carbon particles include metal elements constituting the metal oxide, such as alkali metals such as phosphorus, sodium, potassium, and lithium, and alkaline earth metals such as magnesium and calcium. These metal elements can be oxidized by an oxidation treatment such as a heat treatment in an air atmosphere to form a substance that exhibits hydrophilicity. The metal elements may be used alone or in combination of two or more. The metal element may be added in advance to the conductive carbon as a compound containing the metal element, such as sodium chloride (NaCl) or phosphorous lime (Ca ₅ F (PO ₄ ) ₃ ).

  In order to add an element that forms a substance exhibiting hydrophilicity by oxidation treatment to the surface of the conductive carbon, a method of immersing the conductive carbon in a solution containing the above-described element may be used, and there is no particular limitation.

  The carbon layer (1) preferably contains a hydrophobic agent or a hydrophilic agent in addition to the conductive carbon subjected to the hydrophilic treatment described above. As a result, the carbon layer (1) having a stable porous structure is obtained in which conductive carbon coated with a hydrophilic agent or a hydrophobic agent is aggregated. The specific types of the hydrophilic agent and the hydrophobic agent are the same as those described above.

  In the carbon layer (1), the mass ratio of the conductive carbon subjected to hydrophilic treatment and the hydrophobic or hydrophilic agent is preferably 90:10 to 60:40, more preferably 80:20 to 70:30. It is good. Thereby, the water vapor adsorption performance of the conductive carbon in the carbon layer (1) can be sufficiently enhanced.

  In the carbon layer having a configuration in which at least two layers of the carbon layer (1) and the carbon layer (2) are laminated, when the carbon layer (1) has a configuration including conductive carbon subjected to a hydrophilic treatment, As the carbon layer (2), the same layer as described above such as one containing a hydrophobic agent and conductive carbon may be used.

  When the carbon layer has a structure of three or more layers, another carbon layer may be disposed between the carbon layer (1) and the carbon layer (2). At this time, another carbon further disposed between the carbon layer (1) and the carbon layer (2) so that the adsorption performance of the conductive carbon increases in the thickness direction in the entire carbon layer. The specific surface area of the conductive carbon in the layer may be adjusted. Specifically, an intermediate value may be taken with respect to the specific surface area of the conductive carbon in the carbon layer (2) and the carbon layer (1).

  In the gas diffusion layer of the present invention, the thickness of the carbon layer is preferably 25 to 100 μm, more preferably about 50 to 75 μm. If the thickness of the carbon layer is less than 25 μm, the desired effect of the carbon layer may not be obtained. If the thickness exceeds 100 μm, the gas diffusion path becomes long and the gas diffusibility may be reduced.

  Further, when the carbon layer has a carbon layer (1) and a carbon layer (2) having at least a two-layer structure, the thickness of the carbon layer (1) is preferably 12.5 to 50 μm, more preferably May be about 25 to 37.5 μm. Further, the thickness of the carbon layer (2) is preferably 12.5 to 50 μm, more preferably about 25 to 37.5 μm.

  The porosity of the carbon layer may be appropriately determined so as to obtain a desired gas diffusion layer, but may be about 60 to 90% by volume. Moreover, when the carbon layer has at least a two-layer structure of the carbon layer (1) and the carbon layer (2), the porosity in the carbon layer (1) and the carbon layer (2) is not particularly limited. It suffices if it falls within the above range.

  The average pore diameter of the carbon layer may be appropriately determined so as to obtain a desired gas diffusion layer, but may be about 50 to 100 nm. When the carbon layer has at least a two-layer structure of the carbon layer (1) and the carbon layer (2), the average pore diameter in the carbon layer (1) and the carbon layer (2) is not particularly limited. However, what is necessary is just to make it become in the said range.

  The gas diffusion layer of the present invention has a conductive porous substrate layer in addition to the carbon layer described above. The conductive porous substrate layer has a porous structure for sufficiently diffusing an externally supplied fuel gas or oxidant gas, and has a sufficient conductivity for collecting electrons generated by a power generation reaction. What is necessary is just to consist of a base material which has property.

  If the said electroconductive porous base material layer is a conventionally well-known thing, it can be especially used without a restriction | limiting. Specifically, a sheet-like material having conductivity and porosity such as a carbon woven fabric, a paper-like paper body, a felt, and a non-woven fabric can be used. More specifically, base materials such as carbon paper, carbon cloth, and carbon non-woven fabric are preferred. A commercial item can also be used for the said electroconductive porous base material layer, for example, Toray Corporation carbon paper TGP series, Toho Tenax Co., Ltd. carbon cloth, etc. are mentioned.

  The thickness of the conductive porous base material layer may be appropriately determined in consideration of the characteristics of the obtained gas diffusion layer, but may be about 30 to 500 μm. If the thickness is less than 30 μm, sufficient mechanical strength or the like may not be obtained, and if it exceeds 500 μm, the distance through which gas or water permeates is undesirably increased.

  The conductive porous substrate layer preferably contains a water repellent in order to further improve drainage and prevent flooding. Although it does not specifically limit as said water repellent, It is fluorine-type, such as a polytetrafluoroethylene (PTFE), a polyvinylidene fluoride (PVDF), a polyhexafluoropropylene, a tetrafluoroethylene-hexafluoropropylene copolymer (FEP). Examples thereof include polymer materials, polypropylene, and polyethylene.

  The method for producing the gas diffusion layer of the present invention is not particularly limited and can be used by appropriately referring to known methods.

  First, as a water repellent treatment method for the conductive porous substrate layer, a general water repellent treatment method may be used. Examples include a method in which a base material used for the conductive porous base material layer is immersed in an aqueous dispersion solution or an alcohol dispersion solution of a water repellent and then heated and dried in an oven or the like. In view of ease of exhaust gas treatment during drying, it is preferable to use an aqueous dispersion solution of a water repellent.

  Next, as a method for producing the carbon layer, a conventionally known method may be referred to as appropriate. For example, in the case of a carbon layer having conductive carbon and a hydrophobic agent, conductive carbon having a desired water vapor adsorption performance, a hydrophobic agent, and the like are selected from alcohols such as water, perfluorobenzene, dichloropentafluoropropane, methanol, and ethanol. A slurry is prepared by dispersing in a solvent such as a solvent. In the slurry, a plurality of conductive carbons having desired water vapor adsorption performance are mixed. Next, the slurry is applied and dried on the conductive porous substrate layer. Thereby, a carbon layer containing at least two kinds of conductive carbons having different water vapor adsorption performances is obtained.

  In addition, as a method for producing a carbon layer in which at least two layers of the carbon layer (1) and the carbon layer (2) having different contents of the hydrophobic agent and the conductive carbon are laminated, a slurry is prepared in the same manner as described above. In doing so, a plurality of slurries with different hydrophobic agent contents are prepared. Then, the process of apply | coating and drying on an electroconductive porous base material layer in an order from the slurry with little content of a hydrophobic agent is repeated.

  In addition, as a method for producing a carbon layer formed by laminating at least two layers of a carbon layer (1) and a carbon layer (2) having different specific surface areas of conductive carbon, a slurry is prepared in the same manner as described above. A plurality of slurries having different specific surface areas of conductive carbon are prepared. Then, the process of apply | coating and drying on a conductive porous base material layer in order from the slurry containing conductive carbon with a large specific surface area is repeated.

  In addition, as a method for producing a carbon layer containing conductive carbon and a hydrophilic agent, conductive carbon having a desired water vapor adsorption performance and a hydrophilic agent, such as water, perfluorobenzene, dichloropentafluoropropane, methanol, ethanol, etc. A slurry may be prepared by dispersing in a solvent such as an alcohol solvent, and the slurry may be applied and dried on the conductive porous substrate layer. Thereafter, by further applying and drying a slurry containing conductive carbon and a hydrophobic agent, a carbon layer (1) containing conductive carbon and a hydrophobic agent, and a carbon layer containing conductive carbon and a hydrophilic agent ( A carbon layer obtained by laminating at least two layers with 2) is obtained.

  Furthermore, as a method for producing a carbon layer containing conductive carbon that has been subjected to a hydrophilic treatment, a slurry containing conductive carbon and a hydrophobic agent or a hydrophilic agent is prepared in the same manner as described above, and a conductive porous substrate layer is formed on the conductive porous substrate layer. A method of applying and drying may be used. Thereafter, by further applying and drying a slurry containing conductive carbon and a hydrophobic agent, the carbon layer (1) containing the conductive carbon and the hydrophobic agent, and the conductive carbon and the hydrophobic agent or hydrophilic agent having been subjected to hydrophilic treatment. A carbon layer obtained by laminating at least two layers with a carbon layer (2) containing an agent is obtained.

  In the method described above, a slurry containing at least conductive carbon is applied and dried on the conductive porous substrate layer. However, the slurry is first dried and then pulverized, and the resulting powder is electrically conductive. Even if it is the method of spraying on a porous porous base material layer, a carbon layer can be produced.

  The carbon layer obtained by each method described above is preferably heat-treated at about 250 to 400 ° C. using a muffle furnace or a firing furnace. Thereby, the strength of the carbon layer can be increased.

  The second of the present invention is a membrane electrode assembly for a fuel cell using the first gas diffusion layer of the present invention described above. Examples of the fuel cell in which the membrane electrode assembly is used include a polymer electrolyte fuel cell (PEFC), a phosphoric acid fuel cell (PAFC), and a solid oxide fuel cell (SOFC). From the viewpoint of practicality and safety, it is preferably used as a polymer electrolyte fuel cell (PEFC). Accordingly, the following description will be made by taking a solid polymer fuel cell as an example.

  If the structure of the said membrane electrode assembly is a conventionally well-known thing, it will be used without a restriction | limiting in particular. For example, as shown in FIG. 2, on both sides of the solid polymer electrolyte membrane 200, an anode side electrode catalyst layer 210a and an anode side gas diffusion layer 220a, a cathode side electrode catalyst layer 210c and a cathode side gas diffusion layer 220c, Examples of the arrangement are listed. Further, when the first gas diffusion layer of the present invention having a structure in which the carbon layer is composed of two or more layers is used, the carbon layers (2) 223a and 223c and the electrode catalyst layers 210a and 210c are brought into contact with each other to form a conductive porous layer. The porous base material layers 221a and 221c are preferably disposed outside the membrane electrode assembly. Accordingly, excess water in the electrode catalyst layer can be absorbed by the capillary force due to the porous structure of the carbon layer, and flooding in the electrode catalyst layer can be prevented.

  As described above, the first gas diffusion layer of the present invention has both drainage and moisture retention. Therefore, according to the gas diffusion layer, the wettability of the solid polymer electrolyte membrane can be maintained while preventing the flooding phenomenon. Therefore, a membrane electrode assembly that can stably exhibit high power generation performance under a wide range of operating conditions can be obtained. Furthermore, since the wettability of the solid polymer electrolyte membrane can be kept constant, it is possible to suppress the deterioration of the solid polymer electrolyte membrane and improve the durability of the membrane electrode assembly.

  In the membrane electrode assembly, the first gas diffusion layer of the present invention may be used for at least one of the anode side gas diffusion layer and the cathode side gas diffusion layer. Therefore, it is preferably used for both the anode-side gas diffusion layer and the cathode-side gas diffusion layer.

  The membrane electrode assembly has the same configuration as a conventionally known membrane electrode assembly except that the first gas diffusion layer of the present invention is used. Therefore, detailed description of the solid polymer electrolyte membrane, the electrode catalyst layer, etc. in the membrane electrode assembly is omitted.

  A third aspect of the present invention is a fuel cell using the membrane electrode assembly described above. According to the membrane electrode assembly, the flooding phenomenon can be suppressed even under operating conditions in which a large amount of water such as high current density and high humidification is likely to be generated. The wettability of the solid polymer electrolyte membrane can be maintained even under operating conditions where the molecular electrolyte membrane tends to dry. Therefore, according to the present invention, high power generation performance can be stably exhibited even under a wide range of operating conditions, and a fuel cell having excellent durability can be obtained.

  The structure of the fuel cell is not particularly limited, and examples thereof include a structure in which a membrane electrode assembly is sandwiched between separators.

  The separator has a function of separating air and fuel gas, and any conventional separator can be used without particular limitation. As the separator, conventionally known separators such as those made of carbon such as dense carbon graphite and a carbon plate and those made of metal such as stainless steel can be used without particular limitation. Moreover, in order to ensure the flow path of air and fuel gas, a gas distribution groove | channel may be formed and a conventionally well-known technique can be utilized suitably. The shape of the separator is not particularly limited, and may be appropriately determined in consideration of the output characteristics of the obtained fuel cell.

  Furthermore, a stack in which a plurality of membrane electrode assemblies are stacked via a separator and connected in series may be formed so that the fuel cell can obtain a desired voltage or the like. The shape of the fuel cell is not particularly limited, and may be determined as appropriate so that desired battery characteristics such as voltage can be obtained.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to the following Example.

Example 1
(1) Water-repellent treatment of conductive porous substrate layer Carbon paper (TGP-H-060 manufactured by Toray Industries, Inc., thickness 200 μm) was used as the conductive porous substrate layer, and this was punched into a 100 mm × 100 mm square. Then, an aqueous dispersion of PTFE (D1 manufactured by Daikin Industries, Ltd., containing 60% by mass of PTFE) was immersed in a solution diluted with pure water to a predetermined concentration for 2 minutes, and then in an oven at 60 ° C. for 10 minutes. By drying, the water-repellent treatment of the conductive porous substrate was performed. At this time, the PTFE content in the conductive porous substrate layer was 20% by mass.

(2) Preparation of carbon layer First, carbon black A (product name Vulcan XC-72R, average particle size 1 μm, specific surface area 260 m ² / g), the same aqueous PTFE dispersion solution as in the above step (1), and water The slurry (1) was prepared by mixing and dispersing the carbon black and PTFE in a mass ratio of 60:40 and using a homogenizer for 3 hours. Next, a slurry (2) was prepared in the same manner as in the preparation of the slurry (1) except that carbon black B (product name Denka black, average particle size 1 μm, specific surface area 64 m ² / g) was used.

  The slurry (1) is applied on the conductive porous substrate layer that has been subjected to the water-repellent treatment previously using a bar coater, and then dried in an oven at 80 ° C. for 1 hour to obtain a carbon layer (1). Then, the slurry (2) was applied onto the carbon layer (1) using a bar coater and then dried in an oven at 80 ° C. for 1 hour to obtain a carbon layer (2). Thereby, the gas diffusion layer 1 in which the carbon layer (1) and the carbon layer (2) were formed on the conductive porous substrate layer was obtained. The thicknesses of the carbon layer (1) and the carbon layer (2) are each 25 μm, the average pore diameter in the carbon layer (1) is 100 nm, and the average pore diameter in the carbon layer (2) is 100 nm. It was. Table 1 summarizes the water vapor adsorption performance [ml / g] of each carbon black surface in the carbon layer (1) and the carbon layer (2).

( Reference Example 2)
Carbon black C (Ketjen Black EC) was heat treated in an inert gas atmosphere of nitrogen gas at 2500 ° C. for 24 hours to produce graphitized carbon (product name: graphitized Ketjen black, average particle size 1 μm, specific surface area). 160 m ² / g).

  In the preparation of the slurry (1), a gas diffusion layer 2 was obtained in the same manner as in Example 1 except that the graphitized carbon was used in place of the carbon black A. The average pore diameter in the carbon layer (1) was 100 nm, and the average pore diameter in the carbon layer (2) was 100 nm. Table 1 summarizes the water vapor adsorption performance [ml / g] of each carbon black surface in the carbon layer (1) and the carbon layer (2).

( Reference Example 3)
First, carbon black A (product name Vulcan XC-72R, average particle size 1 μm, specific surface area 260 m ² / g), the same PTFE aqueous dispersion solution as in step (1) of Example 1, and water were added to carbon black. And PTFE were adjusted to a mass ratio of 80:20, and a slurry (4) was prepared by mixing and dispersing with a homogenizer for 3 hours. Next, a slurry (5) was prepared in the same manner as in the preparation of the slurry (4) except that the mass ratio of carbon black and PTFE was 60:40.

  After applying the slurry (4) on a conductive porous substrate layer subjected to the same water-repellent treatment as in Example 1 using a bar coater, carbon is obtained by drying in an oven at 80 ° C. for 1 hour. After obtaining the layer (1), the slurry (5) was applied using a bar coater and then dried in an oven at 80 ° C. for 1 hour to obtain a carbon layer (2). Thereby, the gas diffusion layer 3 in which the carbon layer (1) and the carbon layer (2) were formed on the conductive porous substrate layer was obtained. The thicknesses of the carbon layer (1) and the carbon layer (2) are each 25 μm, the average pore diameter in the carbon layer (1) is 100 nm, and the average pore diameter in the carbon layer (2) is 100 nm. It was. Table 1 summarizes the water vapor adsorption performance [ml / g] of each carbon black surface in the carbon layer (1) and the carbon layer (2).

( Reference Example 4)
Carbon Black A (product name Vulcan XC-72R, average particle size 1 μm, specific surface area 260 m ² / g), Nafion solution (registered trademark DuPont DE520, Nafion content 5 wt%), and 2-propanol And Nafion were adjusted to a mass ratio of 80:20, and mixed and dispersed for 3 hours with a homogenizer to obtain slurry (6).

A gas diffusion layer 4 was obtained in the same manner as in Reference Example 3 except that the slurry (6) was used instead of the slurry (4). The average pore diameter in the carbon layer (1) was 100 nm, and the average pore diameter in the carbon layer (2) was 100 nm. Table 1 summarizes the water vapor adsorption performance [ml / g] of each carbon black surface in the carbon layer (1) and the carbon layer (2).

(Comparative Example 1)
A gas diffusion layer 6 was obtained in the same manner as in Example 1 except that only the slurry (1) prepared in Example 1 was applied onto the water-repellent conductive porous layer. In addition, the thickness of the carbon layer produced in the said conductive porous layer was 50 micrometers.

(Comparative Example 2)
A gas diffusion layer 7 was obtained in the same manner as in Example 1 except that only the slurry (2) prepared in Example 1 was applied onto the water-repellent conductive porous layer. In addition, the thickness of the carbon layer produced in the said conductive porous layer was 50 micrometers.

(Comparative Example 3)
A gas diffusion layer 7 was obtained in the same manner as in Example 1 except that only the slurry (4) prepared in Reference Example 3 was applied on the water-repellent conductive porous layer. In addition, the thickness of the carbon layer produced in the said conductive porous layer was 50 micrometers.

(Evaluation)
By using each gas diffusion layer prepared in Example 1, Reference Example 3, and Comparative Examples 1 to 3, a membrane electrode assembly was prepared according to the following procedure, and the power generation performance of the membrane electrode assembly was measured. Each gas diffusion layer was evaluated.

(1) Preparation of catalyst ink Platinum-supported carbon (TEC10E50E, Tanaka Kikinzoku Kogyo Co., Ltd., TEC10E50E, platinum content 46.5 wt%) 10 g, solid polymer electrolyte solution (DuPont NAFION solution DE520, electrolyte content 5 wt%) 90 g, pure water 25 g Then, 10 g of 2-propanol (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was mixed and dispersed for 3 hours using a homogenizer in a glass container in a water bath set to be kept at 20 ° C. to obtain a catalyst ink. .

(2) Preparation of electrode catalyst layer The catalyst ink prepared previously using a screen printer was applied to one side of a 200-μm-thick PTFE sheet (Naflon (registered trademark) sheet manufactured by Nichias) and 100 in an oven. After drying at ° C. for 30 minutes, it was cut into a 10 cm square.

(3) Assembly of membrane electrode assembly and single cell Formation of two electrode catalyst layers prepared in advance by sandwiching a solid polymer electrolyte membrane (NAFION NR-112 manufactured by DuPont) with a square of 10 cm on a side and a thickness of 30 μm The PTFE sheet is stacked so that the electrode catalyst layer forming sides face each other, and hot pressed at 130 ° C. for 10 minutes at a pressure of 3 MPa per one side PTFE sheet. The electrode catalyst layer was transferred to the membrane to obtain a joined body. At this time, the transfer rate of the electrode catalyst layer from the PTFE sheet to the solid polymer electrolyte is 100%, and the platinum weight per 1 cm ² of the single-sided electrode catalyst layer area on the solid polymer electrolyte membrane is 0.40 mg. did. Moreover, the thickness of the electrode catalyst layer was 10 μm, respectively.

  The obtained joined body was put in a state where the conductive porous base material layer was sandwiched between two gas diffusion layers prepared in advance, and sandwiched with a graphite separator, and further, A single cell for evaluation was obtained by sandwiching between gold-plated stainless steel current collector plates.

(4) Single cell evaluation The electric power generation test of each single cell for evaluation of Example 1, Reference example 3, and Comparative Examples 1-3 was done.

(Power generation test 1)
Hydrogen is supplied to the anode and air is supplied to the cathode, and the gas flow rate is anode / cathode = 1.5 S.V. R. /2.5S. R. , Relative humidity anode 100% R.V. H. / Cathode 30% R.V. H. A power generation test was performed under the conditions of a cell temperature of 70 ° C. Table 2 shows the resistance and voltage of the cell at a current density of 1 A / cm ² .

Next, hydrogen was supplied to the anode and air was supplied to the cathode, and the gas flow rate was anode / cathode = 1.5 S.V. R. /2.5S. R. , Relative humidity anode 100% R.V. H. / Cathode 100% R.V. H. A power generation test was performed under the conditions of a cell temperature of 70 ° C. Table 2 shows the resistance and voltage of the cell at a current density of 1 A / cm ² .

  “S.R.” (Stoichiometric Ratio) means the ratio of the amount of hydrogen or oxygen required to flow a predetermined amount of current, and “anode S.R. = 1.5” This means that hydrogen is supplied at a flow rate 1.5 times the amount of hydrogen necessary for supplying a predetermined amount of current.

From Table 2, the relative humidity at the cathode was 30% R.D. H. Since the solid polymer electrolyte membrane at a current density of 1 A / cm ² is easy to dry, the comparative example 1 having only a carbon layer having a small water vapor adsorption performance of carbon is less likely to cause water vapor adsorption. It can be seen that the humidity of the polymer electrolyte membrane is kept high and the cell resistance is low. In Comparative Example 2 having only a carbon layer with high carbon water vapor adsorption performance, the solid polymer electrolyte membrane is easy to dry and the cell resistance is high. On the other hand, in Example 1, cell resistance close to that of Comparative Example 1 was obtained, and it was found that even under low humidification conditions, drying of the solid polymer electrolyte membrane was suppressed and high power generation performance was obtained. .

The relative humidity at the cathode is 100% R.D. H. It can be seen that under conditions where flooding with high humidification and high current density at a current density of 1 A / cm ² is likely to occur, the voltage of Comparative Example 1 is reduced, causing flooding. In Comparative Example 2, flooding is suppressed and a high voltage is obtained. On the other hand, in Example 1, a higher cell voltage is obtained than in Comparative Example 2, and it is understood that flooding is suppressed and a high cell voltage can be obtained even under conditions of high humidification and high current density. .

In addition, although power generation evaluation 1 using the gas diffusion layer produced in Reference Example 2 was not carried out, from the measurement result of water vapor adsorption performance in Table 1, Reference Example 2 is under a low humidification condition as compared with Example 1. Although the power generation performance is slightly inferior, it can be estimated that the power generation performance under high humidification conditions is equivalent.

  As described above, according to the gas diffusion layer of the present application, drying and flooding of the solid polymer electrolyte membrane can be suppressed, and a fuel cell capable of stably exhibiting high power generation performance under a wide range of operating conditions can be obtained. I understand that

(Power generation test 2)
Hydrogen is supplied to the anode and air is supplied to the cathode, and the gas flow rate is anode / cathode = 1.5 S.V. R. /2.5S. R. , Relative humidity anode 100% R.V. H. / Cathode 30% R.V. H. The durability was evaluated by continuously operating with the current density fixed at 1 A / cm ² under the condition of the cell temperature of 70 ° C. Table 3 shows the resistance value and voltage of the cell after 0 seconds from the start of power generation (initial performance) and after 100 hours.

From Table 3, the resistance of Reference Example 3 is low, and the solid polymer electrolyte membrane is prevented from being dried, so that the damage to the solid polymer electrolyte membrane is small and the voltage drop is small. On the other hand, in Comparative Example 3, it can be seen that the solid polymer electrolyte membrane is easily dried, so that the solid polymer electrolyte membrane is greatly damaged and the voltage gradually decreases. Note that power generation evaluation 2 using the gas diffusion layer produced in Reference Example 4 was not performed, but from the water vapor adsorption performance shown in Table 1, Reference Example 4 is a power generation under low humidification conditions as compared to Reference Example 3. The performance is equivalent or better, and it can be estimated that the power generation performance under high humidification conditions is slightly inferior compared to Comparative Example 3. Therefore, according to the gas diffusion layer of the present invention, the wettability of the solid polymer electrolyte membrane can be kept constant, so that deterioration of the solid polymer electrolyte membrane can be suppressed, and durability is improved. A fuel cell is obtained.

  According to the gas diffusion layer of the present invention, it is possible to provide a fuel cell that can stably exhibit high power generation performance under a wide range of operating conditions.

The cross-sectional schematic diagram of the gas diffusion layer of this invention is shown. The cross-sectional schematic diagram of the membrane electrode assembly which is one Embodiment of this invention is shown.

Explanation of symbols

121 ... conductive porous substrate layer,
122 ... carbon layer (1),
123 ... carbon layer (2),
200 ... solid polymer electrolyte membrane,
210a ... anode side electrode catalyst layer,
210c ... cathode-side electrode catalyst layer,
220a ... anode side gas diffusion layer,
220c ... Cathode side gas diffusion layer.

221a ... anode side conductive porous substrate layer,
221c ... cathode-side conductive porous substrate layer,
222a ... anode side carbon layer (1),
222c ... cathode side carbon layer (1),
223a ... anode side carbon layer (2),
223c ... cathode side carbon layer (2).

Claims (9)

In the gas diffusion layer for fuel cells having a carbon layer on the conductive porous substrate layer,
The carbon layer includes at least two kinds of conductive carbons having different water vapor adsorption performances, and at least two layers of a carbon layer (1) and a carbon layer (2) are laminated,
The water vapor adsorption performance of the conductive carbon contained in the carbon layer (1) is larger than the water vapor adsorption performance of the conductive carbon contained in the carbon layer (2),
In the carbon layer (1), the conductive carbon has a specific surface area of 200 m ² / g or more,
The gas diffusion layer for a fuel cell, wherein the specific surface area of the conductive carbon is less than 200 m ² / g in the carbon layer (2).   The gas diffusion layer for a fuel cell according to claim 1, wherein the carbon layer (1) is disposed in contact with the conductive porous substrate layer.   The fuel cell according to claim 1 or 2, wherein the carbon layer (2) includes the conductive carbon and a hydrophobic agent, and a mass ratio of the conductive carbon and the hydrophobic agent is 80:20 to 60:40. Gas diffusion layer.   The carbon layer (1) includes the conductive carbon and a hydrophobic agent, and a mass ratio of the conductive carbon and the hydrophobic agent is 90:10 or more and less than 80:20. The gas diffusion layer for fuel cells as described. The gas diffusion layer for a fuel cell according to any one of claims 1 to 4, wherein the conductive carbon contained in the carbon layer (2) is graphitized. The gas diffusion layer for a fuel cell according to any one of claims 1 to 3, wherein the carbon layer (1) includes the conductive carbon and a hydrophilic agent.   The gas diffusion layer for a fuel cell according to any one of claims 1 to 6, wherein the carbon layer (1) contains the conductive carbon subjected to a hydrophilic treatment.   A membrane electrode assembly for a fuel cell using the gas diffusion layer for a fuel cell according to any one of claims 1 to 7.   A fuel cell using the fuel cell membrane electrode assembly according to claim 8.

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