Apparatus for production of fuel cell catalyst layer, method for production of fuel cell catalyst layer, polyelectrolyte solution, and process for production of polyelectrolyte solution

An apparatus for production of a fuel cell catalyst layer forming a catalyst layer by a catalyst paste, the apparatus including a device for removal of water to obtain a polyelectrolyte solution by reducing, to a predetermined value or less, the concentration of water in a pre-solution in which a polyelectrolyte having a side chain including a hydrophilic functional group is dissolved in a solvent; and an agitator means for obtaining the catalyst paste by mixing a pre-paste obtained by mixing a catalyst with water and the polyelectrolyte solution.

TECHNICAL FIELD

The present invention relates to an apparatus for production of a fuel cell catalyst layer, a method for production of the fuel cell catalyst layer, a polyelectrolyte solution, and a process for production of the polyelectrolyte solution.

BACKGROUND ART

Conventionally, there is known a fuel cell system using a membrane electrode assembly (MEA)90as disclosed in Patent Document 1. This MEA90includes, as shown inFIG. 4, an electrolyte membrane91composed of a solid polymer membrane such as Nation (registered trademark of DuPont), a cathode93that is bonded to one surface of the electrolyte membrane91and supplied with air, and an anode92that is bonded to the other surface of the electrolyte membrane91and supplied with fuel such as hydrogen.

The cathode93is composed of a gas-permeable base material93b, such as carbon cloth, carbon paper, or carbon felt, and a cathode catalyst layer93aformed on one surface of the base material93b. The other part of the cathode93than the cathode catalyst layer93ais the base material93b, which serves as a cathode diffusion layer that diffuses air to the cathode catalyst layer93aon the nonelectrolyte side.

The anode92is also composed of a base material92bsimilar to the base material described above, and an anode catalyst layer92aformed on one surface of the base material92b. The other part of the anode92than the anode catalyst layer92ais the base material92b, which serves as an anode diffusion layer that diffuses fuel to the anode catalyst layer92aon the nonelectrolyte side.

The cathode catalyst layer93aand the anode catalyst layer92ainclude, as shown inFIG. 5, innumerable pieces of catalysts81each composed of a support81amade of carbon black supporting catalyst metal fine particles81bof a material such as platinum (Pt), and a polyelectrolyte82that binds the pieces of the catalysts81to each other and binds them to a base material (not shown). As the polyelectrolyte82, a similar material to that of the electrolyte membrane91is used.

Then, the MEA90is sandwiched between separators (not shown) to form a fuel cell serving as a minimum unit of electric power generation, and then, a large number of the cells are stacked together to form a fuel cell stack. The cathode catalyst layer93ais supplied with air by air supply means, and the anode catalyst layer92ais supplied with hydrogen or the like by hydrogen supply means or the like. Thus, the fuel cell system is formed.

In the MEA90, hydrogen ions (H+: protons) and electrons are generated from the fuel by an electrochemical reaction in the anode catalyst layer92a. Then, the protons move in the electrolyte membrane91toward the cathode catalyst layer93ain the form of H3O+accompanied by water molecules. The electrons flow into the cathode catalyst layer93athough a load connected to the fuel cell system. On the other hand, in the cathode catalyst layer93a, water is generated from oxygen contained in air, the protons, and the electrons. The electrochemical reaction as described above occurs continuously, whereby the fuel cell system can generate an electromotive force continuously.

RELATED ART DOCUMENT

Patent Document

Patent Document 1: Japanese Patent Application Publication No. JP-A-2009-104905

DISCLOSURE OF THE INVENTION

Problems to be Solved by the Invention

However, the conventional MEA90described above is subject to performance degradation due to drying of the polyelectrolyte in the electrolyte membrane and the catalyst layers under low humidified conditions. On the other hand, under over-humidified conditions, performance degradation is caused by blockage of gas supply (flooding) due to accumulation of water. For these reasons, the fuel cell provided with the MEA90has a problem of reduction in power generation capacity under the environments described above.

In view of the conventional circumstances described above, it is a problem to be solved by the present invention to obtain a fuel cell catalyst layer that allows an electrochemical reaction to proceed smoothly. In addition, it is another problem to be solved by the present invention to provide a polyelectrolyte solution for obtaining the fuel cell catalyst layer, and a process for producing the polyelectrolyte solution.

Means for Solving the Problems

An apparatus for production of a fuel cell catalyst layer forming a catalyst layer by a catalyst paste according to the present invention is characterized by including water removing means for obtaining a polyelectrolyte solution by reducing to a predetermined value or less a concentration of water in a pre-solution in which a polyelectrolyte having a side chain including a hydrophilic functional group is dissolved in a solvent, and agitating means for obtain the catalyst paste by mixing a pre-paste obtained by mixing a catalyst with water with the polyelectrolyte solution (claim1).

According to the knowledge of the inventor of the present invention, it is inferred that protons and entrained water are smoothly moved, and generated water is smoothly diffused back and discharged by virtue of the following effect: In the cathode catalyst layer93aand the anode catalyst layer92a, a hydrophilic layer83is formed by a hydrophilic functional group at an end of a side chain101of the polyelectrolyte82between the catalyst81and a layer of the polyelectrolyte82. In the catalyst layer in which the hydrophilic layer83is aligned in one direction and formed uniformly in a continuous state, the generated water produced in the cathode93can be diffused back to the anode92while being held in the hydrophilic layer83even under low humidified conditions. As a result, the polyelectrolyte82in the electrolyte membrane91and the catalyst layers is prevented from drying, whereby high performance can be maintained. Also, under over-humidified conditions, the generated water is discharged through the hydrophilic layer83in the same manner, whereby performance can be prevented from being degraded.

Therefore, in order to allow the hydrophilic layer83to be formed uniformly, the inventor has focused attention on the state of the polyelectrolyte82in the polyelectrolyte solution, and has discovered the following knowledge. That is, as shownFIGS. 8A and 8B, the polyelectrolyte82has a hydrophobic main chain100and the side chain101including the hydrophilic functional group. The hydrophilic functional group is formed of, for example, a sulfone group (SO3−). If the catalyst81is mixed with water to form the pre-paste, and then the pre-paste is mixed with the polyelectrolyte solution to form the catalyst paste, the hydrophilic functional group is attracted to the water adhering to the catalyst81, and thus, the hydrophilic layer83is formed in the cathode catalyst layer93aand the anode catalyst layer92a.

The inventor has discovered that, when the concentration of water in the polyelectrolyte solution is reduced, the viscosity of the polyelectrolyte solution increases even if the concentration of the polyelectrolyte82in the polyelectrolyte solution stays the same. The inventor has also discovered that, when, by contrast, the concentration of water in the polyelectrolyte solution is increased, the viscosity of the polyelectrolyte solution is reduced. From these discoveries, the inventor has inferred that, if the concentration of water in the polyelectrolyte solution is high, the water adheres to the side chain101of the polyelectrolyte82, and as shown inFIG. 8A, the polyelectrolyte82is placed in a tightened state in the polyelectrolyte solution, thereby resulting in the reduction in viscosity of the polyelectrolyte solution. The inventor has also inferred that, when the concentration of water in the polyelectrolyte solution is slightly reduced, the polyelectrolyte82is loosened in the polyelectrolyte solution by an effect of an organic solvent contained in the polyelectrolyte solution as shown inFIG. 8B, thereby resulting in the increase in viscosity of the polyelectrolyte solution.

If, for example, the cathode catalyst layer93ais produced by mixing the polyelectrolyte solution containing the polyelectrolyte82that has advanced to be tightened, the cathode catalyst layer93ais considered to be in the state shown inFIG. 9. That is because the polyelectrolyte82is tightened in the cathode catalyst layer93a, the side chain101extends in several directions. Then, the side chain101and water in the cathode catalyst layer93aadhere to each other, whereby the hydrophilic layer83is formed in a dispersed manner in the cathode catalyst layer93a. As a result, in the place where the polyelectrolyte82is tightened in the cathode catalyst layer93a, the protons and the water are difficult to move in the cathode catalyst layer93adue to ionic resistance in the cathode catalyst layer93a. Accordingly, performance degradation is caused by drying of the polyelectrolyte82in the electrolyte membrane91and the catalyst layers under low humidified conditions, and caused by flooding under over-humidified conditions.

In order to solve the above-described problems, the inventor has repeatedly made eager studies to invent the apparatus for production of a fuel cell catalyst layer of the present invention. That is, because the concentration of water has the predetermined value or less in the polyelectrolyte solution obtained by the water removing means included in the apparatus, the polyelectrolyte solution has a high viscosity, and the side chain101of the polyelectrolyte82is difficult to adhere to the water in the polyelectrolyte solution. For this reason, the internal state of the polyelectrolyte solution is considered to be as shown inFIG. 1, that is, a state in which the polyelectrolyte82is loosened in the polyelectrolyte solution. Accordingly, in the catalyst paste obtained by mixing with the pre-paste using the agitating means, and also in the fuel cell catalyst layer obtained from the catalyst paste, the hydrophilic functional group such as a sulfone group adheres to water in the pre-paste. As a result, as shown inFIG. 6, in the fuel cell catalyst layer, the hydrophilic layer83of the polyelectrolyte82is formed in an oriented state to a surface of the catalyst81. It is further considered that, because the sulfone group adheres to the water in the pre-paste as described above, the hydrophilic functional group in the side chain101of the polyelectrolyte82is placed in an oriented state toward the side of the catalyst81(PFF structure) so as to form the hydrophilic layer83on the catalyst81in the fuel cell catalyst layer. For this reason, in the fuel cell catalyst layer obtained with this production apparatus, as shown inFIG. 5, the protons and the water easily move, thus allowing the electrochemical reaction to proceed smoothly. As a result, in the MEA90having the fuel cell catalyst layer, the power generation capacity can be made high both under low humidified conditions and under over-humidified conditions.

Therefore, with the apparatus for production of a fuel cell catalyst layer of the present invention, it is possible to obtain the fuel cell catalyst layer in which the electrochemical reaction is smoothly performed.

In the apparatus for production of a fuel cell catalyst layer of the present invention, the water removing means is preferably a warming operation in hot water (claim2). In this case, the concentration of water in the pre-solution can easily have the predetermined value or less, and thus, the polyelectrolyte solution of the present invention can be obtained easily.

The polyelectrolyte solution of the present invention is characterized in that a polyelectrolyte having a side chain including a hydrophilic functional group is dissolved in a solvent, and a concentration of water is 10% or less (claim3).

Because the concentration of water is as low as 10% or less, the state of the polyelectrolyte solution of the present invention is considered to be as shown inFIG. 1, that is, the state in which the polyelectrolyte82is loosened in the polyelectrolyte solution. In the polyelectrolyte82in such a loosened state, the main chain100extends in one direction. For this reason, it is considered that, in the fuel cell catalyst layer in which the polyelectrolyte solution is mixed, the hydrophilic functional group and the water adhere to each other in one direction, and the hydrophilic layer83is aligned in one direction and placed in a continuous state in the fuel cell catalyst layer. As a result, in the fuel cell catalyst layer in such a state, the protons and the water easily move, thus allowing the electrochemical reaction to proceed smoothly.

Therefore, the polyelectrolyte solution of the present invention is preferable as a polyelectrolyte solution forming the fuel cell catalyst layer.

According to test results obtained by the inventor, the concentration of water in the polyelectrolyte solution is preferably 5% or less (claim4). In this case, because the concentration of water in the polyelectrolyte solution is further reduced, the polyelectrolyte82in the polyelectrolyte solution is placed in a more loosened state, thus being easily placed in the state shown inFIG. 1.

The solvent preferably contains at least one type of secondary alcohols and tertiary alcohols (claim5). According to tests conducted by the inventor, when the solvent contains a primary alcohol such as methanol or ethanol, the viscosity of the polyelectrolyte solution does not increase even if the water concentration is reduced. When the solvent contains a secondary alcohol such as isopropyl alcohol (IPA) or a tertiary alcohol such as tertiary butyl alcohol (TBA), the polyelectrolyte82in the polyelectrolyte solution is placed in a more loosened state. In addition, according to tests conducted by the inventor, when the solvent contains a secondary alcohol and a tertiary alcohol, the polyelectrolyte82in the polyelectrolyte solution is placed in a still more loosened state.

A process for production of a polyelectrolyte solution of the present invention is characterized by including a pre-solution preparing step for preparing a pre-solution in which a polyelectrolyte having a side chain including a hydrophilic functional group is dissolved in a solvent, and a solution preparation step for obtaining a polyelectrolyte solution by reducing a concentration of at least water in the pre-solution to 10% or less (claim6).

With the process for production of the polyelectrolyte solution of the present invention, the polyelectrolyte solution having the above-described characteristics can be produced in a stable manner.

A method for production of a fuel cell catalyst layer forming a catalyst layer by a catalyst paste according to the present invention is characterized by including a water removal step for obtaining a polyelectrolyte solution by reducing to 10% or less a concentration of water in a pre-solution in which a polyelectrolyte having a side chain including a hydrophilic functional group is dissolved in a solvent, a pre-paste preparation step for producing a pre-paste by mixing a catalyst with water, and an agitation step for obtaining the catalyst paste by mixing the polyelectrolyte solution into the pre-paste (claim7).

With the production method of the present invention, the concentration of water in the polyelectrolyte solution is reduced to 10% or less in the water removal step. Therefore, the polyelectrolyte solution has the above-described characteristics. As a result, the fuel cell catalyst layer formed by the catalyst paste obtained through the agitation step has the above-described characteristics.

Consequently, with the method for production of the fuel cell catalyst layer, it is possible to obtain the fuel cell catalyst layer in which the electrochemical reaction is smoothly performed.

BEST MODES FOR CARRYING OUT THE INVENTION

Description will be made below of examples 1 and 2 embodying the present invention, and experimental examples 1 and 2, with reference to the accompanying drawings.

Experimental Example 1

First, experiments described below were conducted to produce a cathode catalyst layer93a, an anode catalyst layer92a, and an MEA90that has the catalyst layers93aand92a, of each of the examples 1 and 2 shown inFIG. 4. In the experimental example 1, six types of polyelectrolyte solutions with different compositions and production steps were prepared, and the viscosity of each of the polyelectrolyte solutions was measured. Note that all of the polyelectrolyte solutions used in the examples 1 and 2, and the experimental example 1 were ionomer solution.

(Production of Sample A)

First, as a pre-solution, DE2020 (made by DuPont) was prepared to produce a polyelectrolyte solution of Sample A. Then, 10 g of DE2020 was put in a container and warmed in hot water at 85° C. as shown inFIG. 2Ato evaporate water and normal propyl alcohol (NPA) that serve as a solvent in DE2020. By this warming operation in hot water, each content of water and NPA in DE2020 was reduced to 2 g. As a result, the content of each of water and NPA in DE2020 was equivalent to 5% when converted to a concentration in the polyelectrolyte solution of Sample A.

Next, 6.8 g of water was mixed into DE2020 after being warmed in hot water (refer toFIG. 2B), and the mixture was agitated for 3 minutes with a rotation-revolution type centrifugal mixer35(refer toFIG. 2C). Note that a Hybrid Mixer HM-500 (made by Keyence) was employed as the rotation-revolution type centrifugal mixer35.

Next, as shown inFIG. 2D, 7.2 g of NPA was mixed into the mixture of DE2020 and water. Thereafter, the mixture thus made was agitated in the rotation-revolution type centrifugal mixer35(refer toFIG. 2E). As shown inFIG. 2F, 20 g of IPA serving as an organic solvent was mixed into the mixture of DE2020, water, and NPA thus obtained. Then, the mixture thus made was agitated in the rotation-revolution type centrifugal mixer35(refer toFIG. 20) to obtain the polyelectrolyte solution of Sample A (refer toFIG. 2H).

(Production of Sample B)

To produce a polyelectrolyte solution of Sample B, in the same manner as production of the polyelectrolyte solution of Sample A, 10 g of DE2020 was warmed in hot water at 85° C. to reduce each content of water and NPA in DE2020 to 2 g. As a result, the content of each of water and NPA in DE2020 was equivalent to 5% when converted to a concentration in the polyelectrolyte solution of Sample B.

Next, 20 g of WA was mixed into DE2020 after being warmed in hot water, and the mixture was agitated for 3 minutes with the rotation-revolution type centrifugal mixer35. Then, 7.2 g of NPA was mixed into the mixture of DE2020 and IPA, and agitated in the rotation-revolution type centrifugal mixer35. Then, 6.8 g of water was mixed into the mixture of DE2020, IPA, and NPA thus obtained. The mixture thus made was agitated in the rotation-revolution type centrifugal mixer35to obtain the polyelectrolyte solution of Sample B.

(Production of Sample C)

To produce a polyelectrolyte solution of Sample C, 20 g of IPA was mixed into 10 g of DE2020, and agitated for 3 minutes with the rotation-revolution type centrifugal mixer35. Thereafter, 4.7 g of NPA was mixed into the mixture of DE2020 and IPA, and agitated in the rotation-revolution type centrifugal mixer35. Then, 5.3 g of water was mixed into the mixture of DE2020, IPA, and NPA thus obtained. Then, the mixture thus made was agitated in the rotation-revolution type centrifugal mixer35to obtain the polyelectrolyte solution of Sample C. Because the warming operation in hot water was not applied to the production of the polyelectrolyte solution of Sample C, the content of water in DE2020 was equivalent to approximately 9% when converted to a concentration in the polyelectrolyte solution of Sample C. The content of NPA in DE2020 was equivalent to approximately 11% when converted to a concentration in the polyelectrolyte solution of Sample C.

(Production of Sample D)

Also in the production of a polyelectrolyte solution of Sample D, 10 g of DE2020 was warmed in hot water at 85° C. to reduce each content of water and NPA in DE2020 to 2 g. As a result, the content of each of water and NPA in DE2020 was equivalent to 5% when converted to a concentration in the polyelectrolyte solution of Sample D. Next, 34 g of NPA was mixed into DE2020 thus obtained, and the mixture was agitated for 3 minutes with the rotation-revolution type centrifugal mixer35. Thus, the polyelectrolyte solution of Sample D was obtained.

(Production of Sample E)

Also in the production of a polyelectrolyte solution of Sample E, 10 g of DE2020 was warmed in hot water at 85° C. to reduce each content of water and NPA in DE2020 to 2 g. As a result, the content of each of water and NPA in DE2020 was equivalent to 5% when converted to a concentration in the polyelectrolyte solution of Sample E. Next, 34 g of IPA was mixed into DE2020 thus obtained, and the mixture was agitated for 3 minutes with the rotation-revolution type centrifugal mixer35. Thus, the polyelectrolyte solution of Sample E was obtained.

(Production of Sample F)

Also in the production of a polyelectrolyte solution of Sample F, 10 g of DE2020 was warmed in hot water at 85° C. to reduce each content of water and NPA in DE2020 to 2 g. As a result, the content of each of water and NPA in DE2020 was equivalent to 5% when converted to a concentration in the polyelectrolyte solution of Sample F. Next, 34 g of a solution in a ratio of IPA:TBA=1:1 was mixed into DE2020 thus obtained, and the mixture was agitated for 3 minutes with the rotation-revolution type centrifugal mixer35. Thus, the polyelectrolyte solution of Sample F was obtained.

(Production of Sample G)

Also in the production of a polyelectrolyte solution of Sample 10 g of DE2020 was also warmed in hot water at 85° C. However, each content of water, NPA, and a polyelectrolyte82in DE2020 was made to be approximately 33%. Next, 7.2 g of NPA was mixed into DE2020 after being warmed in hot water, and the mixture was agitated for 3 minutes with the rotation-revolution type centrifugal mixer35. Thereafter, 6.8 g of water was added and further agitated. Then, 20 g of IPA was added and agitated to obtain Sample G.

A viscosity of each of the polyelectrolyte solutions of Samples A to G was measured at 20° C. Table 1 shows the measurement results. Note that Table 1 shows viscosity ratios of Samples B to G relative to the viscosity of Sample A that serves as a reference value. Table 1 also lists composition ratios of the polyelectrolyte, IPA, NPA, H2O, and TBA, as well as the order of addition of the solvents in each of the polyelectrolyte solutions of Samples A to G.

As shown in Table 1, the polyelectrolyte solutions of Samples A to C differed from each other in viscosity in spite of having the same composition ratio. From this fact, it was found out that the order of the solvents mixed into DE2020 is related to the change in viscosity. More in detail, by comparing the polyelectrolyte solution of Sample A with the polyelectrolyte solutions of Samples B and C, it was found that the viscosity is reduced by first mixing water into DE2020. In addition, by comparing the polyelectrolyte solution of Sample B with the polyelectrolyte solution of Sample C, it was found that the viscosity of polyelectrolyte solution is lower before IPA is mixed, that is, as the ratio of water and NPA is larger in DE2020 serving as a pre-solution.

Moreover, from the measurement results for the polyelectrolyte solution of Sample D, it was found that the viscosity is lower when NPA alone is mixed into DE2020. On the other hand, from the measurement results for the polyelectrolyte solutions of Samples E and F, it was found that the viscosity is higher when IPA is mixed and when IPA and TBA are mixed. Because the viscosity is higher as the ratio of water, that is, the concentration of water, in the polyelectrolyte solution is lower, it is considered that the polyelectrolyte82in the polyelectrolyte solutions of Samples E and F is in a state in which a main chain100and side chains101are loosened as shown inFIG. 1. That is, it can be inferred that IPA, and a combination IPA and TBA have an effect of loosening the polyelectrolyte82in the polyelectrolyte solution whereas, in contrast, water and NPA have an effect of tightening the polyelectrolyte82in the polyelectrolyte solution. It can also be inferred that NPA has a high effect of tightening the polyelectrolyte82in the polyelectrolyte solution.

Thus, it can be inferred that primary alcohols, such as NPA and ethanol, and water have an effect of tightening the polyelectrolyte whereas secondary alcohols, such as IPA, and tertiary alcohols, such as TBA, have an effect of loosening the polyelectrolyte. The above-described effect of secondary alcohols and tertiary alcohols is considered to result from permittivity. It can be inferred that solvents having a permittivity of 20 or less have a high effect of loosening the tightness of polyelectrolytes.

Production of Cathode Catalyst Layer93aand Anode Catalyst Layer92a

Based on the experimental results described above, the MEA90of the example 1 shown inFIG. 4was produced. A cathode93of this MEA90is, as shown above, composed of the cathode catalyst layer93aserving as a fuel cell catalyst layer and a base material93bformed of gas diffusion layer base material.

First of all, a catalyst paste42forming the cathode catalyst layer93awas produced. To produce the catalyst paste42, first, a catalyst81was prepared, in which a support81amade of carbon black supports Pt fine particles serving as catalyst metal fine particles82bat a supporting density of 50 wt %. Then, the catalyst81and water were mixed at a ratio of 1 g of the catalyst81to 5 g of water, and the mixture was agitated in the rotation-revolution type centrifugal mixer35to obtain a pre-paste40(refer toFIG. 3A).

Next, a polyelectrolyte solution41to be mixed with the pre-paste40was prepared. The polyelectrolyte solution41had the same composition as that of the polyelectrolyte solution produced as Sample B in the above-described experimental example 1. That is, the polyelectrolyte solution41had a concentration of water of 22%. Note that the warming operation in hot water conducted to obtain the polyelectrolyte solution41, that is the warming operation in hot water in the production of the polyelectrolyte solution of Sample B corresponds to water removing means in an apparatus for production of a fuel cell catalyst layer of the present invention and a water removal step in a method for production of a fuel cell catalyst layer of the present invention.

Then, 10 g of the polyelectrolyte solution41was mixed into the pre-paste40, and the mixture was agitated in the rotation-revolution type centrifugal mixer35as shown inFIG. 3B. Thus, the catalyst paste42was produced (refer toFIG. 3C). Note that the rotation-revolution type centrifugal mixer35corresponds to agitating means in the apparatus for production of a fuel cell catalyst layer of the present invention, and the agitation by the rotation-revolution type centrifugal mixer35corresponds to an agitation step in the method for production of a fuel cell catalyst layer of the present invention.

The catalyst paste42produced above was applied onto the base material93bto form the cathode catalyst layer93a. The base material93bwas obtained by laminating carbon black provided with water-repellent treatment with PTFE and carbon cloth serving as an electron-conductive base material. Note that it is possible to employ, as the base material93b, a material such as carbon paper on which a water-repellent layer composed of a mixture of carbon black and PTFE. As a method of applying the catalyst paste42onto the base material93b, it is possible to employ means such as screen printing, a spraying method, and an ink-jet method.

The cathode93was obtained as a result of drying of the cathode catalyst layer93aon the base material93b. The anode catalyst layer92aand an anode92were also obtained by the same process.

Then, the anode92, an electrolyte membrane (Nation membrane NR-211)91, and the cathode93are stacked in this order, and bonded to each other by hot pressing at a temperature of 140° C. and a pressure of 40 kgf/cm2. Thus, the MEA90was produced.

In the MEA90, the polyelectrolyte solution41in which the concentration of water is 5% has been mixed with the pre-paste40when producing the catalyst paste42forming the cathode catalyst layer93aand the anode catalyst layer92a. As shown inFIG. 3A, it is considered that the polyelectrolyte82is in a loosened state in the polyelectrolyte solution41. It is also considered that the main chain100is placed in an extending state in one direction in the polyelectrolyte82in such a loosed state. Accordingly, as shown inFIG. 3C, a sulfone group adheres to water in the pre-paste40. As a result, in the cathode catalyst layer93aand the anode catalyst layer92athat are obtained from the catalyst paste42, a layer of the polyelectrolyte82is formed in an oriented state to a surface of the catalyst81, as shown inFIG. 6. It is further considered that, because the sulfone group adheres to the water in the pre-paste40as described above, the hydrophilic functional group in the side chain101of the polyelectrolyte82is placed in an oriented state toward the side of the catalyst81(PFF structure) so as to form a hydrophilic layer83on the catalyst81in the cathode catalyst layer93aand the anode catalyst layer92a, as shown inFIG. 6. For this reason, in the cathode catalyst layer93aand the anode catalyst layer92aobtained with this production method, as shown inFIG. 5, protons and water easily move, thus allowing an electrochemical reaction to proceed smoothly. As a result, in the MEA90having the cathode catalyst layer93aand the anode catalyst layer92aobtained as described above, power generation capacity can be made high both under low humidified conditions and under over-humidified conditions.

Therefore, with the production method of the example 1, it is possible to obtain the cathode catalyst layer93aand the anode catalyst layer92ain which the electrochemical reaction is smoothly performed, and consequently to obtain the MEA90in which the electrochemical reaction is smoothly performed.

In an MEA90of the example 2, a cathode catalyst layer and an anode catalyst layer are formed by a catalyst paste obtained by mixing the pre-paste40with the polyelectrolyte solution of Sample E (with water concentration of 5%) in the above-described experimental example 1. Other compositions and the production method are the same as those of the example 1.

Next, in order to know voltage characteristics of the MBA90obtained in the examples 1 and 2, verification by experiments was conducted using cells provided with the MEA90and a cell provided with an MEA of a comparative example shown below. Note that a composition and a production method of the cells are the same as known composition and method.

Comparative Example

In an MEA of the comparative example, a cathode catalyst layer and an anode catalyst layer are formed by a catalyst paste obtained by mixing the pre-paste40with the polyelectrolyte solution of Sample A (with water concentration of 22%) in the above-described experimental example 1. Other compositions and the production method are the same as those of the examples 1 and 2.

In this experimental example 2, a cell temperature of each of the cells provided with the MEAs90of the examples 1 and 2, and the cell provided with the MEA of the comparative example was set to 50″C, and under the measurement environment of a humidity of 100%, the change in current and voltage of each of the cells was measured when hydrogen was supplied to the anode92and oxygen was supplied to the cathode93.FIG. 7shows results of the measurement.

InFIG. 7, the horizontal axis represents a current density (A/cm2) of a cell, and the vertical axis represents a cell voltage (V). As shown inFIG. 7, the reduction in the voltage as the current density increases is the smallest for the cell provided with the MEA90of the example 2. That is, it can be stated that the MEA90of the example 2 has the highest power generation capacity.

In addition, from these experimental results, it was found that the power generation capacity of the MEA is higher, that is, the electrochemical reaction is performed more smoothly, as the viscosity of the polyelectrolyte solution is higher. Moreover, it was found from comparison between the comparative example and the example 1 that the power generation capacity of the MEA tends to be higher as the viscosity of the polyelectrolyte solution is higher even if the concentration of water in the polyelectrolyte solution is the same. That is, it was found that the power generation capacity of the MEA changes depending on the order of mixing the solvent into the polyelectrolyte solution.

The present invention has been described above in accordance with the examples 1 and 2. However, the present invention is not limited to the examples 1 and 2, but can obviously be applied by making appropriate changes as far as they do not depart from the gist of the present invention.

INDUSTRIAL APPLICABILITY

The present invention can be used in a power supply for moving an object such as an electric vehicle, or in a stationary power supply.

DESCRIPTION OF THE REFERENCE NUMERALS