JP5682390B2 - Electrode catalyst layer and production method thereof, membrane electrode assembly and production method thereof, polymer electrolyte fuel cell, composite particle and production method thereof - Google Patents

Description

  The present invention relates to an electrode catalyst layer and a production method thereof, a membrane electrode assembly and a production method thereof, a polymer electrolyte fuel cell, and composite particles and a production method thereof. More specifically, the present invention relates to an electrode catalyst layer exhibiting high power generation characteristics using a non-platinum catalyst and a production method thereof, a membrane electrode assembly and a production method thereof, a polymer electrolyte fuel cell, and composite particles and a production method thereof.

  A fuel cell is a power generation system that generates electricity simultaneously with heat by causing a hydrogen gas-containing fuel gas and an oxygen-containing oxidant gas to undergo reverse reaction of water electrolysis at an electrode including a catalyst. This power generation system has features such as high efficiency, low environmental load, and low noise as compared with conventional power generation systems, and is attracting attention as a clean energy source in the future. There are several types depending on the type of ion conductor used, and those using proton conductive polymer membranes are called solid polymer fuel cells.

  Among fuel cells, polymer electrolyte fuel cells can be used at about room temperature, and are therefore promising for use in in-vehicle power sources and household stationary power sources. In recent years, various research and development have been conducted. Yes. A polymer electrolyte fuel cell is a cell in which a membrane electrode assembly (hereinafter also referred to as MEA) is sandwiched between a pair of separator plates. The membrane electrode assembly is a assembly in which a pair of electrodes are arranged on both surfaces of a polymer electrolyte membrane, and one of the pair of separator plates is supplied with a fuel gas containing hydrogen to one of the electrodes. A gas flow path is formed, and a gas flow path for supplying an oxidant gas containing oxygen to the other of the electrodes is formed on the other of the pair of separator plates.

Here, the electrode on the side supplying the fuel gas is called a fuel electrode, and the electrode on the side supplying the oxidant is called an air electrode. These electrodes generally comprise an electrode catalyst layer formed by laminating carbon particles carrying a catalyst material such as a platinum-based noble metal and a polymer electrolyte, and a gas diffusion layer having both gas permeability and electronic conductivity. .
Although the problem toward the practical use of the polymer electrolyte fuel cell as described above includes improvement of output density and durability, the biggest problem is cost reduction.

In current polymer electrolyte fuel cells, expensive platinum is used as an electrode catalyst, and for the full-scale diffusion, development of alternative materials is strongly demanded. In particular, since the air electrode uses more platinum than the fuel electrode, development of platinum substitute materials (non-platinum catalysts) that exhibit high oxygen reduction catalytic activity in the air electrode has been actively conducted.
As an example of the non-platinum catalyst in the air electrode, for example, Patent Document 1 describes a mixture of iron nitride and noble metal, which is a transition metal. Patent Document 2 describes a nitride of molybdenum, which is a transition metal. However, the catalyst materials described in Patent Document 1 and Patent Document 2 have insufficient oxygen reducing ability in the acidic electrolyte, and the catalyst material may be dissolved.

On the other hand, Non-Patent Document 1 describes a partially oxidized tantalum carbonitride, which indicates that it has excellent stability and catalytic ability. However, although this oxide-based non-platinum catalyst exhibits high oxygen reduction catalytic ability as a single catalyst, it is necessary to optimize the electrode catalyst layer preparation method in order to bring out high output performance as MEA.
As a preparation method used in the platinum catalyst, as described in Patent Documents 3 to 5, a plurality of types of conductive carbon is added to the electrode catalyst layer to improve durability and water repellency of the electrode catalyst layer. The MEA has been devised to bring out high output performance. However, there is a problem that the preparation method used in these platinum catalysts is not suitable when a non-platinum catalyst is used.

JP 2005-44659 A JP 2005-63677 A JP 2007-059253 A JP 2005-129457 A JP 2010-123571 A

"Journal of The Electrochemical Society, Vol.155, No.4" pp.B400-B406 2008

  The present invention provides an electrode catalyst layer exhibiting high power generation characteristics using an oxide-based non-platinum catalyst as a catalyst material, a production method thereof, a membrane electrode assembly, a production method thereof, a polymer electrolyte fuel cell, and composite particles The purpose is to do.

As a result of intensive studies, the present inventor has been able to solve the above-mentioned problems and has completed the present invention.
The invention according to claim 1 of the present invention is a method for producing composite particles used in an electrode catalyst layer comprising a polymer electrolyte and a catalyst substance and at least two types of carbon particles having different graphitization rates. ,
The two types of carbon particles include first carbon particles and second carbon particles having a graphitization rate lower than that of the first carbon particles,
Said catalyst material, said first carbon particles specific surface area is greater than the catalytic material, a first adjusting step of the first polyelectrolyte to adjust the first catalyst ink obtained by dispersing in a solvent,
A composite particle forming step of drying the first catalyst ink to form composite particles embedded with the first polymer electrolyte ; and
The composite particles are prepared by adjusting the second catalyst ink in which the composite particles, the second carbon particles, and the second polymer electrolyte are dispersed in a solvent, and then the second catalyst ink is added to the gas diffusion layer. there is provided a method of manufacturing composite particles, wherein are used Rukoto in the step of forming the electrode catalyst layer is coated on a substrate selected from the transfer sheet and polymer electrolyte membrane.

Next, the invention described in claim 2 is characterized in that the graphitization rate of the first carbon particles is higher than the graphitization rate of other carbon particles compared to the configuration described in claim 1, and the first carbon lattice spacing _{C 0} of X-ray diffraction of the particles, and wherein the at least 6.60Å 6.95Å or less.
Next, the invention described in claim 3 is directed to the structure described in claim 1 or claim 2, in the composite particle forming step, in the composite particles embedded with the first polymer electrolyte, The mass ratio with respect to the first carbon particles is in the range of 1: 0.01 to 1: 1.

Next, the invention described in claim 4 is a composite particle embedded in the composite particle forming step with the first polymer electrolyte in the configuration described in any one of claims 1 to 3. The mass ratio of the first carbon particles to the polymer electrolyte is in the range of 1: 0.2 to 1:50.
Next, the invention described in claim 5 has a heat treatment temperature range for drying the first catalyst ink in the composite particle forming step with respect to the configuration described in any one of claims 1 to 4. , 30 ° C. or more and 140 ° C. or less.

Next, the invention described in claim 6 is directed to the structure described in any one of claims 1 to 5, wherein the catalyst material is an oxygen reduction electrode used as a positive electrode of a polymer electrolyte fuel cell. An electrode active material for use in the present invention includes at least one transition metal element selected from Ta, Nb, Ti, and Zr.
Next, the invention described in claim 7 is directed to the structure described in any one of claims 1 to 6, wherein the catalyst material is selected from Ta, Nb, Ti, and Zr. It is characterized by being a partial oxide of one transition metal element carbonitride or an oxide of the transition metal element.

Next, the invention described in claim 8 is a method for producing composite particles according to any one of claims 1 to 7,
The composite particles embedded with the first polymer electrolyte formed by the composite particle manufacturing method, the second carbon particles having a specific surface area larger than that of the catalyst substance, and the second polymer electrolyte are dispersed in a solvent. A second adjustment step for adjusting the second catalyst ink;
An electrode catalyst layer forming step of forming an electrode catalyst layer by applying the second catalyst ink on a substrate selected from a gas diffusion layer, a transfer sheet and a polymer electrolyte membrane;
The manufacturing method of the electrode catalyst layer for fuel cells characterized by providing is provided.

Next, in the invention described in claim 9, in the configuration described in claim 8, the second adjustment step is performed by removing the composite particles embedded with the first polymer electrolyte and the second carbon particles. A mixing step of mixing with a solvent is provided.
Next, the invention described in claim 10 is the heat treatment step of heat-treating the composite particles embedded with the first polymer electrolyte and the second carbon particles in the configuration described in claim 9 in the mixing step. It is characterized by providing.

Next, in the invention described in claim 11, the heat treatment temperature range of the composite particles embedded in the first polymer electrolyte and the second carbon particles in the heat treatment step is compared with the structure described in claim 10. 50 ° C. or more and 180 ° C. or less.
Next, the invention described in claim 12 is a composite particle embedded with a polymer electrolyte manufactured by the method for manufacturing a composite particle according to any one of claims 1 to 7. Is to provide.

Next, the invention described in claim 13 is manufactured by the method for manufacturing an electrode catalyst layer for fuel cell described in any one of claims 8 to 11. A catalyst layer is provided.
Next, the invention described in claim 14 is a method for producing a membrane electrode assembly for a fuel cell in which a proton conductive polymer electrolyte membrane sandwiched between a pair of electrode catalyst layers is sandwiched between a pair of gas diffusion layers. At least one of the electrode catalyst layers comprises the electrode catalyst layer according to claim 13, and a method for producing a membrane electrode assembly for a fuel cell is provided.

Next, the invention described in claim 15 provides a membrane electrode assembly for a fuel cell manufactured by the method for manufacturing a membrane electrode assembly for a fuel cell described in claim 14. is there.
Next, in the invention described in claim 16, the membrane electrode assembly according to claim 15 is sandwiched between a pair of gas diffusion layers, and the membrane electrode assembly sandwiched between the pair of gas diffusion layers is Furthermore, the present invention provides a polymer electrolyte fuel cell characterized by being sandwiched by a pair of separators.
Next, the invention described in claim 17 is a method for producing composite particles contained in an electrode catalyst layer comprising a polymer electrolyte and a catalyst substance, and at least two types of carbon particles having different graphitization rates,
The two types of carbon particles include first carbon particles and second carbon particles having a graphitization rate lower than that of the first carbon particles,
A first adjustment step of adjusting the catalyst material, the first carbon particles having a specific surface area larger than that of the catalyst material, and a first catalyst ink in which a first polymer electrolyte is dispersed in a solvent;
And a composite particle forming step of forming a composite particle embedded with a first polymer electrolyte by drying the first catalyst ink. .

  According to the present invention, for an electrode catalyst layer comprising a polymer electrolyte, a catalyst material, and at least two types of carbon particles having different graphitization rates, a catalyst material having a specific surface area smaller than that of the carbon particles, for example, graphitization treatment In addition to embedding the polymer electrolyte in the first carbon particles, the proton conductivity on the surface of the catalyst is increased, the contact between the catalyst substance and the carbon particles is increased, and further the first carbon particles By providing the second carbon particles having a low graphitization rate compared to the above, an electrode catalyst layer having an increased reaction active point by increasing the gas diffusibility of the electrode catalyst layer and improving the output performance, and this manufacturing method, A membrane electrode assembly and a production method thereof, a polymer electrolyte fuel cell, and composite particles can be provided.

It is a cross-sectional schematic diagram of the membrane electrode assembly which concerns on embodiment of this invention. 1 is an exploded schematic view of a polymer electrolyte fuel cell according to an embodiment of the present invention. It is a figure which shows the electric power generation characteristic evaluation result of the membrane electrode assembly in an Example.

Below, the membrane electrode assembly which concerns on embodiment of this invention is demonstrated. The embodiments of the present invention are not limited to the embodiments described below, and modifications such as design changes can be added based on the knowledge of those skilled in the art. The described embodiments can also be included in the scope of the embodiments of the present invention.
(Membrane electrode assembly)
FIG. 1 is a schematic cross-sectional view showing a membrane electrode assembly 12 according to an embodiment of the present invention. As shown in FIG. 1, a membrane electrode assembly 12 according to an embodiment of the present invention includes a polymer electrolyte membrane 1 and an electrode catalyst layer 2 a on the air electrode side disposed on one surface of the polymer electrolyte membrane 1. And an electrode catalyst layer 2 b on the fuel electrode side disposed on the other surface of the polymer electrolyte membrane 1.

(Solid polymer fuel cell)
FIG. 2 is an exploded schematic view of a polymer electrolyte fuel cell according to an embodiment of the present invention. In the polymer electrolyte fuel cell according to the present invention, as shown in FIG. 2, the gas diffusion layer 3 on the air electrode side is opposed to the electrode catalyst layer 2a and the electrode catalyst layer 2b of the membrane electrode assembly 12, respectively. And the gas diffusion layer 4 on the fuel electrode side is arranged. As a result, an air electrode (cathode) 5 and a fuel electrode (anode) 6 are formed. Further, a pair of separators 9 are disposed with the gas diffusion layer 3, the membrane electrode assembly 12, and the gas diffusion layer 4 interposed therebetween. The pair of separators 9 includes a gas flow path 7 for gas flow, and is made of a conductive and impermeable material having a cooling water flow path 8 for cooling water flow on the opposing main surface. For example, hydrogen gas is supplied as a fuel gas from the gas flow path 7 of the separator 9 on the fuel electrode 6 side. On the other hand, for example, a gas containing oxygen is supplied as an oxidant gas from the gas flow path 7 of the separator 9 on the air electrode 5 side. An electromotive force can be generated between the fuel electrode and the air electrode by causing an electrode reaction between the fuel gas hydrogen and oxygen gas in the presence of the catalyst.

The solid polymer fuel cell shown in FIG. 2 is a so-called single cell solid in which a solid polymer electrolyte membrane 1, electrode catalyst layers 2a and 2b, and gas diffusion layers 3 and 4 are sandwiched by a pair of separators. Although it is a polymer fuel cell, in the application of the present invention, a fuel cell in which a plurality of cells are stacked via a separator 9 may be used.
At least one of the electrode catalyst layers of the present embodiment is an electrode catalyst layer comprising a polymer electrolyte, a catalyst substance, and at least two types of carbon particles having different graphitization rates, and having a specific surface area smaller than that of the carbon particles. A polymer electrolyte is embedded in the catalyst material and the first carbon particles subjected to graphitization. With this configuration, not only the proton conductivity on the catalyst surface can be increased, but also the contact property between the catalyst substance and the carbon particles can be increased. The electrode catalyst layer further includes a second carbon particle that is not graphitized or has a lower graphitization rate than the first carbon particle, thereby increasing the gas diffusibility of the electrode catalyst layer. The active point can be increased and the output performance can be improved.

Here, in the conventional method of manufacturing an electrode catalyst layer that does not embed composite particles with a polymer electrolyte, the polymer electrolyte is preferentially embedded in carbon particles having a large specific surface area when the electrode catalyst layer is formed. Therefore, the proton conductivity on the catalyst surface is low and the reaction active point cannot be increased. Even with the conventional manufacturing method, it is possible to increase the proton conductivity on the catalyst surface by increasing the concentration of the polymer electrolyte in the electrode catalyst layer, but the gas flow path in the electrode catalyst layer is reduced and the output performance is improved. It is difficult to make it.
As the at least two types of carbon particles having different graphitization rates according to the embodiment of the present invention, first carbon particles that have been graphitized and second carbon particles that have not been graphitized can be used.

Although it does not specifically limit as 1st carbon particle which concerns on embodiment of this invention, Carbon black, activated carbon, etc. can be used as a raw material by heat-treating at 1000 degreeC or more in inert atmosphere, and graphitizing-treated .
The second carbon particles according to the embodiment of the present invention may be any particles as long as they are in the form of fine particles and have conductivity and are not exposed to the catalyst. For example, carbon black or activated carbon can be used as the second carbon particles. If the particle size of the carbon particles is too small, it becomes difficult to form an electron conduction path. If the particle size is too large, the gas diffusibility of the electrode catalyst layer decreases or the utilization factor of the catalyst decreases. Is preferred. More preferably, it is 10 nm or more and 100 nm or less.

  In general, carbon particles with a high graphitization rate are often more hydrophobic than carbon particles with a low graphitization rate due to heat treatment in the production process, and the affinity with a polymer electrolyte having a sulfonic acid group is reduced. To do. Carbon particles having a high graphitization rate have higher conductivity than carbon particles having a low graphitization rate, but tend to have a small specific surface area.

The electrode catalyst layer of the present embodiment includes at least two types of carbon particles having different graphitization rates, and the graphitization rate of the first carbon particles is higher than the graphitization rate of the second carbon particles. lattice spacing _{C 0} is an electrode catalyst layer having a first carbon particles is 6.60～6.95A. With this configuration, the affinity of the first carbon particles embedded in the polymer electrolyte together with the catalyst substance can be reduced, and the catalyst substance can be covered with a sufficient polymer electrolyte. Moreover, by making the electrode catalyst layer the graphitization rate of the second carbon particles lower than the graphitization rate of the first carbon particles, sufficient gas diffusibility can be ensured and the output performance can be improved. .
Here, the lattice spacing C ₀ is an index serving as a measure of the graphitization rate, and is the spacing of the carbon six-membered ring plane based on the graphite structure of the carbon particles, and is calculated from the X diffraction pattern. This represents the distance between ½ layers of the lattice constant C in the C-axis direction of the member ring plane.

If the lattice spacing C ₀ of X-ray diffraction of the first carbon particles contained in the composite particles is less than 6.60Å, the graphitization rate is too high affinity to the polymer electrolyte becomes too low It is difficult to agglomerate only with carbon particles and sufficiently increase the reaction active point. Further, when the lattice spacing C ₀ of the X-ray diffraction of the first carbon particles contained in the composite particles exceeds 6.95 mm, the graphitization rate is too low and the affinity for the polymer electrolyte is increased. It is difficult to sufficiently increase the reactive site due to a lack of polymer electrolyte embedding the surface.
Moreover, when the graphitization rate of the second carbon particles is higher than that of the first carbon particles, the specific surface area of the carbon particles is small and the electrode catalyst layer becomes dense, and the gas diffusibility of the electrode catalyst layer is reduced, It is difficult to sufficiently improve the output performance.

(Production method)
What is necessary is just to manufacture the composite particle embedded with the 1st polymer electrolyte by the process including the following 1st adjustment process and composite particle formation process.
In the first adjustment step, a first catalyst ink in which the catalyst material, first carbon particles having a specific surface area larger than that of the catalyst material, and a first polymer electrolyte are dispersed in a solvent is prepared.
In the composite particle forming step, the first catalyst ink is dried to form composite particles embedded with the first polymer electrolyte.

Further, the fuel cell electrode catalyst layer may be manufactured by a process including the following processes.
That is, in the second adjustment step, the composite particles embedded with the first polymer electrolyte formed by the composite particle manufacturing method, the second carbon particles having a specific surface area larger than that of the catalyst substance, and the second A second catalyst ink in which a polymer electrolyte is dispersed in a solvent is prepared.
In the electrode catalyst layer forming step, the electrode catalyst layer is formed by applying the second catalyst ink on a substrate selected from a gas diffusion layer, a transfer sheet, and a polymer electrolyte membrane.

In the manufacturing method of the electrode catalyst layer of this embodiment, in the first step of preparing the first catalyst ink in which the catalyst substance, the first carbon particles, and the polymer electrolyte are dispersed in the solvent, the first catalyst ink is formed by drying. In the composite particles to be produced, the mass ratio of the catalyst substance, the first carbon particles, and the polymer electrolyte can be controlled by setting the ink composition.
The mass ratio between the catalyst substance and the first carbon particles in the composite particles embedded with the polymer electrolyte is preferably in the range of 1: 0.01 or more and 1: 1 or less. When the mass ratio of the first carbon particles to the catalyst material is less than 0.01, the contact property between the catalyst material and the first carbon particles is low, and the reaction active point may be increased. Since it is difficult, output performance may not improve. Further, when the mass ratio of the first carbon particles to the catalyst substance exceeds 1, the proton conductivity on the catalyst surface does not change and it is difficult to increase the reaction active point. The output performance may not improve.

  The mass ratio of the first carbon particles to the polymer electrolyte in the composite particles embedded with the polymer electrolyte is preferably in the range of 1: 0.2 or more and 1:50 or less. If the mass ratio of the polymer electrolyte to the first carbon particles is less than 0.2, the first carbon particles may be embedded and the proton conductivity on the catalyst surface may be improved. Since it is difficult and it is difficult to increase the reaction active point, the output performance may not be improved. In addition, when the mass ratio of the polymer electrolyte exceeds 50 with respect to the first carbon particles, the gas diffusibility to the reaction active site is hindered, and the output performance may not be improved.

  In the method for producing an electrode catalyst layer of this embodiment, in the composite particle forming step of drying the first catalyst ink in which the catalyst substance, the first carbon particles, and the polymer electrolyte are dispersed in a solvent, The temperature of the heat treatment is preferably 30 ° C. or higher and 140 ° C. or lower. When the drying temperature is less than 30 ° C., in the second adjustment step of adjusting the second catalyst ink, most of the polymer electrolyte in the composite particles is dissolved in the solvent, and the output performance may not be improved. is there. Even when the drying temperature exceeds 140 ° C., the proton conductivity of the polymer electrolyte in the composite particles is hindered, and the output performance may not be improved.

  In the method for producing an electrode catalyst layer of this embodiment, a second adjustment step of adjusting a second catalyst ink in which composite particles embedded with a polymer electrolyte, second carbon particles, and a polymer electrolyte are dispersed in a solvent. In this case, it is preferable to include a mixing step in which the composite particles and the second carbon particles are mixed without a solvent before being dispersed in the solvent. If this mixing step is not performed, the output performance may not be improved because the contact between the composite particles and the second carbon particles is low and it is difficult to increase the reaction active point.

 Moreover, it is preferable to provide a heat treatment step after the mixing step of mixing without solvent. If this heat treatment step is not performed, the reaction active point may decrease in the step of adjusting the second catalyst ink. In this heat treatment step, the heat treatment temperature is preferably 50 ° C. or higher and 180 ° C. or lower. When the drying temperature is less than 50 ° C., in the step of preparing the second catalyst ink, most of the polymer electrolyte in the composite particles is dissolved in the solvent, and the reaction active sites formed are reduced. Output performance may not improve. Even when the drying temperature exceeds 180 ° C., the proton conductivity of the polymer electrolyte in the composite particles is hindered, and the output performance may not be improved.

In the step of preparing the second catalyst ink in which the composite particles and the second carbon particles and the polymer electrolyte are dispersed in the solvent, the polymer electrolyte is added by adding the solvent to the composite particles without adding the polymer electrolyte. It may be partly eluted.
As the catalyst material according to the embodiment of the present embodiment, a commonly used catalyst material may be used. Preferably, in the present embodiment, a substance containing at least one transition metal element selected from Ta, Nb, Ti, or Zr, which is used as a positive electrode of a polymer electrolyte fuel cell as a platinum substitute material in an air electrode, is used. May be. More preferably, it is a partial oxide or oxide of a carbonitride of these transition metal elements.
The membrane electrode assembly and the polymer electrolyte fuel cell according to the embodiment of the present invention will be described in more detail.

  The polymer electrolyte membrane according to the embodiment of the present invention may be any one having proton conductivity, such as a fluorine-based polymer electrolyte, for example, Dupont Nafion (registered trademark), Asahi Glass Co., Ltd. Flemion (registered). Trademark), Asahi Kasei Corporation's Aciplex (registered trademark), and Gore Select Gore Select (registered trademark) may be used. Moreover, you may use hydrocarbon type polymer electrolyte membranes, such as sulfonated polyether ketone and sulfonated polyether sulfone. Among the electrolyte membranes, a Nafion (registered trademark) material manufactured by Dupont may be suitably used as the polymer electrolyte membrane.

  The polymer electrolyte contained in the catalyst ink according to the embodiment of the present invention is not limited as long as it has proton conductivity, and the same fluorine-based polymer electrolyte and hydrocarbon-based polymer electrolyte as the polymer electrolyte membrane are used. Also good. Among these, a Nafion (registered trademark) material manufactured by Dupont may be suitably used as the polymer electrolyte membrane. In consideration of the adhesion between the electrode catalyst layer and the polymer electrolyte membrane, it is preferable to use the same material as the polymer electrolyte membrane.

  The solvent used as a dispersion medium for the catalyst ink is not particularly limited as long as it does not erode the catalyst particles and the polymer electrolyte and can dissolve or disperse the polymer electrolyte in a highly fluid state as a fine gel. However, it is desirable that at least a volatile organic solvent is contained, and is not particularly limited. However, alcohols, ketone solvents, ether solvents, other dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, You may use polar solvents, such as diethylene glycol, diacetone alcohol, and 1-methoxy-2-propanol. Moreover, you may use what mixed 2 or more types among these solvents.

In addition, those using lower alcohol as the solvent have a high risk of ignition, and when using such a solvent, it is preferable to use a mixed solvent with water. Water that is compatible with the polymer electrolyte may be contained. The amount of water added is not particularly limited as long as the polymer electrolyte is not separated to cause white turbidity or gelation.
In order to disperse the catalyst substance and the carbon particles, the catalyst ink may contain a dispersant. Examples of the dispersant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Among them, sulfonic acid type anionic surfactants such as alkylbenzene sulfonic acid, oil-soluble alkyl benzene sulfonic acid, α-olefin sulfonic acid, sodium alkyl benzene sulfonate, oil-soluble alkyl benzene sulfonate, α-olefin sulfonate, carbon dispersion Considering effects, changes in catalyst performance due to residual dispersant, etc. are preferable.

The catalyst ink is subjected to a dispersion treatment as necessary. The viscosity and particle size of the catalyst ink can be controlled by the conditions for the dispersion treatment of the catalyst ink. Distributed processing can be performed using various apparatuses. For example, examples of the dispersion process include a process using a ball mill and a roll mill, and an ultrasonic dispersion process.
If the solid content in the catalyst ink is too high, the viscosity of the catalyst ink will be high, so that the surface of the electrode catalyst layer will easily crack, and conversely if it is too low, the deposition rate will be very slow and productivity will be reduced. Therefore, the content is preferably 150% by mass or more and 50% by mass or less. The solid content is composed of a catalyst substance, carbon particles, and a polymer electrolyte. When the carbon particles are increased, the viscosity is increased even when the solid content is the same, and when the carbon content is decreased, the viscosity is decreased. Therefore, the proportion of carbon particles in the solid content is preferably 10% by mass or more and 80% by mass or less. Further, the viscosity of the catalyst ink at this time is preferably about 0.1 cP or more and 500 cP or less, and more preferably 5 cP or more and 100 cP or less. Further, the viscosity may be controlled by adding a dispersant when the catalyst ink is dispersed.

The catalyst ink may contain a pore forming agent. According to the pore forming agent, pores can be formed by removing after the formation of the electrode catalyst layer. A substance that dissolves in acid, alkali, or water, a sublimation substance such as camphor, or a substance that thermally decomposes may be used. If the substance is soluble in hot water, it may be removed with water generated during power generation.
In the method for producing an electrode catalyst layer of the present embodiment, composite particles embedded with a polymer electrolyte are coated with a catalyst material, carbon particles, and a first catalyst ink in which a polymer electrolyte is dispersed in a solvent, on a transfer sheet, It may be obtained by drying. Alternatively, the composite particles may be obtained directly by spraying in a dry atmosphere.

In the method for producing an electrode catalyst layer of this embodiment, an electrode for producing an electrode catalyst layer from composite particles embedded with a polymer electrolyte and second catalyst ink in which second carbon particles and the polymer electrolyte are dispersed in a solvent In the catalyst layer forming step, the catalyst ink is applied on the substrate, and an electrode catalyst layer is formed through a drying step. When a gas diffusion layer or a transfer sheet is used as the substrate, the electrode catalyst layers are bonded to both surfaces of the polymer electrolyte membrane by a bonding process. Further, in the membrane electrode assembly of the present embodiment, a polymer electrolyte membrane is used as a substrate, a catalyst ink is directly applied to both sides of the polymer electrolyte membrane, and an electrode catalyst layer is directly applied to both sides of the polymer electrolyte membrane. It may be formed.
At this time, as a coating method, a doctor blade method, a dipping method, a screen printing method, a roll coating method, a spray method, or the like may be used.

As a substrate in the method for producing an electrode catalyst layer of the present embodiment, a gas diffusion layer, a transfer sheet, or a polymer electrolyte membrane may be used. As the gas diffusion layer, a material having gas diffusibility and conductivity may be used. The transfer sheet may be any material having good transferability, and for example, a fluororesin film may be used.
When a transfer sheet is used as the substrate, the transfer sheet may be peeled after the electrode catalyst layer is bonded to the polymer electrolyte membrane, and a membrane electrode assembly having catalyst layers on both sides of the polymer electrolyte membrane may be obtained. It is not necessary to peel off the base material that is the gas diffusion layer after the bonding step.

  As the gas diffusion layer and the separator, those used in ordinary fuel cells may be used. Specifically, a porous carbon material such as carbon cloth, carbon paper, and nonwoven fabric may be used as the gas diffusion layer. As the separator, a carbon type or a metal type may be used. The fuel cell is manufactured by assembling other accompanying devices such as a gas supply device and a cooling device.

The method for producing a fuel cell electrode catalyst layer according to the present invention will be described below with reference to specific examples and comparative examples. However, the present invention is not limited by the following examples.
(Example 1)
[Adjustment of first catalyst ink]
Catalyst material (TaCNO, specific surface area about 10 m ² / g), first carbon particles (C ₀ = 6.87 Å) that have been heat-treated to increase the graphitization rate, and 20% by mass polymer An electrolyte solution (Nafion: Nafion (registered trademark), manufactured by Dupont) was mixed in a solvent, and dispersion treatment was performed using a planetary ball mill (trade name: P-7, manufactured by Fritsch Japan). The composition ratio of the catalyst ink was 1: 0.1 in terms of the mass ratio of the catalyst substance and the carbon particles, and 1: 0.8 in terms of the mass ratio of the carbon particles to the polymer electrolyte. The solvent was 1: 1 by volume ratio of ultrapure water and 1-propanol. A PTFE sheet was used as a substrate for drying the first catalyst ink.

[Method of forming catalyst material embedded in polymer electrolyte]
The first catalyst ink was applied onto the substrate by a doctor blade and dried at 80 ° C. for 5 minutes in an air atmosphere. Thereafter, the composite particles embedded with the polymer electrolyte were collected from the substrate.
[Mixing and heat treatment of composite particles and carbon particles]
The composite particles and the second carbon particles (Ketjen Black (registered trademark), trade name: EC-300J, manufactured by Lion Corporation) were mixed without solvent in a planetary ball mill. Thereafter, the mixture of composite particles and carbon particles was heat-treated at 100 ° C. The composition ratio of the mixture was 1: 0.4 in terms of the mass ratio of the catalyst material and the carbon particles not included in the composite particles.

[Adjustment of second catalyst ink]
A mixture of the composite particles and carbon particles subjected to heat treatment and a 20% by mass polymer electrolyte solution were mixed in a solvent and subjected to dispersion treatment using a planetary ball mill. The composition ratio of the catalyst ink was such that the mass ratio of the catalyst substance, the carbon particles, and the polymer electrolyte was 1: 0.5: 0.5, which was used as the second catalyst ink. The solvent was 1: 1 by volume ratio of ultrapure water and 1-propanol. A PTFE sheet was used as a transfer sheet.
[Method for forming electrode catalyst layer]
The second catalyst ink was applied to the transfer sheet with a doctor blade, and dried at 80 ° C. for 5 minutes in an air atmosphere. The thickness of the electrode catalyst layer was adjusted so that the amount of the catalyst substance supported was 0.5 mg / cm ^2, and the electrode catalyst layer 2 on the air electrode side was formed.

(Example 2)
[Method for producing electrode catalyst layer]
In the step of preparing the second catalyst ink, the same procedure as in Example 1 was performed, except that the second carbon particles (C ₀ = 6.89 た) that were heat-treated and increased in graphitization rate were used. The electrode catalyst layer 2 on the air electrode side was formed.
(Comparative example)
[Adjustment of catalyst ink]
A catalyst substance, carbon particles, and a 20% by mass polymer electrolyte solution were mixed in a solvent, and dispersion treatment was performed using a planetary ball mill. The composition ratio of the catalyst ink was such that the mass ratio of the catalyst substance, the carbon particles, and the polymer electrolyte was 1: 0.5: 0.5. The solvent was 1: 1 by volume ratio of ultrapure water and 1-propanol. Moreover, the same transfer sheet as the Example was used for the base material.

[Method for producing electrode catalyst layer]
In the same manner as in the example, the catalyst ink was applied to the transfer sheet and dried. The thickness of the electrode catalyst layer was adjusted so that the amount of the catalyst substance supported was 0.5 mg / cm ² to form the electrode catalyst layer 2a on the air electrode side.
[Preparation of electrode catalyst layer for fuel electrode]
For Examples and Comparative Examples, a platinum-supported carbon catalyst (trade name: TEC10E50E, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) having a platinum-supported amount of 50% by mass and a 20% by mass polymer electrolyte solution were mixed in a solvent, and a planetary ball mill The catalyst ink was subjected to a dispersion treatment as described above to obtain a catalyst ink. The composition ratio of the catalyst ink was 1: 1 by mass ratio of carbon in platinum-supported carbon and polymer electrolyte, and the solvent was 1: 1 by volume ratio of ultrapure water and 1-propanol. In the same manner as the electrode catalyst layer 2a, the catalyst ink was applied to the substrate and dried. In both Examples and Comparative Examples, the thickness of the electrode catalyst layer was adjusted so that the amount of the catalyst material supported was 0.3 mg / cm ^2, and the electrode catalyst layer 2b on the fuel electrode side was formed.

(Production of membrane electrode assembly)
The base material on which the air electrode side electrode catalyst layer 2a and the base material on which the fuel electrode side electrode catalyst layer 2b were formed in the examples and comparative examples were punched into squares of 5 cm ² each to form a polymer electrolyte membrane A transfer sheet was placed so as to face both surfaces (Nafion (registered trademark) 212, manufactured by Dupont), and hot pressing was performed at 130 ° C. to obtain a membrane electrode assembly 12. Carbon cloths 3 and 4 each having a sealing layer formed as a gas diffusion layer are disposed on both surfaces of the membrane electrode assembly 12 thus obtained, and further sandwiched between a pair of separators 9 to form a single-cell solid polymer fuel A battery was produced.

[Power generation characteristics]
(Evaluation conditions)
Using a KIT-50156 fuel cell measuring device manufactured by NF Circuit Design Block Co., Ltd., power generation characteristics were evaluated at a cell temperature of 80 ° C. under conditions of 100% RH for both the anode and the cathode. Using pure hydrogen as the fuel gas and pure oxygen as the oxidant gas, the flow rate was controlled at a constant flow rate.

(Measurement result)
FIG. 3 shows the evaluation results of the power generation characteristics of the membrane electrode assemblies produced in Examples 1 and 2 and the comparative example. In FIG. 3, cell voltages at 0.3 A / cm ² and 1.0 A / cm ² are shown.
As can be seen from FIG. 3, the membrane electrode assemblies produced in Example 1 and Example 2 showed a power generation evaluation superior to the membrane electrode assemblies produced in Comparative Examples. Further, Example 1 showed power generation performance superior to that of Example 2. This is presumably because, in Examples 1 and 2, the proton conductivity on the catalyst surface was increased by embedding the polymer electrolyte in part of the catalyst material and carbon particles, and the reaction active points increased. . In contrast, in the comparative example, the catalyst material, the carbon particles, and the polymer electrolyte are dispersed in the solvent in one step, so that the polymer electrolyte is preferentially adsorbed on the carbon particles having a larger specific surface area than the catalyst material. Therefore, it is presumed that sufficient proton conductivity was not ensured on the catalyst surface. Moreover, in Example 2, the graphitization rate of the 2nd carbon particle is too high, and it is guessed that the gas diffusibility fell rather than Example 1. From the above, it was confirmed that according to the present invention, a polymer electrolyte fuel cell having a membrane electrode assembly exhibiting high power generation characteristics is provided.

  According to the method for producing an electrocatalyst layer of the present invention, in an electrocatalyst layer using an oxide-based non-platinum catalyst as a catalyst material, a solid material having a higher output performance than that of the conventional production method is obtained. Since the polymer fuel cell can be provided with a remarkable effect, the industrial utility value is high. Therefore, the present invention can be suitably used for a single fuel cell or a stack in a polymer fuel cell, particularly in a home fuel cell system or a fuel cell vehicle.

DESCRIPTION OF SYMBOLS 1 Solid polymer electrolyte membrane 2a Electrode catalyst layer 2b Electrode catalyst layer 12 Membrane electrode assembly 3 Gas diffusion layer 4 Gas diffusion layer 5 Air electrode (cathode)
6 Fuel electrode (anode)
7 Gas flow path 8 Cooling water flow path 9 Separator

Claims (17)

A method for producing composite particles used in an electrode catalyst layer comprising a polymer electrolyte and a catalyst substance and at least two types of carbon particles having different graphitization rates,
The two types of carbon particles include first carbon particles and second carbon particles having a graphitization rate lower than that of the first carbon particles,
Said catalyst material, said first carbon particles specific surface area is greater than the catalytic material, a first adjusting step of the first polyelectrolyte to adjust the first catalyst ink obtained by dispersing in a solvent,
A composite particle forming step of drying the first catalyst ink to form composite particles embedded with the first polymer electrolyte ; and
The composite particles are prepared by adjusting the second catalyst ink in which the composite particles, the second carbon particles, and the second polymer electrolyte are dispersed in a solvent, and then the second catalyst ink is added to the gas diffusion layer. method for producing composite particles, characterized in used Rukoto in the step of forming the electrode catalyst layer is coated on the transfer sheet and polymer electrolyte membrane on a base material selected from the. The graphitization rate of the first carbon particles is higher than the graphitization rate of the other carbon particles, and the lattice spacing C ₀ of the X-ray diffraction of the first carbon particles is 6.60 mm or more and 6.95 mm or less. The method for producing composite particles according to claim 1, wherein:   In the composite particle forming step, the mass ratio of the catalyst substance and the first carbon particles in the composite particles embedded with the first polymer electrolyte is in the range of 1: 0.01 to 1: 1. The method for producing composite particles according to claim 1 or 2, wherein:   In the composite particle forming step, the mass ratio of the first carbon particles to the polymer electrolyte in the composite particles embedded with the first polymer electrolyte is set within the range of 1: 0.2 to 1:50. The manufacturing method of the composite particle of any one of Claims 1-3 characterized by the above-mentioned.   5. The heat treatment temperature range for drying the first catalyst ink in the composite particle forming step is set in a range of 30 ° C. or more and 140 ° C. or less. 5. Method for producing composite particles.   The catalyst material is an electrode active material for an oxygen reduction electrode used as a positive electrode of a polymer electrolyte fuel cell, and includes at least one transition metal element selected from Ta, Nb, Ti, and Zr. The method for producing composite particles according to any one of claims 1 to 5.   The catalyst material is a partial oxide of a carbonitride of at least one transition metal element selected from Ta, Nb, Ti, or Zr, or an oxide of the transition metal element. The method for producing composite particles according to any one of claims 6 to 7. The method for producing composite particles according to any one of claims 1 to 7,
The composite particles embedded with the first polymer electrolyte formed by the composite particle manufacturing method, the second carbon particles having a specific surface area larger than that of the catalyst substance, and the second polymer electrolyte are dispersed in a solvent. A second adjustment step for adjusting the second catalyst ink;
An electrode catalyst layer forming step of forming an electrode catalyst layer by applying the second catalyst ink on a substrate selected from a gas diffusion layer, a transfer sheet and a polymer electrolyte membrane;
A method for producing an electrode catalyst layer for a fuel cell, comprising:   The fuel cell for fuel cell according to claim 8, wherein the second adjustment step includes a mixing step of mixing the composite particles embedded with the first polymer electrolyte and the second carbon particles without a solvent. A method for producing an electrode catalyst layer.   The method for producing an electrode catalyst layer for a fuel cell according to claim 9, wherein the mixing step includes a heat treatment step of heat-treating the composite particles embedded with the first polymer electrolyte and the second carbon particles. .   The heat treatment temperature range of the composite particles embedded with the first polymer electrolyte and the second carbon particles in the heat treatment step is within a range of 50 ° C or higher and 180 ° C or lower. Method for producing a fuel cell electrode catalyst layer.   A composite particle embedded with a polymer electrolyte produced by the method for producing a composite particle according to any one of claims 1 to 7.   A fuel cell electrode catalyst layer produced by the method for producing a fuel cell electrode catalyst layer according to any one of claims 8 to 11. In a method for producing a membrane electrode assembly for a fuel cell in which a proton conductive polymer electrolyte membrane sandwiched between a pair of electrode catalyst layers is sandwiched between a pair of gas diffusion layers,
A method for producing a membrane electrode assembly for a fuel cell, wherein at least one of the electrode catalyst layers comprises the electrode catalyst layer according to claim 13.   A fuel cell membrane / electrode assembly manufactured by the method for manufacturing a fuel cell membrane / electrode assembly according to claim 14.   The membrane electrode assembly according to claim 15 is sandwiched between a pair of gas diffusion layers, and the membrane electrode assembly sandwiched between the pair of gas diffusion layers is further sandwiched between a pair of separators. Solid polymer fuel cell. A method for producing composite particles contained in an electrode catalyst layer comprising a polymer electrolyte and a catalyst substance, and at least two types of carbon particles having different graphitization rates,
The two types of carbon particles include first carbon particles and second carbon particles having a graphitization rate lower than that of the first carbon particles,
A first adjustment step of adjusting the catalyst material, the first carbon particles having a specific surface area larger than that of the catalyst material, and a first catalyst ink in which a first polymer electrolyte is dispersed in a solvent;
A composite particle forming step of drying the first catalyst ink to form composite particles embedded with the first polymer electrolyte.

Images