Patent Application
20230335760
The present invention relates to a catalyst for electrode having a porous carbon as a support. More particularly, the present invention relates to a catalyst for electrode suitably used for a gas diffusion electrode, and more particularly, to a catalyst for electrode suitably used for a gas diffusion electrode of a fuel cell.
Further, the present invention relates to a composition for forming gas diffusion electrode, a membrane-electrode assembly, and a fuel cell stack comprising the above-described catalyst for electrode particles.
Polymer electrolyte fuel cells (Polymer Electrolyte Fuel Cell: hereinafter referred to as “PEFC” as required) are being researched and developed as power sources for fuel cell vehicles and household cogeneration systems.
A noble metal catalyst composed of noble metal particles of a platinum group element such as platinum (Pt) is used for a catalyst used for a gas diffusion electrode of a PEFC.
For example, as a typical conventional catalyst, a “Pt supported carbon catalyst” (hereinafter, referred to as “Pt/C catalyst” as needed) is known which is a powder of catalyst particles in which Pt fine particles are supported on conductive carbon powder.
Among the production cost of PEFC, the ratio of the cost occupied by noble metal catalysts such as Pt is large, which has become a problem toward the cost reduction of PEFC and the popularization of PEFC.
Among these research and development, in order to reduce the amount of platinum used, conventionally, a powder of catalyst particles (hereinafter, referred to as “core-shell catalyst particles” if necessary) having a core-shell structure formed of a core portion made of a non-platinum element and a shell portion made of Pt (hereinafter, referred to as “core-shell catalyst particles”) has been studied, and a large number of reports have been made.
For example, Patent Document 1 discloses a particle composite (corresponding to the core-shell catalyst particles) having a structure in which palladium (Pd) or a Pd alloy (corresponding to the core portion) is coated by an atomic thin layer of Pt atoms (corresponding to the shell portion). Further, in Patent Document 1, there is described as an example, a core-shell catalyst particle having a structure in which the core portion is Pd particles and the shell portion is a layer comprising Pt.
On the other hand, as a support of a catalyst for electrode, there are porous carbon having many pores inside the primary particle and solid carbon having fewer pores inside the primary particle compared with the porous carbon, and studies have been made for improving performance utilizing the respective characteristics thereof.
For example, Patent Document 2 discloses an example of an investigation in which porous carbon is adopted as a support. In addition, Patent Document 3 discloses an example of an investigation in which solid carbon is adopted as a support. For example, in Patent Document 2, as shown in
In Patent Document 2, it is mentioned that, thereby, adsorption of the polymer electrolyte on the surface of the catalyst particles 230 existing in the primary vacancy P220 is prevented, and the gas transportability can be sufficiently secured while preventing the effective reaction surface area of the catalyst from being lowered. As a result, it has been mentioned that a catalyst layer for a fuel cell exhibiting excellent power generation performance can be provided in which the activity per catalyst weight is improved even when the amount of catalyst is reduced.
Further, for example, Patent Document 3 discloses a catalyst (PtCo/C catalyst) for electrode for a fuel cell having a solid carbon support and a catalyst particle containing an alloy of platinum and cobalt supported on the support. The catalyst for electrode has a molar ratio of platinum to cobalt of 4 to 11:1 in the alloy and is acid treated at 70 to 90° C.
In Patent Document 3, when a PtCo alloy is supported on a porous carbon support, a part of PtCo alloy is encompassed inside the porous carbon support, and even if an acid treatment for suppressing elution of Co is performed, it is difficult to sufficiently treat PtCo alloy present inside the support, and as a result, Co is easily eluted from PtCo alloy present inside the support, and it has been viewed as a problem.
Therefore, in Patent Document 3, it is mentioned that, by using a solid carbon support instead of a porous carbon support, it is possible to avoid inclusion of a PtCo alloy inside the support. In addition, thus, it is disclosed that it becomes possible to sufficiently acid-treated the PtCo alloy and to suppress the elution of Co. It is mentioned that it is possible to balance both the initial performance and durability performance of the fuel cell, as a result.
Here, in Patent Document 3, the solid carbon is defined as follows. Namely, it is referred in Patent Document 3 that the solid carbon is a carbon having fewer voids inside carbon as compared with a porous carbon, and specifically, a carbon in which a ratio (t-Pot surface area/BET surface area) of BET surface area determined by N2 adsorption to outer surface area by t-Pot (surface area outside particle was calculated from particle size) is 40% or more.
Note that the “t-Pot surface area” described in Patent Document 3 is understood to indicate, for example, “t-plot (t-plot) surface area” described in the technical report “Analysis of Micropore Surface Area by t-plot Method” published on the internet by “MCEvatec Co., Ltd” on Feb. 1, 2019. The analysis of the micropore surface area by t-plot method is one of the methods to analyze from the adsorption isotherm (adsorption temperature: 77K) of nitrogen. This method is a method to compare and convert the data of adsorption isotherm with the standard isotherm, and to graph the relationship between thickness t of adsorption layer and adsorption amount. In addition to the fact that the specific surface area can be separated into the inside and the outside of the pores and quantified, the tendency of the pores can be known from the shape of the graph.
Examples of the solid carbon include, for example, the carbon described in Japanese Patent No. 4362116, and specifically, it is disclosed that Denkablack (registered trademark) manufactured by Electrochemical Industry Co., Ltd. may be exemplified.
Furthermore, Patent Document 4 discloses a catalyst for electrode (core-shell catalyst) where the catalyst particles are supported both inside and outside the mesopores of the porous carbon support {more specifically, the nanopores formed in the primary particles of the porous carbon support}. This catalyst for electrode has a structure that a ratio of the catalyst particles supported inside the mesopore (more specifically, the nanopores formed in the primary particles of the porous carbon support) is 50% or more when an analysis of a particle size distribution of the catalyst particles is performed by using a three-dimensional reconstructed image obtained by an electron beam tomography measurement using an STEM (scanning transmission electron microscopy).
Here, in the present specification, as described later, the “nanopore” of the porous carbon support means a pore having a pore size of 1 to 20 nm.
In Non-Patent Document 1 and Non-Patent Document 2 mentioned below, with respect to the catalyst particles supported on the porous carbon support, there is disclosed that the ratio of the catalyst particles supported inside the pores (nanopore described above) and the ratio of the catalyst particles supported on the outside of the {nanopore described above} are analyzed by a method different from that of Patent Document 4 described above.
More specifically, in Non-Patent Document 1, Strasser et al. of a group of Berlin Institute of Technology, with respect to the Pt/C catalyst in which Pt catalyst particles are highly dispersed on the commercially available porous carbon (trade name: “Ketjenblack EC-300J”, manufactured by Akzo Nobel, specific surface area: about 839 m2g−1), report the results of simultaneous imaging of SEM (Scanning Electron Microscopy) images and TSEM (Transmission SEM) images of the specific Pt/C catalyst particles of interest in the same measurement area. is doing. For example, see Table 1,
In their method, the SEM image provides information on the Pt catalyst particles present only on the observed portion (one outer surface) of the outer surface of the porous carbon support particles. That is, information on the number of particles of the catalyst particles supported on the outside of the nanopores of the porous carbon support particles can be obtained. On the other hand, from the TSEM image (transmission image), information on all the catalyst particles supported on the outside and the inside of the porous carbon support particles (the above-mentioned primary particles) in the observed Pt catalyst particles can be obtained. Then, from the information from the TSEM image and the information from the SEM image, among the Pt catalyst particles supported on the porous carbon support particles, they tried the attempt to distinguish the Pt catalyst particles supported on the outer surface (outside the nanopores) from the Pt catalyst particles supported on the inside.
Here, in Non-Patent Document 1, as to the SEM images, they do not carry out the measurement of “the back surface on the opposite side” with respect to the observed portion (“outer surface on one side”) of the outer surface (outside of the nanopores) of the porous carbon support particles. They assume that the state of the “outer surface on one side” and the state of the “back surface on the other side” are the same. That is, it is assumed that the number of particles of the catalyst particles supported on the “outer surface on one side” and the number of particles of the catalyst particles supported on the “back surface on the opposite side” are the same.
Next, in Non-Patent Document 2, Mr. Uchida et al. of a group at Yamanashi University report the results of photographing a Pt/C catalyst in which Pt catalyst particles are highly dispersed on the commercially available porous carbon (Product name: “Ketjenblack”, manufactured by Ketjen Black International, specific surface area: approx. 875 m2g−1), by using STEM (Scanning Transmission Electron Microscope) device capable of photographing SEM images and TEM (transmission electron microscopy) images of Pt catalyst particles. For example, see
First, they obtain information on the number of particles of all Pt catalyst particles supported on the porous carbon support particles from the TEM image of the catalyst particles of the specific Pt/C catalyst of interest. Next, they obtain information on the number of Pt catalyst particles present only on the back surface of the porous carbon support particles from the measurement of the SEM image of the same Pt/C catalyst particles as those taken by the TEM image. Next, they use a special 3D sample holder to rotate the specific Pt/C catalyst particle (measuring sample) of interest by exactly 180° C., to measure the SEM image of only the back surface of the same Pt/C catalyst particle. Using the information, among the Pt catalyst particles supported on the porous support particles, they tried the attempt to distinguish the Pt catalyst particles supported on the outer surface from the Pt catalyst particles supported on the inside.
They report that the “internal loading ratio”=“100×(number of Pt catalyst particles supported inside)/(total number of Pt catalyst particles)” measured by this method of the commercially available 30 wt % Pt/C catalyst (trade name: “TEC10E30E”, manufactured by Tanaka Metal Industry Co., Ltd., expressed as “c-Pt/CB,” in the specification) is 62%, the internal loading ratio of the commercially available 46 wt % Pt/C catalyst (trade name: “TEC10E50E”, Tanaka Metal Industry Co., Ltd, expressed as “Pt/CB” in the specification.) is 50% or more.
As described above, the present inventors recognize that the analysis methods of Non-Patent Document 1 and Non-Patent Document 2 are different from the analysis method of Patent Document 4 in the following points.
That is, the analysis method by electron tomography measurement in Patent Document 4 is a three-dimensional reconstructed method using an electron microscope, in which the same field of view of the sample to be measured of interest (the size of the target sample to be measured is a mass of about 100 to 300 nm in major axis or minor axis; see
On the other hand, the analysis method of Non-Patent Document 1 performs analysis by using two-dimensional images such as an SEM image and a TSEM image obtained by taking a sample to be measured from a specific one direction.
Further, in the analysis method of Non-Patent Document 2, the analysis is performed by using a two-dimensional image such as the SEM image of the sample to be measured taken from two specific directions (the directions of two axes orthogonal to each other obtained by rotating the sample holder by 180° C.) and the TSEM image of the sample to be measured taken from the specific one direction. In these analysis methods of Non-Patent Document 1 and Non-Patent Document 2, the present inventors consider that, for example, when the sample to be measured (catalyst particles for electrodes) has concave and convex portions, among such the catalyst particles, there is a high possibility that there is something that cannot be sufficiently determined whether the supporting position is inside or outside of the porous carbon support.
In the analysis method of Patent Document 4 where a three-dimensional tomographic image (tomogram) of the sample to be measured is used and this can be observed from various reports, the present inventors consider that, with respect to the sample to be measured of interest (the size of the target sample to be measured is a mass of about 100 to 300 nm in major axis or minor axis; see
The applicant of the present patent application presents the following publications as a publication in which the known inventions described in the above publications are described.
Patent Document
Toward the spread of PEFC, in order to reduce the amount of Pt used and the material cost, further improvement in catalytic activity is required for the catalyst for electrode.
The present inventors have found that, as to the catalyst for electrode such as Pt/C catalyst, there is no report that, when an analysis of a particle size distribution of the catalyst particles is performed by using a three-dimensional reconstructed image obtained by an electron beam tomography measurement using an STEM (scanning transmission electron microscopy), an improved product having a structure in which the catalyst particles are supported more inside than the outside of the nanopore of the primary particles of the porous carbon support could be actually synthesized, and there is still room for improvement.
The present invention was achieved in view of such technical circumstances, and it is an object of the present invention to provide a catalyst for electrode having excellent catalytic activity capable of contributing to cost reduction of PEFC.
Further, it is an object of the present invention to provide a composition for forming gas diffusion electrode, a gas diffusion electrode, a membrane-electrode assembly (MEA), and a fuel cell stack, which include the above-described catalyst for electrode.
The present inventors have intensively studied a configuration of a catalyst for electrode in which a large number of catalyst particles of a catalyst for electrode such as Pt/C catalyst are supported in a nanopore of a porous carbon to realize further improvement in catalytic activity.
As a result, it has been found that the catalyst particles are supported on a support so as to satisfy the following conditions, which is effective for improving the catalytic activity, and thus the present invention was completed.
More specifically, the present invention is composed of the following technical matters.
That is, the present invention provides a catalyst for electrode which includes an conductive porous carbon support having a nanopore of a pore size of 1 to 20 nm, and a plurality of catalyst particles supported on the support, wherein
When the microstructure of the catalyst for electrode is observed by using a three-dimensional reconstructed image of STEM, by satisfying the condition (a) that the ratio of the catalyst particles supported inside the nanopore is 50% or more and the condition (6) that the nanopores are formed to have the shape of the interconnected pores described above, the catalyst for electrode of the present invention can exhibit an excellent catalytic activity capable of contributing to cost reduction of PEFC.
The detailed reason why the catalyst for electrode of the present invention has excellent catalytic activity has not been sufficiently elucidated.
However, the present inventors consider as follows.
Namely, as to the catalyst for electrode of the present invention which has (a) the ratio of the catalyst particles supported inside the nanopore is 50% or more when the microstructure is observed by using a three-dimensional reconstructed image of STEM, there are many catalyst particles having a relatively small particle size with high activity inside the nanopore of the support as compared with a conventional catalyst for electrode.
When using in the catalyst layer of the gas diffusion electrode of PEFC, the catalyst particles supported inside the nanopores of such a support are supported on the support in a state in which these catalyst particles are hardly in direct contact with the polymer electrolyte present in the catalyst layer. Therefore, the catalyst for electrode of the present invention reduces the decrease in catalytic activity due to poisoning of the Pt component and can exhibit an excellent catalytic activity when made into an electrode as compared with a conventional catalyst for electrode. In addition, the catalyst for electrode of the present invention also reduces the dissolution of the Pt component from the catalyst particles.
Furthermore, in the catalyst for electrode of the present invention, from the viewpoint of obtaining the effect of the present invention more reliably, it is preferable that the ratio of the catalyst particles supported inside the nanopore is 70% or more when an analysis of a particle size distribution of the catalyst particles is performed by using a three-dimensional reconstructed image obtained by an electron beam tomography measurement using an STEM (scanning transmission electron microscopy).
Further, in the case that the microstructure is observed with the three-dimensional reconstructed image of STEM, when using in the catalyst layer of the gas diffusion electrode of PEFC, since the catalyst for electrode of the present invention in which (6) the nanopores are so as to be formed to have the shape of the interconnected pores described above has excellent diffusivity of water, protons and reaction gases (hydrogen, oxygen, or air) included therein, the catalyst particles supported inside the nanopore can be easily utilized. Therefore, also from this point of view, the catalyst for electrode of the present invention can exhibit excellent catalytic activity.
Here, in the present invention, the “analysis method of a particle size distribution of the catalyst particles is performed by using a three-dimensional reconstructed image obtained by an electron beam tomography measurement using an STEM (scanning transmission electron microscopy)” is an analysis method (analysis method name: “USAL-KM3D analysis method”) using STEM (scanning transmission electron microscope) at UBE Scientific Analysis Center Co., Ltd., in which electron tomography measurement is performed, and the obtained measurement data is subjected to image analysis using an image analysis software (“Avizo” available from FEI).
In the USAL-KM3D analysis method, a sample to be measured to be measured is prepared according to the following procedure and conditions.
First, in order to optimally measure the structure of the sample to be measured, the sample to be measure is prepared on the “Cu grid mesh with carbon support film” for TEM observation by the dispersion method, which is a general electron microscope sample preparation method to satisfy the following conditions.
(A) On the grid mesh, there is a mass of powder (catalyst for electrode) to be measured (a mass having a major axis or a minor axis in the range of about 60 to 300 nm, see
(B) When the grid mesh is rotated at a rotation angle of ±80° on its rotation axis, the captured image of the powder mass of the sample to be measured does not overlap with the captured image of the other fine powder mass. If the captured image of the powder mass of the sample to be measured overlaps with the captured image of the other fine powder mass, three-dimensional analysis cannot be performed.
(C) A plurality of powder masses visible in the measurement area are arranged so as to be apart from each other to the extent that 3D tomography observation is possible for the powder masses of the sample to be measured.
Nanopores of 1 nm or more among the pores contained in the powder mass of the above-mentioned target sample to be measured (catalyst for electrode) are subjected to the 3D tomography observation under the three-dimensionally visually distinguishable conditions (for example, adjustment of the acceleration voltage of the electron beam) without damaging the powder mass of the measurement target sample (catalyst for electrode).
Furthermore, here, in the present invention, the “nanopore” of the porous carbon support indicates a pore having a pore diameter of 1 to 20 nm, and the “micropore” indicates a pore having a pore diameter of less than 1 nm. Then, in the present invention, the “pore diameter of nanopore” indicates the “size of the inlet of nanopore”. The “pore diameter of micropore” indicates the “size of the inlet of micropore”.
In the present invention, the “pore diameter (size of the inlet of the pore)” of nanopore indicates the size of the “nanopore inlet” which can be determined by utilizing the three-dimensional reconstructed image obtained by an electron beam tomography measurement using a usual STEM (scanning transmission electron microscopy).
More preferably, the “pore diameter (size of the inlet of the pore)” of nanopore indicates the size of the “nanopore inlet” obtained by the “USAL-KM3D analysis method” described above.
More specifically, the “size of the inlet of nanopore” indicates the diameter of a circle (circle equivalent diameter) having the same area as the area of the inlet obtained from the image of the inlet of the nanopore obtained by the “USAL-KM3D analysis method”.
Further, in the present invention, the procedure by using the three-dimensional reconstructed image of STEM for confirming the conditions (8) that the nanopores are formed to have the shape of the interconnected pores described above will be described.
Confirmation of the condition (8) can be performed by using the three-dimensional reconstructed image obtained by the analysis of the catalyst for electrode by the electron beam tomography measurement with a general STEM (scanning transmission electron microscope). However, from the viewpoint of confirming the condition (B) more reliably, it is preferable to use the three-dimensional reconstructed image of STEM obtained in the process of carrying out the aforementioned USAL-KM 3D analysis method.
The procedure for confirming the condition (B) will be described below.
(D) First, a three-dimensional reconstructed image of STEM of the catalyst to be measured is obtained. From among the catalyst aggregates (aggregates composed of catalyst particles and porous carbon supports) in the three-dimensional reconstructed image, a catalyst aggregate which has a size that can be accommodated in a rectangular space with one side of 60 to 300 nm (region of interest) is selected. This procedure can be easily understood, for example, by referring to the stereoscopic images extracted from the 3D-STEM images (three-dimensional reconstructed images) of the catalyst aggregates of the catalysts of Example 1, Example 2, and Comparative Example 2 described later. (See
(E) Next, a stereoscopic image (20 to 50 nm on one side) is extracted from the inner region of the catalyst aggregate selected in the step (D). This procedure can be easily understood, for example, by referring to the stereoscopic images (three-dimensional reconstructed images of STEM) obtained for the catalyst aggregates of the catalysts of Example 1, Example 2, and Comparative Example 2 described later (
(F) Next, the stereoscopic image (three-dimensional reconstructed image of STEM) inside the catalyst aggregate obtained in the step (E) is observed, and by utilizing the difference in luminance, the part of the void (part of pore such as nanopore) and the part of the porous carbon support are segmented.
More specifically, this stereoscopic image (three-dimensional reconstructed image of STEM) is composed of divided smaller cubic pixels (voxels). Each pixel (voxel) stores luminance (no unit). Then, by setting an appropriate threshold for the luminance, the analyst clearly segments (binarizes) the part of the void (part of pore such as nanopore) and the part of the porous carbon support in the stereoscopic image (three-dimensional reconstructed image of STEM). When the luminance of a certain pixel (voxel) is above the threshold, it is automatically determined to be a carbon part. Also, if the luminance of a certain pixel (voxel) is less than the threshold value, it is automatically determined to be a void part. This segmentation can be performed by setting the same luminance threshold for all pixels (voxels) included in the same stereoscopic image (three-dimensional reconstructed image of STEM). For different stereoscopic images (three-dimensional reconstructed images of STEM), the analyst sets different luminance thresholds (thresholds suitable for segmentation).
From the viewpoint of performing segmentation more accurately, the size of a pixel (voxel) is preferably a cube with one side of 1 nm or less.
In the present invention, when measuring the porosity of the stereoscopic image (three-dimensional reconstructed image of STEM) of the catalyst aggregate described later, the catalyst particles are regarded as voids during the segmentation.
Further, for the step (F), for example, it can be easily understood by referring to the stereoscopic images extracted from the 3D-STEM images (three-dimensional reconstructed images) of the catalyst aggregates of the catalysts of Example 1, Example 2, and Comparative Example 2 described later. (See
Furthermore, it can be easily understood by referring to the three cross-sections (three cross-sections after the segmentation) of the stereoscopic images (three-dimensional reconstructed images of STEM) obtained for the catalyst aggregates of the catalysts of Example 1, Example 2, and Comparative Example 2 described later (
(G) Next, when observing the six square cross-sections of the stereoscopic image (three-dimensional reconstructed image of STEM) after performing segmentation in the step (F), it is confirmed whether or not at least one cross section has at least one of the following shaped nanopore (interconnected pore) is formed.
That is, it is confirmed whether or not the nanopore (interconnected pore) observed in the cross-section of the square of interest has at least one opening in contact with a first side of four sides of the cross section, and at least one opening in contact with a second side which is parallel to the first side. In addition, it is confirmed whether or not the nanopore has a shape of an interconnected pore which extends continuously from the opening on the first side to the opening on the second side without blocking.
For example, referring to Example 1 described later, as shown in
Furthermore, from the viewpoint of obtaining the effects of the present invention more reliably, in the catalyst for electrode of the present invention, it is preferable that the nanopore (interconnected pore) observed in the square cross-section of the stereoscopic image of interest has a shape having a plural of branches (see
Furthermore, from the viewpoint of obtaining the effects of the present invention more reliably, for the same reason as described above, in the catalyst for electrode of the present invention, it is preferable that the nanopore (interconnected pore) observed in the square cross section of the stereoscopic image of interest has two or more openings on the first side (see
Further, from the viewpoint of obtaining the effects of the present invention more reliably, for the same reason as described above, in the catalyst for electrode of the present invention, it is preferable that the nanopore (interconnected pore) observed in the square cross section of the stereoscopic image of interest has two or more openings on the second side (see
Furthermore, from the viewpoint of obtaining the effects of the present invention more reliably, for the same reason as described above, in the catalyst for electrode of the present invention, it is preferable that the nanopore (interconnected pore) observed in the square cross section of the stereoscopic image of interest has at least one opening on the third side perpendicular to the first side.
For example, referring to Example 1 described later, as shown in
Further, from the viewpoint of obtaining the effects of the present invention more reliably, for the same reason as described above, in the catalyst for electrode of the present invention, it is preferable that the nanopore (interconnected pore) observed in the square cross section of the stereoscopic image of interest has at least one opening on the fourth side perpendicular to the first side.
For example, referring to Example 1 described later, as shown in
Furthermore, from the viewpoint of obtaining the effects of the present invention more reliably, in the catalyst for electrode of the present invention, it is preferable that a porosity measured by using the three-dimensional reconstructed image of STEM (stereoscopic image of interest) is 35% or more, more preferably 40% or more, more preferably 45% or more, furthermore preferably 50% or more, furthermore preferably 55% or more, furthermore preferably 60% or more, furthermore preferably 65% or more.
On the other hand, from the viewpoint of durability, in the catalyst for electrode of the present invention, it is preferable that a porosity measured by using the three-dimensional reconstructed image of STEM (stereoscopic image of interest) is 80% or less, more preferably 75% or less.
Further, in the catalyst for electrode of the present invention, it is preferable that the porous carbon support contains more nanopores having a pore diameter (size of the inlet of the pore) of 1 to 10 nm among the nanopores. It has been reported that the micellar diameter of the polyelectrolyte used for the anode and cathode catalyst layers of MEA is about 10 nm (for example, Y. S. Kim, et al, DOE Hydrogen Program Merit Review and Peer Meeting FC16, (2009)). Therefore, by using the porous carbon support containing more pores having a pore diameter (size of the inlet of the pore) of 1 to 10 nm, it becomes difficult for the polyelectrolyte to penetrate into the nanopores, and it is more reliably prevented the contact between the catalyst particles supported inside the nanopores and the polyelectrolyte.
Furthermore, in the catalyst for electrode of the present invention, within the range where the effects of the present invention can be obtained, the porous carbon support may further have micropore having a pore diameter of less than 1 nm.
Furthermore, from the viewpoint of obtaining the effect of the present invention more reliably, the porous carbon support is preferably one which can satisfy the above conditions (α) and (β) when used as an catalyst for electrode among “CNovel (manufactured by Toyo Tanso Co., Ltd., product name, registered trademark)” (for example, the porous carbons described in Japanese Patent No. 5636171, Japanese Patent No. 5695147, Japanese Patent No. 5860600, Japanese Patent No. 5860601, Japanese Patent No. 5860602).
CNovel is a porous carbon which has at least nanopores (pore diameter of 1 to 20 nm) and a carbonaceous wall forming the outline of the nanopore; wherein the carbonaceous wall has a portion forming a layered structure, the carbonaceous wall has a three-dimensional network structure, the nanopores are open pores and has the shape of continuous nanopores (the shape of interconnected pores. Referring “interconnected pore P1 where a plural of nanopore P22 are connected in
Further, in the catalyst for electrode of the present invention, the catalyst particle may be made of Pt (0 valence).
Furthermore, in the catalyst for electrode of the present invention, the catalyst particle may be made of a Pt alloy. A metal specie other than Pt, which is an element of the alloy is not particularly limited. From the viewpoint of obtaining excellent catalytic activity, it is preferable that the metal species other than Pt, which is an element of the alloy, is at least one metal of Co and Ni.
Further, in the catalyst for electrode of the present invention, the catalyst particle may be a core-shell catalyst particle. In this case, from the viewpoint of obtaining excellent catalytic activity, it is preferable that the core-shell catalyst particle is composed of a core particle and a Pt shell layer (a region composed of Pt (0 valence)) formed on at least a part of the surface of the core particle. The metal specie constituting the core particles is not particularly limited, but at least one of Pd, Ni and Co is preferable from the viewpoint of obtaining excellent catalytic activity. Further, the core particle may be an alloy of at least one of Pd, Ni and Co and other metal. From the viewpoint of reducing the amount of precious metal used, the core particle may contain at least one of a base metal other than precious metal and a base metal oxide, a base metal nitride, and a base metal carbide.
Furthermore, in the catalyst for electrode of the present invention, from the viewpoint of obtaining the effect of the present invention more reliably, it is preferable to satisfy the following equation (1) when an analysis of a particle size distribution of the catalyst particles is performed by using a three-dimensional reconstructed image obtained by an electron beam tomography measurement using an STEM (scanning transmission electron microscopy).
(D10/D20)≤0.80 (1)
Here, in the equation (1), D10 indicates the arithmetic mean value of the sphere-equivalent diameter of the catalyst particles supported on the inside of the nanopores of the support, D20 indicates the arithmetic mean value of the sphere-equivalent diameter of the catalyst particles supported on the outside of the nanopores of the support.
When supporting the catalyst particles on the porous carbon support so as to simultaneously satisfy the condition of the above equation (1), it is possible that the catalyst for electrodes of the present invention more reliably exhibits excellent catalytic activity that can contribute to cost reduction of PEFC.
Here, from the viewpoint of obtaining the effect of the present invention more reliably, it is preferable that the value of (D10/D20) of the above equation (1) is 0.85 or more, more preferably 0.90 or more.
Further, in the catalyst for electrode of the present invention, from the viewpoint of more reliably obtaining the effect of the present invention, when the analysis of the particle size distribution of the catalyst particles is performed by using three-dimensional reconstructed images obtained by electron beam tomography (electron tomography) measurement with an STEM (scanning transmission electron microscopy), it is more preferable that the conditions of the following the equation (2) and the equation (3) are further simultaneously satisfied.
D1≤D2 (2)
(N1/N2)>1.0 (3)
Here, in the equation (2) and the equation (3), D1 indicates a sphere equivalent diameter of particles exhibiting a maximum frequency (maximum number of particles) among the catalyst particles supported inside the nanopores of the support. In the equation (2) and the equation (3), D2 indicates a sphere equivalent diameter of particles exhibiting a maximum frequency (maximum number of particles) among the catalyst particles supported outside the nanopores of the support.
Further, in the equation (2) and the equation (3), N1 indicates a frequency of particles (number of particles) exhibiting a maximum frequency (maximum number of particles) among the catalyst particles supported inside the nanopores of the support. In the equation (1) and the equation (2), N2 indicates a frequency of particles exhibiting a maximum frequency (maximum number of particles) among the catalyst particles supported outside the nanopores of the support.
By supporting the catalyst particle on the porous carbon support so as to simultaneously satisfy the conditions of the equation (2) and the equation (3) described above, the catalyst for electrode of the present invention can more reliably exhibit an excellent catalytic activity capable of contributing to cost reduction of PEFC.
Further, in the catalyst for electrode of the present invention, at least a region made of Pt (0 valence) is formed on at least a part of the surface of the catalyst particle may be covered with a Pt oxide film as long as the catalyst particles can exhibit excellent catalytic activity.
Further, from the viewpoint of obtaining the effect of the present invention more reliably, in the catalyst for the electrode of the present invention, the BET specific surface area (nitrogen adsorption specific surface area) of the porous carbon support is preferably 200 to 1500 m2/g.
When the catalyst for the electrode is used for the cathode, the BET specific surface area (nitrogen adsorption specific surface area) of the porous carbon support is preferably 700 to 1500 m2/g from the viewpoint of more reliably obtaining the effect of the present invention, more preferably 750 to 1400 m2/g. Furthermore, when the catalyst for the electrode is used for the cathode from the viewpoint that it is preferable to have a predetermined durability in consideration of the operating environment (temperature fluctuation range, potential fluctuation range) of the cathode, the BET specific surface area (nitrogen adsorption specific surface area) of the porous carbon support is preferably 750 to 900 m2/g.
Further, the present invention provides a powder of the catalyst for electrode containing 10 wt % or more of the above-mentioned catalyst for electrode of the present invention.
In the powder of the catalyst for electrode, the “containing component other than the above-mentioned catalyst for electrode of the present invention” is “the catalyst for electrode other than the above-mentioned catalyst for electrode of the present invention”. That is, the powder of the catalyst for electrode of the present invention does not include the powder which does not function as the catalyst for electrode.
Since the powder of the catalyst for electrode of the present invention contains the above-mentioned catalyst for electrode of the present invention, it is possible to exhibit excellent catalytic activity that can contribute to cost reduction of PEFC.
Here, from the viewpoint of more reliably obtaining the effect of the present invention, the content of the above-mentioned catalyst for electrode of the present invention in the powder of the catalyst for electrode of the present invention is preferably 30 wt % or more, more preferably 50 wt % or more, further preferably 70 wt % or more, and most preferably 90 wt % or more.
The powder of the catalyst for electrode of the present invention may contain a catalyst for electrode having the following configuration (for convenience, referred to as “catalyst for electrode P”) in addition to the above-mentioned catalyst for electrode of the present invention.
That is, the catalyst for an electrode P has a structure where the catalyst contains a porous carbon support having nanopores of a pore diameter of 1 to 20 nm, and a plurality of catalyst particles supported on
The powder of the catalyst for electrode of the present invention may be composed of the above-mentioned catalyst for electrode of the present invention and the catalyst for electrode P.
Also in this case, from the viewpoint of more reliably obtaining the effect of the present invention, the content of the above-mentioned catalyst for electrode of the present invention in the powder of the catalyst for electrode of the present invention is preferably 30 wt % or more, more preferably 50 wt %, further preferably 70 wt % or more, most preferably 90 wt % or more.
Furthermore, the powder of the catalyst for electrode of the present invention may contain one or more kinds of conductive carbon supports that are different from the porous carbon support of the catalyst for electrode of the present invention, within the range where the effects of the present invention can be obtained. For example, one or more of Ketjen black and acetylene black may be contained. For example, 10 wt % to 100 wt % of different kinds of the conductive carbon supports may be contained with respect to the weight of the porous carbon support of the catalyst for electrode of the present invention.
Further, the present invention provides a gas diffusion electrode containing the above-described catalyst for electrode of the present invention or the powder of the catalyst for electrode of the present invention.
Since the gas diffusion electrode of the present invention includes the catalyst for electrode of the present invention or the powder of the catalyst for electrode of the present invention, it becomes easy to have a configuration having excellent catalytic activity (polarization property) which can contribute to cost reduction of PEFC.
Further, the present invention provides a gas diffusion electrode containing the above-described catalyst for electrode of the present invention or the powder of the catalyst for electrode of the present invention.
The gas diffusion electrode of the present invention includes the catalyst for electrode of the present invention. Therefore, it becomes easy to have a configuration having excellent catalytic activity (polarization property) which can contribute to cost reduction of PEFC.
Furthermore, the present invention provides a membrane-electrode assembly (MEA) including the above-mentioned gas diffusion electrode of the present invention.
Since the membrane-electrode assembly (MEA) of the present invention includes the gas diffusion electrode of the present invention, it becomes easy to have a configuration having a cell property capable of contributing to cost reduction of PEFC.
Further, the present invention provides a fuel cell stack, in which the membrane-electrode assembly (MEA) of the present invention described above is included.
According to the fuel cell stack of the present invention, since the membrane-electrode assembly (MEA) of the present invention is included, it is easy to have a configuration having a cell property capable of contributing to cost reduction of PEFC.
According to the present invention, there is provided a catalyst for electrode having excellent catalytic activity capable of contributing to cost reduction of PEFC.
Further, according to the present invention, there is provided a composition for forming gas diffusion electrode, a gas diffusion electrode, a membrane-electrode assembly (MEA), and a fuel cell stack, each of which includes such a catalyst for electrode.
Hereinafter, with reference to figures as appropriate, a suitable embodiment of the present invention is explained in detail.
The MEA10 shown in
In this MEA10, at least one of the cathode 1 and the anode 2 has a configuration in which a catalyst for electrode 20 (Pt catalyst 20) to be described later is contained.
The MEA10 can be produced by laminating the cathode 1, the anode 2, and the PEM 3 as shown in
<Gas Diffusion Electrode (GDE)>
The cathode 1 as a gas diffusion electrode has a configuration including a gas diffusion layer 1gd and a catalyst layer 1c, which is formed on the PEM 3 side surface of the gas diffusion layer lgd. Further, the cathode 1 has a water repellent layer (Micro Porous Layer, hereinafter, referred to as “MPL” as needed) 1m arranged between the gas diffusion layer lgd and the catalyst layer 1c.
Similar to the cathode 1, the anode 2, which is a gas diffusion electrode, has a configuration including a gas diffusion layer 2gd and a catalyst layer 2c, which is formed on the PEM 3 side surface of the gas diffusion layer 2gd, and a MPL 2m, which is arranged between the gas diffusion layer 2gd and the catalyst layer 2c.
In the cathode 1, the catalyst layer 1c is a layer in which a reaction proceeds such that water is generated from air (oxygen gas) sent from the gas diffusion layer lgd and hydrogen ions moving through the PEM 3 from the anode 2.
In addition, in the anode 2, the catalyst layer 2c is a layer in which a reaction in which hydrogen ions and electrons are generated from hydrogen gas sent from the gas diffusion layer 2gd proceeds.
At least one of the catalyst layer 1c of the cathode 1 and the catalyst layer 2c of the anode 2 includes the catalyst for electrode 20 of the present invention.
Hereinafter, the preferred embodiment of the catalyst for electrode of the present invention will be described with reference to
As shown in
Further, the catalyst for electrode 20 shown in
That is, as described above, when the microstructure is observed by using the three-dimensional reconstructed image of STEM as described above, the catalyst for electrode 20 has the structure which satisfies the condition (a) the ratio of the catalyst particle supported inside the nanopore is 50% or more, and the condition (8) the nanopore is formed so as to have the aforementioned shape.
To explain the condition (a) in detail, when observing the fine structure of the catalyst for electrode 20 according to the information of the three-dimensional reconstructed image of STEM obtained in the above-described steps (A) to (C), the ratio of the catalyst particle 23 supported inside the nanopore P22 is 50% or more.
Furthermore, from the viewpoint of obtaining the effect of the present invention more reliably, when the particle size distribution of the catalyst particle 23 is analyzed by using the above-described three-dimensional reconstructed image, the ratio of the catalyst particle 23 supported inside the nanopore P22 in the catalyst for electrode 20 is preferably 55% or more, more preferably 60% or more, further more preferably 70% or more.
To explain the condition (B) in detail, when observing according to the information of the three-dimensional reconstructed image of STEM obtained in the above-described steps (D) to (G), the catalyst for electrode 20 has the following structure.
More specifically explaining, when looking at six square cross sections of “the stereoscopic image(one side of 20 to 50 nm) extracted from “the catalyst aggregate composed of the catalyst particle 20 (catalyst aggregate composed of the catalyst particle 23 which has a size that can be accommodated in a rectangular space with one side of 60 to 300 nm and the support 22)” which can be observed by the 3D-STEM image (three-dimensional reconstructed image), in at least one cross section, the catalyst for electrode 20 has the structure where at least one “interconnected pore P1 in which a plurality of nanopores P22 are connected” having the following shape is formed.
That is, in the catalyst for electrode 20, when the fine structure of the catalyst for electrode is observed with the 3D-STEM image (three-dimensional reconstructed image), at least, the nanopore P22 formed in at least one of the six square cross sections of the stereoscopic image obtained by cutting the inside of the catalyst aggregate has at least one opening in contact with the first side of four sides of the square cross section, and at least one opening in contact with the second side of the cross section of the square which is parallel to the first side. In addition, the nanopore P22 has the shape of an interconnected pore P1 which extends continuously from the opening on the first side to the opening on the second side without blocking.
In the following, more specific description will be made by referring the example of the catalyst for electrode of Example 1 shown in
(D) First, with respect to the catalyst for electrode of Example 1 to be measured, a three-dimensional reconstructed image of STEM is obtained.
From among the catalyst aggregates in the three-dimensional reconstructed image, a catalyst aggregate which has a size that can be accommodated in a rectangular space with one side of 60 to 300 nm (region of interest) is selected (
(E) Next, a stereoscopic image (20 to 50 nm on one side) is extracted from the inner region of the catalyst aggregate of the catalyst for electrode of Example 1 selected in the step (D) (
(F) Next, the stereoscopic image (three-dimensional reconstructed image of STEM) inside the catalyst aggregate of the catalyst for electrode of Example 1 obtained in the step (E) is observed, and by utilizing the difference in luminance, the part of the void (part of pore such as nanopore) and the part of the porous carbon support are segmented (
(G) Next, when observing the six square cross-sections of the stereoscopic image inside the catalyst aggregate of the catalyst for electrode of Example 1 after performing segmentation in the step (F), as shown in
From the viewpoint of obtaining the effects of the present invention more reliably, as shown in the example of Example 1 of
Furthermore, from the viewpoint of obtaining the effects of the present invention more reliably, as shown in the example of Example 1 of
Further, from the viewpoint of obtaining the effects of the present invention more reliably, as shown in the example of Example 1 of
Furthermore, from the viewpoint of obtaining the effects of the present invention more reliably, as shown in the example of Example 1 of
Furthermore, from the viewpoint of obtaining the effects of the present invention more reliably, as shown in the example of Example 1 of
Furthermore, from the viewpoint of obtaining the effects of the present invention more reliably, in the catalyst for electrode 20, it is preferable that a porosity measured by using the three-dimensional reconstructed image of STEM (stereoscopic image of interest) is 35% or more, more preferably 40% or more, more preferably 45% or more, furthermore preferably 50% or more, furthermore preferably 55% or more, furthermore preferably 60% or more, furthermore preferably 65% or more.
On the other hand, from the viewpoint of durability, in the catalyst for electrode 20, it is preferable that a porosity measured by using the three-dimensional reconstructed image of STEM (stereoscopic image of interest) is 80% or less, more preferably 75% or less.
Here, a region made of Pt (0 valence) is formed on at least a part of the surface of the catalyst particle 23. Provided that, within the range where the effects of the present invention can be obtained, a Pt oxide layer may be formed on the region of the surface made of Pt (0 valence) of the catalyst particle 23.
As a more specific structure of the catalyst particle 23, when the catalyst particle 23 is made of Pt (0 valence), not particularly limited, when the catalyst particle 23 is made of a Pt alloy, it is preferable that the catalyst particle 23 is a core-shell catalyst particle.
When the catalyst particle 23 is made of a Pt alloy, the metal specie other than Pt, which is an element of the alloy is not particularly limited. From the viewpoint of obtaining excellent catalytic activity, it is preferable that the metal species other than Pt, which is an element of the alloy, is at least one metal of Co and Ni.
When the catalyst particle 23 is the core-shell catalyst particle, from the viewpoint of obtaining excellent catalytic activity, it is preferable that the core-shell catalyst particle is composed of a core particle and a Pt shell layer (a region composed of Pt (0 valence)) formed on at least a part of the surface of the core particle. The metal specie constituting the core particles is not particularly limited, but at least one of Pd, Ni and Co is preferable from the viewpoint of obtaining excellent catalytic activity. Further, the core particle may be an alloy of at least one of Pd, Ni and Co and other metal.
From the viewpoint of reducing the amount of precious metal used, the core particle may contain at least one of a base metal other than precious metal and a base metal oxide, a base metal nitride, and a base metal carbide.
Further, the catalyst for electrode 20 preferably has an average value of crystallite size of 3 to 16.0 nm as measured by powder X-ray diffraction (XRD).
Further, a Pt loading ratio of the catalyst for electrode 20 is preferably 5.6 to 66.5 wt %.
The support 22 preferably satisfies the above conditions (α) and (β) when used as an catalyst for electrode. From this point of view, as the support 22, a carbon selected among CNovel (manufactured by Toyo Tanso Co., Ltd., product name, registered trademark) which can satisfy the above conditions (α) and (β) when used as an catalyst for electrode is preferable.
As shown in
Usually, this layered structure is produced by heat-treating the carbon materials at a certain temperature or higher.
However, in general, since carbon materials shrink during the heat treatment, the pores tend to collapse and the specific surface area tends to decrease, and thus, when crystallinity develops, it is difficult to obtain a porous carbon having a high specific surface area.
On the other hand, since the support 22 has the nanopore P22 and the carbonaceous wall forming the outlines of the nanopores P22, it can withstand the shrinkage during the heat treatment, and the layered structure is sufficiently formed in the carbonaceous walls, and the specific surface area is sufficiently secured.
Further, since the carbonaceous wall has a three-dimensional network structure, the support 22 can carry catalyst particles as small as several nanometers in a highly dispersed state, and is suitable as a support for the catalyst layer of the fuel cell. It should be noted that the support 22 does not need to have the layered structure in the entire carbonaceous wall, and may partially have an amorphous portion.
Further, it is preferable that the support 22 has a specific surface area of 200 m2/g to 1500 m2/g. When the specific surface area is 200 m2/g or more, it becomes easier to form the three-dimensional network structure more reliably. Thereby, the pores can be sufficiently formed, and it becomes easier to have sufficient gas adsorption ability. On the other hand, when the specific surface area is 1500 m2/g or less, it becomes easier to form the carbonaceous wall more reliably. This makes it easier to sufficiently form the nanopores P22.
Here, as shown in
From the viewpoint of having sufficient electrical conductivity, the support 22 preferably has a specific resistance of 10.0×102 Ω·cm or less, more preferably 5.0×102 Ω·cm or less, and further preferably 1.0×102 Ω·cm or less.
Further, the support 22 may contain micropores having a pore diameter of less than 1 nm (relatively small pores among pores classified as so-called micropores), and micropores having a pore diameter of more than 20 nm to not more than 50 nm (relatively large pores among pores classified as so-called mesopores), within the range where the effects of the present invention can be obtained.
Furthermore, it is preferable that the support 22 is a porous carbon support having good dispersibility in the gas diffusion electrode forming composition including the catalyst for electrode 20 and excellent electrical conductivity.
Here, as shown in
Then, the catalyst for electrode 20 simultaneously satisfies the conditions of the following the equations (1) to (3) in case that a measurement of electron beam tomography (electron tomography) by 3D-STEM is carried out.
(D10/D20)≥0.80 (1)
D1≤D2 (2)
(N1/N2)>1.0 (3)
Here, in the equations (1) to (3), D10 shows the arithmetic mean value of the sphere-equivalent diameter of the catalyst particles 23 supported on the inside of the nanopores P22 of the support 22.
Further, D20 shows the arithmetic mean value of the sphere-equivalent diameter of the catalyst particles 23 supported on the outside of the nanopores P22 of the support 22.
Furthermore, D1 indicates a sphere equivalent diameter (nm) of particles exhibiting a maximum frequency (maximum number of particles) among the catalyst particles 23 supported inside the nanopore P22 of the support 22.
Further, D2 indicates a sphere equivalent diameter (nm) of particles exhibiting a maximum frequency (maximum number of particles) among the catalyst particles 23 supported outside the nanopore P22 of the support 22.
Furthermore, N1 indicates a frequency (number of particles) of particles exhibiting a maximum frequency (maximum number of particles) among the catalyst particles 23 supported inside the nanopore P22 of the support 22.
Further, N2 indicates a frequency (number of particles) of particles exhibiting a maximum frequency (maximum number of particles) among the catalyst particles 23 supported outside the nanopore P22 of the support 22.
In the case of the catalyst for electrode 20 which simultaneously satisfies the conditions of the equations (1) to (3), as compared with a conventional catalyst for electrode 200, there exist many catalyst particles 23 with high activity inside the nanopore P22 of the support 22 in a relatively small particle size. The catalyst particle 23 supported inside the nanopores P22 of such a support 22 exhibits excellent catalytic activity when made into an electrode as compared with a conventional catalyst for electrode 200. Further, the catalyst particle is supported on the support 22 in a state in which it is difficult to directly contact with a polymer electrolyte such as Nafion included in the catalyst layer (catalyst layer 1c or catalyst layer 2c), and the dissolution of the Pt component is also reduced.
Here, from the viewpoint of obtaining the effects of the present invention more reliably, the value of (D10/D20) of the equation (1) is preferably 0.85 or more, more preferably 0.90 or more.
The method for producing the catalyst for electrode 20 is not particularly limited and can be produced by a known method, except that it includes a “support pretreatment step”, a “Pt addition step”, and a “reduction step” for satisfying the conditions of the equations (1) to (3).
In the support pretreatment step, the support 22 is put into an ultrapure water, and a pH adjuster is further added to prepare a dispersion whose pH is adjusted to 2 to 5. Furthermore, the temperature of the dispersion is kept at 80 to 99° C., preferably 90 to 99° C. for a predetermined time while stirring (however, the state of not boiling is maintained). Then, the temperature of the dispersion is lowered to room temperature.
Thus, the gas inside the nanopore P22 of the support 22 is removed, so that ultrapure water can sufficiently enter into inside the nanopore P22. Then, in the subsequent “Pt addition step”, the Pt raw materials are sufficiently held inside the nanopore P22 of the support 22. Thus, a large number of precursors of the Pt catalyst particle are supported inside the nanopore P22 of the support 22.
Note that “ultrapure water” used as the preparation of the aqueous solution in this support pretreatment step is water in which the specific resistance R (reciprocal of the electric conductivity measured by the JIB standard test method (JIB K0552)) represented by the following the equation (4) is 3.0 M Q-cm or more. In addition, it is preferable that “ultrapure water” has a quality equivalent to “A3” or a clean quality equivalent to or higher than that of “A3” defined in “JISK0557 water used for testing of water and waste”.
This ultrapure water is not particularly limited as long as it has an electric conductivity satisfying the relation represented by the following equation (4). For example, ultrapure water produced using an ultrapure water producing apparatus “Milli-Q Series” (manufactured by Merck Co., Ltd.) and “Elix UV Series” (manufactured by Nippon Millipore Co., Ltd.) can be mentioned as the above ultrapure water.
R=1/ρ (4)
In the above equation (4), R represents a specific resistance, and p represents an electric conductivity measured by a JIS standard test method (JIS K0552).
The next step of the “support pretreatment step” is the “Pt addition step”. In this “Pt addition step”, an aqueous solution of a water-soluble Pt salt (N. E. CHEMCAT, trade name “A-salt” (concentration of Fe component: 8 ppm or less)) dissolved in ultrapure water is added to the dispersion liquid of the support 22 obtained through the “support pretreatment step” at room temperature.
The next step of the “Pt addition step” is the “reduction step”. In this “reduction step”, the temperature of the liquid obtained through the “Pt addition step” is raised to 50° C. or higher, and an aqueous solution in which a water-soluble reducing agent (preferably an acidic water-soluble reducing agent) is dissolved is added. After the addition of the reducing agent, the liquid temperature is maintained at 50° C. or higher for a predetermined period of time to allow the reduction reaction to proceed, and then the temperature of the liquid is lowered to room temperature.
The next step of the “reduction step” is the “washing step”. In this “washing step”, the solid component and the liquid component in the liquid obtained through the “reduction step” are separated, and the solid content (a mixture of a Pt/C catalyst and other impurities) is washed. For example, the solid component in the liquid obtained through the “reduction step” may be separated from the liquid component by using a filtering means such as filter paper or a filter cloth. The solid content may be washed with the above-mentioned ultrapure water, a pure water (specific resistance R represented by the above equation (4) is 0.1 MΩ·cm or more and less than 3.0 MΩ·cm), or a pure warm water (temperature of pure water being 40 to 80° C.) may be used. For example, when the pure warm water is used, the filtrate is washed repeatedly until the electrical conductivity after washing becomes less than 10 μS/cm.
The next step after the “washing step” is the “drying step”. In this “drying step”, water is separated from the solid component (mixture of Pt/C catalyst and water) obtained through the “washing step”. First, the solid component is air-dried, and then dried in a dryer at a predetermined temperature for a predetermined time.
The next step after the “drying step” is the “crushing step”. In this “crushing step”, the solid component (Pt/C catalyst) obtained from the “drying step” is crushed to the catalyst powder with a crushing means such as a mixer.
The polymer electrolyte contained in the catalyst layer 1c and the catalyst layer 2c is not particularly limited as long as it has hydrogen ion conductivity, and known ones can be used. For example, the polymer electrolyte can exemplify a known perfluorocarbon resin having a sulfonic acid group and a carboxylic acid group. Examples of easily available polymer electrolytes having hydrogen ion conductivity include Nafion (registered trademark, manufactured by DuPont), Aciplex (registered trademark, manufactured by Asahi Kasei Co., Ltd.), and Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.).
Then, at least one of the catalyst layer 1c of the cathode 1 and the catalyst layer 2c of the anode 2 shown in
The gas diffusion layer lgd provided in the cathode 1 shown in
In addition, the gas diffusion layer 2gd provided in the anode 2 is a layer provided for supplying a reducing agent gas (e.g., hydrogen gas) to the catalyst layer 2c. And, the gas diffusion layer 2gd serves to support the catalyst layer 2c.
The gas diffusion layer (lgd) shown in
The member which can be used for the gas diffusion layer (lgd) is not particularly limited, and a known member can be used. For example, preferably, there are exemplified carbon paper and other material, in which carbon paper is used as a main material and auxiliary materials including carbon powder, ion exchange water, and a polyethylene terephthalate dispersion as a binder is applied on the carbon paper.
(Water Repellent Layer (MPL))
As shown in
The polymer electrolyte membrane (PEM) 3 shown in
While a preferred embodiment of the MEA of the present invention (and the catalyst layer of the present invention, the gas diffusion electrode of the present invention) is described above, the MEA of the present invention is not limited to the configuration of the MEA 10 shown in
For example, the MEA of the present invention may have the configuration of the MEA 11 shown in
Next, a preferred embodiment of the membrane-electrode assembly (CCM: Catalyst Coated Membrane) of the present invention will be described.
While a preferred embodiment of the CCM of the present invention has been described above, the CCM of the present invention is not limited to the configuration of the CCM 12 shown in
For example, the CCM of the present invention may have a configuration of the CCM 13 shown in
Next, a preferred embodiment of the gas diffusion electrode (GDE) of the present invention will be described.
While a preferred embodiment of the GDE of the present invention has been described above, the GDE of the present invention is not limited to the configuration of the GDE 1B shown in
For example, the GDE of the present invention may have the composition of GDE 1C shown in
Next, a preferred embodiment of the composition for forming catalyst layer of the present invention will be described.
A composition for forming catalyst layer of the present embodiment includes the catalyst for electrode 20, a polymer electrolyte, and a main component, and has a mass ratio N/C of mass N of polymer electrolyte to mass C of support 22 of the catalyst for electrode 20 of 0.5 to 1.2, more preferably 0.7 to 1.0.
Here, the composition of the liquid including the polymer electrolyte is not particularly limited. For example, a liquid including a polymer electrolyte may contain a polymer electrolyte having hydrogen ion conductivity described above, water, and an alcohol.
The composition ratio of the catalyst for electrode 20, the polymer electrolyte, and other components (water, alcohol, and the like) included in the composition for forming catalyst layer is appropriately set so that the dispersion state of the catalyst for electrode 20 in the obtained catalyst layer becomes good and the power generation performance of the MEA 10 including the catalyst layer can be improved.
The composition for forming catalyst layer can be prepared by mixing a liquid including the catalyst for electrode 20 and the polymer electrolyte and stirring the mixture. From the viewpoint of adjusting applicability, a polyhydric alcohol such as glycerin and/or water may be contained. When the liquid including the catalyst for electrode 20, the polymer electrolyte is mixed, a pulverizing and mixing machine such as a ball mill, an ultrasonic disperser and the like can be used.
At least one of the catalyst layer 1c of the cathode 1 and the catalyst layer 2c of the anode 2 shown in
Next, an example of a method of producing gas diffusion electrode of the present invention will be described. It is sufficient that the gas diffusion electrode is formed so as to include the catalyst layer of the present invention, and a known method can be employed for the producing method. It can be more reliably produced by using the composition for forming catalyst layer of the present invention.
For example, it may be produced by coating a composition for forming catalyst layer on a gas diffusion layer (or a water repellent layer of a laminate in which a water repellent layer is formed on a gas diffusion layer) and drying the composition.
The fuel cell stack 30 illustrated in
The present invention is further illustrated by the following examples, which are not intended to limit the present invention.
[Pt catalyst particle-supported carbon catalyst “Pt/C catalyst” powder]
Powder of Pt/C catalyst powder in which catalyst particles made of Pt are supported on the following support {Pt loading ratio 48.0 wt %, trade name “SA50BM-A207”, manufactured by N.E. CHEMCAT)} was prepared.
The powder of this Pt/C catalyst (hereinafter, referred to as “Pt/C catalyst A” if necessary) was prepared in the following procedures.
A dispersion liquid, in which a trial sample product “CNovel A” manufactured by Toyo Tanso Co., Ltd. as the porous carbon support (BET specific surface area: 1200 m2/g) was dispersed in the aqueous solution adjusted to pH=2 to 5 (prepared by adding a pH adjuster to ultrapure water), was held at 90 to 99° C. for about 0.5 hours while stirring (although a not boiled state was retained).
Note that “ultrapure water” used in this first step (support pretreatment step) was a water having a specific resistance R (reciprocal of electric conductivity measured by a JIS standard test method (JIS K0552)) represented by the following equation (4) of 3.0 MΩ·cm or more. In addition, ultrapure water had a water quality equivalent to or higher than that of A3 specified in JISK0557 Water for Testing Water and Wastewater.
This ultrapure water was produced using an ultrapure water producing apparatus “Milli-Q Series” (manufactured by Merck Co., Ltd.) and “Elix UV Series” (manufactured by Nippon Millipore Co., Ltd.).
R=1/ρ (4)
In the above general equation (4), R represents a specific resistance, and p represents an electric conductivity measured by a JIS standard test method (JIS K0552).
After preparing a mixed solution by adding an aqueous solution of a water-soluble Pt salt (N. E. CHEMCAT, trade name “A-salt” (concentration of Fe component: 8 ppm or less)) in ultrapure water to the dispersion obtained through the first step, the pH was adjusted to 7 to 12, and the mixture was stirred while maintaining a predetermined temperature of 50° C. or higher for a predetermined time.
By adding an aqueous solution in which an acidic water-soluble reducing agent is dissolved to the liquid obtained through the second step, the Pt ions in the mixed liquid were reduced to obtain the Pt catalyst particle-supported carbon “Pt/C” powder.
By using a filter paper, the solid component and the liquid component in the liquid obtained through the “third step” were separated. Next, the solid content (a mixture of the Pt/C catalyst and other impurities) remaining on the filter paper was washed with the above-mentioned pure water and pure warm water. First, washing with pure water was performed. This washing was repeated until the electric conductivity of the filtrate after washing became less than 20 μS/cm. Next, washing with pure warm water was performed. This washing was repeated until the electric conductivity of the filtrate after washing became less than 10 μS/cm.
The solid component (mixture of Pt/C catalyst and water) on the filter paper obtained through the “fourth step” was air-dried in the air in this state. After this air drying, the solid component on the filter paper was transferred to a magnetic dish and dried in an electric dryer at a predetermined temperature of 60° C. or higher for a predetermined time.
The solid component (Pt/C catalyst) obtained in the “fifth step” was crushed by using a mixer to obtain a powder of Pt/C catalyst A.
For this Pt/C catalyst A, the Pt loading ratio (wt %) was determined by the following methods.
The Pt/C catalyst A was immersed in aqua regia to dissolve the metal. The carbon as the insoluble component was then removed from the aqua regia. Next, the aqua regia from which the carbon was removed was analyzed by ICP.
As a result of the ICP analysis, this Pt/C catalyst A had the Pt loading ratio of 48.0 wt %.
In order to observe the three-dimensional structure of this Pt/C catalyst A of Example 1, the electron tomography measurement was carried out by using the “USAL-KM3D analysis method” with the STEM (scanning transmission electron microscope) at UBE Scientific Analysis Center Co., Ltd.
The electron tomography measurement with the STEM (scanning transmission electron microscope) was carried out according to the sample to be measured preparation method, the conditions and their analytical procedures, the conditions of (A) to (C) and (D) to (G), described above. More detailed information is described hereinbelow.
With respect to the Pt/C catalyst A, by image analysis of a three-dimensional reconstructed image (3D-STEM image) obtained by electron beam tomography (electron tomography) measurement using an STEM (scanning transmission electron microscopy), the Pt catalyst particles (hereinafter, inner particles) present inside the carbon support and the Pt catalyst particles (hereinafter, outer particles) present on the surface portion of the carbon support were separated, and the particle size distribution of the Pt catalyst in each region was calculated.
A three-dimensional reconstructed image (3D-STEM image) of the Pt/C catalyst A is shown in
Among the catalyst particles obtained by image analysis, the particle size analysis results of the catalyst particles supported inside the nanopores of the support and the catalyst particles supported outside the nanopores (particle size distribution indicated by the equivalent sphere diameter) is shown in
The 3D-STEM image was obtained by reconstructing a plurality of two-dimensional STEM images obtained by stepwise tilting the sample stage under the above measuring conditions.
Further, the image analysis (particle size analysis) of three-dimensional reconstructed image (3D-STEM image) was carried out by the following procedures. The regions of the catalytic particles were first selected from the three-dimensional reconstructed images, and the respective catalytic particles were labeled (not shown). Next, the volume of the labeled Pt catalyst particles was obtained, the diameter of a sphere having the same volume as this volume (the equivalent diameter of the sphere) was calculated, and the particle size distribution (
Here, the sphere equivalent diameter was calculated by rounding up the value below the decimal point (value below 1 nm) using the unit of nm.
For this Pt/C catalyst A, the ratio of the catalyst particles supported inside the nanopores of the support and the ratio of the catalyst particles supported outside the nanopores of the support were determined. The values of D10, D20, D1, D2, N1, and N2 were also obtained. The results are shown in Table 2 and Table 3.
Furthermore, the mean value of the particle size of the catalyst particles of the Pt/C catalyst A measured from the STEM image was 3.1 nm (the average value of the particle size of the catalyst particles inside the nanopores: 3.1 nm, the average value of the particle size of the catalyst particles outside the nanopores: 3.2 nm).
The powder {Pt loading ratio: 48.0 wt %, trade name “SA50BM-B237”, manufactured by N.E.CHEMCAT} of the Pt/C catalyst used for the cathode of the MEA of Example 2 (hereinafter, referred to as “Pt/C catalyst B” if necessary) was prepared under the same conditions and procedures as the Pt/C catalyst A used for the cathode of the MEA of Example 1, except that a trial sample product “CNovel B” manufactured by Toyo Tanso Co., Ltd. as the porous carbon support (BET specific surface area: 800 m2/g)” was used as a porous carbon support.
In order to observe the three-dimensional structure of this Pt/C catalyst B of Example 2, in the same method and conditions as the Pt/C catalyst of Example 1, the electron tomography measurement was carried out by using the “USAL-KM3D analysis method” with the STEM (scanning transmission electron microscope) at UBE Scientific Analysis Center Co., Ltd.
For this catalyst for electrode (Pt/C catalyst B), the ratio of the catalyst particles supported inside the nanopores of the support and the ratio of the catalyst particles supported outside the nanopores of the support were determined. The values of D10, D20, D1, D2, N1, and N2 were also obtained. The results are shown in Table 2 and Table 3.
Furthermore, the mean value of the particle size of the catalyst particle of the catalyst for electrode (Pt/C catalyst B) measured from the STEM image was 3.3 nm (the average value of the particle size of the catalyst particles inside the nanopores: 3.2 nm, the average value of the particle size of the catalyst particles outside the nanopores: 3.7 nm).
As a Pt/C catalyst, a Pt/C catalyst manufactured by N.E. CHEMCAT with a Pt loading ratio of 50 wt % (trade name: “SA50BK”) was prepared. As the support of this Pt/C catalyst, a commercially available porous carbon support (manufactured by Lion Co., Ltd., trade name “Carbon ECP” (registered trademark) (Ketjen Black EC300J), specific surface area of 750 to 800 m2/g) was used.
In order to observe the three-dimensional structure of this Pt/C catalyst of Comparative Example 1, in the same method and conditions as the Pt/C catalyst of Example 1,
The electron tomography measurement was carried out by using the “USAL-KM3D analysis method” with the STEM (scanning transmission electron microscope) at UBE Scientific Analysis Center Co., Ltd.
For this Pt/C catalyst, the ratio of the catalyst particles supported inside the nanopores of the support and the ratio of the catalyst particles supported outside the nanopores of the support were determined. The values of D10, D20, D1, D2, N1, and N2 were also obtained. The results are shown in Table 2 and Table 3.
Furthermore, the mean value of the particle size of the catalyst particles of the Pt/C catalyst A measured from the STEM image was 3.1 nm (the average value of the particle size of the catalyst particles inside the nanopores: 3.1 nm, the average value of the particle size of the catalyst particles outside the nanopores: 3.2 nm).
The powder (Pt loading ratio: 48.0 wt %, trade name “SA50BM-B207”, manufactured by N.E.CHEMCAT) of the Pt/C catalyst used for the cathode of the MEA of Example 2 (hereinafter, referred to as “Pt/C catalyst C”, if necessary) was prepared under the same conditions and procedures as the Pt/C catalyst A used for the cathode of the MEA of Example 1, except that a trial sample product “CNovel C” manufactured by Toyo Tanso Co., Ltd. as the porous carbon support (BET specific surface area: 800 m2/g)” was used as a porous carbon support.
In order to observe the three-dimensional structure of this Pt/C catalyst C of Comparative Example 2, in the same method and conditions as the Pt/C catalyst of Example 1, the electron tomography measurement was carried out by using the “USAL-KM3D analysis method” with the STEM (scanning transmission electron microscope) at UBE Scientific Analysis Center Co., Ltd.
Though with respect to this catalyst for electrode (Pt/C catalyst C) of Comparative Example 2, the information of the measurement of electron beam tomography by using the STEM (scanning transmission electron microscope) and the analysis results thereof corresponding to those shown in
For this catalyst for electrode (Pt/C catalyst C) of Comparative Example 2, the ratio of the catalyst particles supported inside the nanopores of the support and the ratio of the catalyst particles supported outside the nanopores of the support were determined. The values of D10, D20, D1, D2, N1, and N2 were also obtained. The results are shown in Table 2 and Table 3.
Furthermore, the mean value of the particle size of the catalyst particles of the catalyst for electrode (Pt/C catalyst C) measured from the STEM image was 3.2 nm (the average value of the particle size of the catalyst particles inside the nanopores: 2.9 nm, the average value of the particle size of the catalyst particles outside the nanopores: 3.5 nm).
With respect to the catalyst for electrodes of Example 1, Example 2 and Comparative Example 2, in order to confirm “whether or not the nanopore is formed so as to have the shape of the interconnected pore according to the present invention”, which is the aforementioned condition (8), the study by using the three-dimensional reconstructed image of STEM was performed. Further, the porosity of each catalyst was determined by using the three-dimensional reconstructed image of STEM.
The results are shown in
As shown in Fid. 24(c) and
Furthermore, as shown in
Furthermore, as shown in
Further, as shown in
Furthermore, as shown in
Further, as shown in
As shown in
Furthermore, as shown in
On the other hand, as shown in
The same Pt/C catalyst as the Pt/C catalyst used for the cathode of the MEA of Comparative Example 1 was used as the P/C catalyst used in the anodes of the MEA of Example 1 and Example 2, Comparative Example 1 and Comparative Example 2.
In the following procedures, an MEA with the same configuration as the MEA 10 shown in
Cathode GDL
Carbon paper (trade name “TGP-H-60” manufactured by Toray Co., Ltd) was prepared as the GDL.
Ink for forming cathode MPL
Into a ball mill container made of Teflon (registered trademark) in which balls made of Teflon (registered trademark) were added, 1.5 g of carbon powder (trade name “Denkablack” manufactured by Electrochemical Industry Co., Ltd.), 1.1 g of ion-exchanged water, and 6.0 g of a surfactant (trade name “Triton” (35 wt % water solution) manufactured by Dow chemical Co., Ltd.) were charged and mixed.
Next, 1.75 g of polytetrafluoroethylene (PTFE) dispersion (trade name “31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) was put into the ball mill container and mixed. Thus, an ink for forming cathode MPL was produced.
Cathode MPL
On one side of the GDL, an ink for forming cathode MPL was applied using a barcoater to form a coating film. Thereafter, the coating film was sufficiently dried in a dryer, and further subjected to a heat and pressure bonding treatment to prepare a laminate in which the MPL was formed on the GDL.
Ink for forming cathode catalyst layer
Into a ball mill container made of Teflon (registered trademark) containing a ball made of Teflon (registered trademark), the above-mentioned Pt/C catalyst A, ion-exchanged water, a 10 wt % Nafion aqueous dispersion (trade name “DE1021CS” manufactured by DuPont Co., Ltd.) and glycerin were charged and mixed to prepare an ink for forming cathode catalyst layer. Note that this ink was adjusted to have a N/C=0.7. Further, the core-shell catalyst A was adjusted to have carbon: ion-exchanged water: glycerin=1: 10: 0.8 (mass ratio).
Cathode Catalyst layer (CL)
An ink for forming cathode catalyst layer described above was applied to the surface of the MPL of a laminate in which MPL was formed on MPL on the GDL described above by a bar coating method to form a coating film. This coating film was dried at room temperature for 30 minutes, and then dried at 60° C. for 1.0 hours to obtain a catalyst layer. In this way, a cathode which is a gas diffusion electrode was prepared. Note that Pt supporting on catalyst layer of the cathode was set to be a numerical value shown in Table 1.
Anode GDL
As the GDL, carbon paper identical to that of the cathode was prepared.
Ink for forming cathode MPL
Into a ball mill container made of Teflon (registered trademark) in which balls made of Teflon (registered trademark) were added, 1.5 g of carbon powder (trade name “Denka black” manufactured by Electrochemical Industry Co., Ltd.), 1.0 g of ion-exchanged water, and 6.0 g of a surfactant (trade name “Triton” (35 wt % water solution) manufactured by Dow chemical Co., Ltd.) were charged and mixed.
Next, 2.5 g of a polytetrafluoroethylene (PTFE) dispersion (trade name “31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) was charged into the ball mill container and mixed. Thus, an ink for forming anode MPL was produced.
Anode MPL
The ink for forming anode MPL was applied to one side of the GDL using a barcoater to form a coating film. Thereafter, the coating film was sufficiently dried in a dryer, and further subjected to a heat and pressure bonding treatment to produce a laminate in which MPL was formed on the GDL.
Ink for forming anode catalyst layer
Into a ball mill container made of Teflon (registered trademark) in which balls made of Teflon (registered trademark) were added, SA50BK (Pt laoding ratio 50 wt %), ion-exchange water, 5 wt % Nafion alcohol dispersion (trade name “Nafion” 5 wt % dispersion, product number 274704, manufactured by SIGMA-ALDRICH's) and glycerin were charged and mixed to prepare an ink for forming anode catalyst layer. Note that this ink was adjusted to have N/C=1.2. Further, SA50BK was adjusted to have carbon: ion-exchanged water: glycerin=1: 6: 4 (mass ratio).
Anode Catalyst layer (CL)
An ink for forming anode catalyst layer described above was applied to the surface of an MPL of a laminate in which MPL was formed on MPL on the GDL described above by a bar coating method to form a coating film. This coating film was dried at room temperature for 30 minutes, and then dried at 60° C. for 1.0 hours to obtain a catalyst layer. In this way, an anode which is a gas diffusion electrode was produced. Note that the Pt supporting amount of the catalyst layer of the anode was set as a 0.3 mg/cm2.
A polymer electrolyte membrane (trade name “Nafion NR212” manufactured by DuPont Co., Ltd.) was prepared. Alaminate in which this polymer electrolyte membrane was arranged between the cathode and the anode was produced, and heated and pressed by a hot pressing machine to produce an MEA. Incidentally, the hot pressing was carried out with the conditions of 140° C. at 5 KN for 5 minutes and, further, 140° C. at 25 KN for 3 minutes.
Each MEA was prepared under the same conditions and procedures as in Example 1, except that the following conditions were changed for the catalyst layer of the cathode.
That is, in preparing the ink for forming the catalyst layer of the cathode,
Each MEA was produced under the same conditions and procedures as in Example 1, except that the following conditions were changed with respect to the cathode catalyst layer.
That is, in the preparation of the ink for forming cathode catalyst layer,
Each MEA was prepared under the same conditions and procedures as in Example 1, except that the following conditions were changed for the catalyst layer of the cathode.
That is, in preparing the ink for forming the catalyst layer of the cathode,
The cell performance of the MEA of Example 1, Example 2, Comparative Example 1 and Comparative Example 2 was carried out by the following cell performance evaluation method.
The MEA of Example 1, Example 2, Comparative Example 1 and Comparative Example 2 were installed in a fuel cell unit cell evaluation device.
Next, the power generation reaction in the MEA was allowed to proceed under the following conditions.
The temperature of the unit cell (MEA) was set to 80° C. The anode was supplied with pure hydrogen humidified with saturated water vapor of 1.0 atm by adjusting the flow rate so that the utilization rate was 70%.
Further, the cathode was supplied with pure oxygen humidified with saturated water vapor of 1.0 atm at 80° C. by adjusting the flow rate so that the utilization rate was 50%.
Evaluation of the unit cells (MEA) was performed by controlling the current by an electronic supporting device attached to the fuel cell unit cell evaluation device, and the current-voltage curves obtained by scanning the current values from 0 to 1.0 A/cm2 were acquired as data.
The X-axis (current density) from the data of the current-voltage curves was plotted as a logarithmic scale to obtain a graph (not shown), and a current density value at a voltage 850 mV (current value per unit area of the electrode) was obtained.
By dividing the current density value thus obtained by the platinum weight per unit area of the cathode, it was calculated as the activity per unit weight (Mass.Act.) for platinum contained in the cathode, and was used as an indicator of the oxygen reduction ability of the catalyst contained in the cathode. The results are shown in Table 1.
In Table 1, a result of comparing Mass.Act. obtained in the other examples as a relative value (relative ratio) using Mass.Act. obtained in Comparative Example 1 as a reference (1.0) is shown.
From the results shown in Table 1 to Table 3, it was clarified that the MEA of Example 1 and Example 2 has a high Pt mass activity compared with the MEA of Comparative Example 1 and Comparative Example 2.
In the above, in the present examples and comparative examples, there have been studied the embodiments where the catalyst particle is the catalyst particle of the simplest Pt. However, the characteristics of the catalyst for electrode of the present invention is that, when the microstructure is observed by using a three-dimensional reconstructed image of STEM, the microstructure has the stereoscopic structure which satisfies the condition (a) that the ratio of the catalyst particles supported inside the nanopore is 50% or more (condition relating the supporting position of the catalyst particle which composes the catalyst for electrode) and the condition (8) that the nanopores are formed to have the shape of the interconnected pores described above (condition of microstructure of the nanopore of the support which composes the catalyst for electrode).
Therefore, it is clear that similar results can be obtained by changing the chemical constituents of the catalyst particles. That is, as long as the stereoscopic structure has the characteristics of the present invention, when a Pt alloy particle containing Pt or core-shell particle having a Pt shell layer is used as the catalyst particle in the same manner as the particle made of Pt, it is clear that the excellent Pt mass activity similar to that of the aforementioned examples can be realized.
The catalyst for electrode of the present invention exhibits excellent catalytic activity. In addition, the GDE, CCM, MEA, and fuel cell stack including the catalyst layer of the present invention exhibit excellent cell properties that can contribute to cost reduction of PEFC.
Therefore, the present invention can be applied not only to the electrical equipment industry such as a fuel cell, a fuel cell vehicle and a portable mobile but also to ENE-FARM, a cogeneration system and the like and, therefore, contributes to the development of energy industry and environmental technology.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-163683 | Sep 2020 | JP | national |
| 2020-173467 | Oct 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/035650 | 9/28/2021 | WO |
