Patent Application
20250101610
This application claims the benefit of Japanese Application No. 2023-155638, filed on Sep. 21, 2023, the disclosure of which is incorporated by reference herein.
The present invention relates to an electrode structure.
In a solid polymer water electrolyzer conventionally known, hydrogen (H2) is produced by electrolysis of water (H2O). The solid polymer water electrolyzer has a cell stack with cells and separators stacked alternately. Each of the cells includes an electrolyte membrane, and a catalyst layer formed on each of both sides of the electrolyte membrane.
During use of the solid polymer water electrolyzer, a voltage is applied between an anode-side catalyst layer and a cathode-side catalyst layer and water is supplied to the anode-side catalyst layer. This causes electrochemical reactions as follows in the anode-side catalyst layer and the cathode-side catalyst layer. As a result, hydrogen is output from the cathode-side catalyst layer.
2H2O→4H++O2+4e− (anode side)
2H++2e−→H2 (cathode side)
The conventional solid polymer water electrolyzer is described in Japanese Patent Application Laid-Open No. 2022-023996, for example.
In the conventional solid polymer water electrolyzer, the catalyst layer is entirely used as an electrode. However, if a formation range of the catalyst layer relative to the electrolyte membrane is determined with low accuracy, using the catalyst layer entirely as an electrode causes fluctuation of an effective region to practically function as an electrode. The same problem might occur not only in the cell of the solid polymer water electrolyzer but also in a cell of a solid polymer fuel cell.
The present invention is intended to provide a technique that achieves reduction in fluctuation of an effective region to function as an electrode even if a formation range of a catalyst layer is determined with low accuracy.
The present invention is intended for an electrode structure comprising: an electrolyte membrane; a first catalyst layer formed on one of surfaces of the electrolyte membrane; a first gas diffusion layer stacked on a surface of the first catalyst layer; a second catalyst layer formed on the other surface of the electrolyte membrane; a porous transport layer or a second gas diffusion layer stacked on a surface of the second catalyst layer; and a subgasket film attached to the electrolyte membrane in a periphery of at least one of the first catalyst layer and the second catalyst layer. A part of the subgasket film extends more inwardly than an outer edge of the first gas diffusion layer, an outer edge of the porous transport layer or the second gas diffusion layer, an outer edge of the first catalyst layer, and an outer edge of the second catalyst layer.
According to the present invention, an effective region of the first catalyst layer and the second catalyst layer is defined using the subgasket film. Thus, even if formation ranges of the first catalyst layer and the second catalyst layer are determined with low accuracy, it is still possible to reduce fluctuation of the effective region to function as an electrode.
In a state viewed in a stacking direction, the first catalyst layer and the second catalyst layer may have an overlapping region where the first catalyst layer and the second catalyst layer overlap each other and the outer edge of the first catalyst layer and the outer edge of the second catalyst layer may be at positions differing from each other, and the part of the subgasket film may be arranged at a more inward position than an outer edge of the overlapping region.
Thus, irrespective of a difference between the positions of the first catalyst layer and the second catalyst layer, it is possible to define the effective region of the first catalyst layer and the second catalyst layer using the subgasket film.
The subgasket film may have a rectangular opening, and the opening may be arranged at a more inward position than the outer edge of the first gas diffusion layer, the outer edge of the porous transport layer or the second gas diffusion layer, the outer edge of the first catalyst layer, and the outer edge of the second catalyst layer.
Thus, it is possible to define the rectangular effective region of the first catalyst layer and the second catalyst layer with high accuracy using the subgasket film.
The subgasket film may include: a first subgasket film bonded to the one surface of the electrolyte membrane; and a second subgasket film bonded to the other surface of the electrolyte membrane, and the opening of one of the first subgasket film and the second subgasket film may be arranged at a more inward position than the opening of the other of the first subgasket film and the second subgasket film, the outer edge of the first gas diffusion layer, the outer edge of the porous transport layer or the second gas diffusion layer, the outer edge of the first catalyst layer, and the outer edge of the second catalyst layer.
The first catalyst layer and the second catalyst layer may be coating films.
These and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
A preferred embodiment of the present invention will be described below by referring to the drawings.
A stacked body composed of the electrolyte membrane 51, the first catalyst layer 61, the first gas diffusion layer 62, the second catalyst layer 71, and the porous transport layer 72 is called a membrane-electrode-assembly (EMA). A stacked body composed of the electrolyte membrane 51, the first catalyst layer 61, and the second catalyst layer 71 is called a catalyst-coated membrane (CCM).
The electrolyte membrane 51 is a membrane having ion conductivity (ion-exchange membrane). The electrolyte membrane 51 of the present preferred embodiment is a proton-exchange membrane that conducts hydrogen ions (H+). A fluorine-based or hydrocarbon-based polymer electrolyte membrane is used as the electrolyte membrane 51. More specifically, a polymer electrolyte membrane containing perfluorocarbon sulfonic acid is used as the electrolyte membrane 51, for example. The electrolyte membrane 51 has a thickness from 5 to 200 μm, for example.
The first catalyst layer 61 is a catalyst layer that causes electrochemical reaction on a cathode side. The first catalyst layer 61 is formed on a cathode-side surface of the electrolyte membrane 51. The first catalyst layer 61 contains a large number of carbon particles on which catalyst particles are supported. The catalyst particles are particles of platinum, for example. Alternatively, the catalyst particles may be prepared by mixing particles of a tiny amount of ruthenium or cobalt into particles of platinum. During use of the water electrolyzer 1, hydrogen ions (H+) and electrons (e−) are supplied to the first catalyst layer 61. Then, the power supply 40 applies a voltage between the first catalyst layer 61 and the second catalyst layer 71. By doing so, by the actions of the applied voltage and the catalyst particles, a reduction reaction is caused in the first catalyst layer 61 to generate hydrogen gas (H2) from the hydrogen ions and the electrons.
The first gas diffusion layer 62 is a layer for transporting electrons from the separator 20 to the first catalyst layer 61 and for transporting hydrogen generated in the first catalyst layer 61 to the separator 20. The first gas diffusion layer 62 is stacked on an external surface of the first catalyst layer 61 (a surface on the opposite side to the electrolyte membrane 51). The first catalyst layer 61 is interposed between the electrolyte membrane 51 and the first gas diffusion layer 62. The first gas diffusion layer 62 is made of a material having electrical conductivity and porosity. The first gas diffusion layer 62 is formed using a porous base material (carbon paper) made of carbon, for example.
The second catalyst layer 71 is a catalyst layer that causes electrochemical reaction on an anode side. The second catalyst layer 71 is formed on an anode-side surface of the electrolyte membrane 51 (a surface on the opposite side to the first catalyst layer 61). The second catalyst layer 71 contains a large number of catalyst particles. The catalyst particles are particles of iridium oxide (IrOx), platinum (Pt), an alloy of iridium (Ir) and ruthenium (Ru), or an alloy of iridium (Ir) and titanium dioxide (TiO2), for example. During use of the water electrolyzer 1, water (H2O) is supplied to the second catalyst layer 71. Then, the power supply 40 applies a voltage between the first catalyst layer 61 and the second catalyst layer 71. By doing so, by the actions of the applied voltage and the catalyst particles, the water is electrolyzed into hydrogen ions (H+), oxygen (O2), and electrons (e−) in the second catalyst layer 71.
The porous transport layer 72 is a layer for supplying water uniformly to the second catalyst layer 71 and for transporting oxygen and electrons generated in the second catalyst layer 71 to the separator 20. The porous transport layer 72 is stacked on an external surface of the second catalyst layer 71 (a surface on the opposite side to the electrolyte membrane 51). The second catalyst layer 71 is interposed between the electrolyte membrane 51 and the porous transport layer 72. The porous transport layer 72 is made of a material having electrical conductivity and porosity. The porous transport layer 72 is formed using a porous base material made of metal such as titanium or stainless steel, for example.
The separator 20 is a layer for moving electrons between the cells 10 next to each other and for forming a passage for water, oxygen, and hydrogen. The separator 20 is interposed between the first gas diffusion layer 62 of one cell 10 and the porous transport layer 72 of the cell 10 next to the one cell 10. The separator 20 is composed of a metal plate 21 having electrical conductivity and impermeable to gas and liquid. The metal plate 21 has a cathode surface 22 contacting the first gas diffusion layer 62, and an anode surface 23 contacting the porous transport layer 72.
The metal plate 21 has a plurality of cathode grooves 24 formed at the cathode surface 22. Hydrogen generated in the first catalyst layer 61 passes through the first gas diffusion layer 62 and is then output to the outside through the cathode grooves 24 of the separator 20.
The metal plate 21 has a plurality of anode grooves 25 formed at the anode surface 23. Water is supplied to the porous transport layer 72 through the anode grooves 25 of the separator 20. Oxygen generated in the second catalyst layer 71 passes through the porous transport layer 72 and is then output to the outside through the anode grooves 25 of the separator 20.
The power supply 40 is a device that applies a voltage to the cell stack 30. As shown in
During use of the water electrolyzer 1, water is supplied from the anode grooves 25 of the separator 20 to the second catalyst layer 71 through the porous transport layer 72. Then, by the actions of a voltage applied from the power supply 40 and the catalyst particles in the second catalyst layer 71, the water is decomposed into hydrogen ions, oxygen, and electrons. The hydrogen ions propagate through the electrolyte membrane 51 into the first catalyst layer 61. The oxygen passes through the porous transport layer 72 and the anode grooves 25 of the separator 20 and is then output to the outside. The electrons pass through the porous transport layer 72 and the separator 20 and then flow into the adjoining cell 10. In the adjoining cell 10, these electrons pass through the first gas diffusion layer 62 to reach the first catalyst layer 61. Then, the hydrogen ions and the electrons are combined with each other to generate hydrogen in the first catalyst layer 61. The generated hydrogen passes through the first gas diffusion layer 62 and the cathode grooves 24 of the separator 20 and is then output to the outside. In this way, hydrogen is produced.
A subgasket film 81 and a subgasket film 82 are attached for handling in a periphery of the cell 10. In the following, a structure composed of the cell 10 and the subgasket films 81 and 82 will be called an “electrode structure 80.”
Each of the electrolyte membrane 51, the first catalyst layer 61, the first gas diffusion layer 62, the second catalyst layer 71, and the porous transport layer 72 has a rectangular shape in a state viewed in the stacking direction. As shown in
The first catalyst layer 61 is a coating film formed by coating one of surfaces of the electrolyte membrane 51 with catalyst ink. The second catalyst layer 71 is a coating film formed by coating the other surface of the electrolyte membrane 51 with catalyst ink. During coating with the catalyst ink, a coating range is controlled in such a manner that the first catalyst layer 61 and the second catalyst layer 71 are formed at the substantially same position when viewed in the stacking direction. Thus, the first catalyst layer 61 and the second catalyst layer 71 have an overlapping region 90 where the first catalyst layer 61 and the second catalyst layer 71 overlap each other in a state viewed in the stacking direction. Meanwhile, it is extremely difficult to make an exact match between ranges of coating of the both surfaces of the electrolyte membrane 51 with the catalyst ink. This causes a slight difference between the position of the outer edge of the first catalyst layer 61 and the position of the outer edge of the second catalyst layer 71, as shown in
The first gas diffusion layer 62 is bonded to the surface of the first catalyst layer 61 on the opposite side to the electrolyte membrane 51. The first gas diffusion layer 62 covers the first catalyst layer 61. An outer edge of the first gas diffusion layer 62 is arranged at a more outward position than the outer edge of the first catalyst layer 61. The porous transport layer 72 is bonded to the surface of the second catalyst layer 71 on the opposite side to the electrolyte membrane 51. The porous transport layer 72 covers the second catalyst layer 71. An outer edge of the porous transport layer 72 is arranged at a more outward position than the outer edge of the second catalyst layer 71.
The first subgasket film 81 and the second subgasket film 82 are films for grasping the electrode structure 80 and provided at the time of manufacture of the cell stack 30. The first subgasket film 81 and the second subgasket film 82 are formed using films having higher mechanical strength than the electrolyte membrane 51. More specifically, the first subgasket film 81 and the second subgasket film 82 are made of a material such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), or polystyrene (PS), for example.
The first subgasket film 81 is bonded to the cathode-side surface of the electrolyte membrane 51 in a periphery of the first catalyst layer 61. In a state viewed in the stacking direction, the first subgasket film 81 has a rectangular shape. As shown in
The first subgasket film 81 has a first opening 810 formed at a substantially central part of the first subgasket film 81. The first opening 810 is a hole penetrating the first subgasket film 81 in the stacking direction. In a state viewed in the stacking direction, the first opening 810 has a rectangular shape. In a state viewed in the stacking direction, at least a part of the first catalyst layer 61 is located in the first opening 810.
The second subgasket film 82 is bonded to the anode-side surface of the electrolyte membrane 51 in a periphery of the second catalyst layer 71. In a state viewed in the stacking direction, the second subgasket film 82 has a rectangular shape. As shown in
The second subgasket film 82 has a second opening 820 formed at a substantially central part of the second subgasket film 82. The second opening 820 is a hole penetrating the second subgasket film 82 in the stacking direction. In a state viewed in the stacking direction, the second opening 820 has a rectangular shape. In a state viewed in the stacking direction, at least a part of the second catalyst layer 71 is located in the second opening 820.
The above-described electrode structure 80 has a region where the first catalyst layer 61, the first gas diffusion layer 62, the second catalyst layer 71, and the porous transport layer 72 overlap each other in the stacking direction and are not covered with the first subgasket film 81 and the second subgasket film 82, and this region is an effective region A to practically function as an electrode.
In the electrode structure 80 of the present preferred embodiment, a part of the second subgasket film 82 extends more inwardly than the outer edge of the first gas diffusion layer 62, the outer edge of the porous transport layer 72, the outer edge of the first catalyst layer 61, and the outer edge of the second catalyst layer 71. This part of the second subgasket film 82 is interposed between the second catalyst layer 71 and the porous transport layer 72. Thus, in the present preferred embodiment, a region more inward than this part of the second subgasket film 82 is the effective region A to practically function as an electrode. By doing so, even if formation ranges of the first catalyst layer 61 and the second catalyst layer 71 are determined with low accuracy, it still becomes possible to reduce fluctuation of the effective region A to function as an electrode.
In particular, if the first catalyst layer 61 and the second catalyst layer 71 are coating films, a slight difference is caused between the position of the outer edge of the first catalyst layer 61 and the position of the outer edge of the second catalyst layer 71, as described above. In this regard, in the present preferred embodiment, the above-described part of the second subgasket film 82 extends more inwardly than an outer edge of the overlapping region 90 where the first catalyst layer 61 and the second catalyst layer 71 overlap each other. Thus, irrespective of a difference between the positions of the first catalyst layer 61 and the second catalyst layer 71, it is possible to define the effective region A of the first catalyst layer 61 and the second catalyst layer 71 using the second subgasket film 82.
In the present preferred embodiment, the rectangular second opening 820 of the second subgasket film 82 is arranged at a more inward position than the rectangular first opening 810 of the first subgasket film 81. The second opening 820 is arranged at a more inward position than the outer edge of the first gas diffusion layer 62, the outer edge of the porous transport layer 72, the outer edge of the first catalyst layer 61, and the outer edge of the second catalyst layer 71. Thus, it is possible to define the rectangular effective region A of the first catalyst layer 61 and the second catalyst layer 71 with high accuracy using the second subgasket film 82.
In the present preferred embodiment, the second opening 820 of the second subgasket film 82 is arranged at a more inward position than the first opening 810 of the first subgasket film 81. Thus, it is possible to define the effective region A of the first catalyst layer 61 and the second catalyst layer 71 using only the second subgasket film 82 of the two subgasket films 81 and 82 while the first subgasket film 81 is not involved in the definition of the effective region A. This makes it possible to define the effective region A with higher accuracy while suppressing influence caused by manufacturing error between the two subgasket films 81 and 82.
While one preferred embodiment of the present invention has been described above, the present invention is not limited to the above-described preferred embodiment. The following describes various modifications by mainly showing differences from the above-described preferred embodiment.
In the above-described preferred embodiment, all the four sides of the rectangular second opening 820 of the second subgasket film 82 are arranged at more inward positions than the outer edge of the first gas diffusion layer 62, the outer edge of the porous transport layer 72, the outer edge of the first catalyst layer 61, and the outer edge of the second catalyst layer 71. In another case, only some of the four sides of the second opening 820 may be arranged at more inward positions than the outer edge of the first gas diffusion layer 62, the outer edge of the porous transport layer 72, the outer edge of the first catalyst layer 61, and the outer edge of the second catalyst layer 71. For example, of the two long sides and the two short sides of the second opening 820 shown in
In the above-described preferred embodiment, a part of the second subgasket film 82 extends more inwardly than the outer edge of the first gas diffusion layer 62, the outer edge of the porous transport layer 72, the outer edge of the first catalyst layer 61, and the outer edge of the second catalyst layer 71. Then, this part of the second subgasket film 82 is used for defining the effective region A of the first catalyst layer 61 and the second catalyst layer 71. In another case, a part of the first subgasket film 81 may extend more inwardly than the outer edge of the first gas diffusion layer 62, the outer edge of the porous transport layer 72, the outer edge of the first catalyst layer 61, and the outer edge of the second catalyst layer 71. Then, this part of the first subgasket film 81 may be used for defining the effective region A of the first catalyst layer 61 and the second catalyst layer 71.
Even in this case, it is still possible to define the effective region A of the first catalyst layer 61 and the second catalyst layer 71 by extending a part of the one subgasket film 82 more inwardly than the outer edge of the first gas diffusion layer 62, the outer edge of the porous transport layer 72, the outer edge of the first catalyst layer 61, and the outer edge of the second catalyst layer 71.
The electrode structure 80 discussed in the above-described preferred embodiment uses a proton-exchange membrane as the electrolyte membrane 51. However, the electrode structure of the present invention may use an anion-exchange membrane as an electrolyte membrane.
The electrode structure 80 discussed in the above-described preferred embodiment is used in the water electrolyzer 1. However, a structure comparable to that of the above-described preferred embodiment may be applied to an electrode structure used in a fuel cell. In the case of the electrode structure for a fuel cell, the porous transport layer 72 is replaced with a second gas diffusion layer. The second gas diffusion layer is formed using a porous base material (carbon paper) made of carbon, for example.
A structure comparable to that of the above-described preferred embodiment may be applied to an electrode structure used in a liquid organic hydrogen carrier (LOHC) process by which an aromatic compound such as toluene is hydrogenated to produce an organic hydride (toluene-methylcyclohexane, for example).
Some of the structures shown in the above-described preferred embodiment or modifications may be deleted or other structures may be added within a scope not deviating from the purport of the present invention.
While the invention has been shown and described in detail, the foregoing description is in all aspects illustrative and not restrictive. It is therefore understood that numerous modifications and variations can be devised without departing from the scope of the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2023-155638 | Sep 2023 | JP | national |
