Patent Application
20230047305
This application is based upon and claims the benefit of priority from Japanese Patent Application No. 2021-132001, filed on Aug. 13, 2021; the entire contents of which are incorporated herein by reference.
Embodiments disclosed herein relate to a metal component for electrochemical stack and an electrochemical stack.
One of new energy resources is hydrogen. As a utilization field of hydrogen, fuel cells attract attention which cause hydrogen and oxygen to electrically react with each other to thereby convert chemical energy into electric energy. The fuel cells have high energy utilization efficiency and are being developed as a large-scale distributed power supply, a domestic power supply, and a mobile power supply. Of the fuel cells, a solid oxide fuel cell (SOFC) which obtains electric energy by an electrochemical reaction using an electrolyte composed of a solid oxide attracts attention from the viewpoint of efficiency and so on. In the manufacture of hydrogen, electrolysis reactions of water are known. A solid oxide electrolysis cell (SOEC) employing a high-temperature water vapor electrolysis method of electrolyzing water vapor at high temperature of the electrolysis reactions of water is being researched. The operation principle of the SOEC is an inverse reaction of the SOFC, and an electrolyte composed of a solid oxide is used as in the SOFC.
The electrochemical cell used in the SOFC or the SOEC has at least a stacked body of an air electrode (oxygen electrode), an electrolyte layer, and a fuel electrode (hydrogen electrode), for which materials having different characteristics are used. The air electrode and the fuel electrode are porous, and different gasses are supplied to the air electrode and the fuel electrode with a dense electrolyte as a boundary. The air electrode and the fuel electrode are electric conductors, and the electrolyte is an ion conductor which does not conduct electricity. Examples of the shape of the electrochemical cell include a flat plate type, a cylinder type, a cylinder-plate type and so on. The flat plate type electrochemical cell has a shape in which the air electrode, the electrolyte, and the fuel electrode are stacked in a plate shape. What is obtained by integrating a plurality of the cells is generally called a stack. In the case of the flat plate type electrochemical cell, the stack is made by stacking a plurality of flat plate type cells, and has a structure in which different gasses are supplied to the air electrode and the fuel electrode of each cell and cells are can be electrically connected in series. The cells are separated by a separator, and the separator partitions gasses for the cells. The separator is conductive and thus also has a role of electrically conducting the cells. A supply flow path and an exhaust flow path for the gasses to each cell are also generally formed in the separator.
A metal component used for the SOFC or the SOEC is required to have sufficient strength and oxidation resistance at a high temperature of 600 to 1000° C. being a working temperature and have a thermal expansion coefficient close to that of the cell, and so on. As the material satisfying the above characteristics, ferritic stainless steel is often used. The metal component used for the SOFC or the SOEC is used at high temperature in a specific environment where one side is in contact with air and the other side is in contact with a mixed gas of hydrogen and water vapor. In the separator of the above stack, a surface on the air electrode side is in contact with air and a surface on the hydrogen electrode is in contact with an atmosphere containing hydrogen such as a mixed gas of hydrogen and water vapor. Further, a pipe for the mixed gas of hydrogen and water vapor has an inner surface in contact with the mixed gas of hydrogen and water vapor and an outer surface in contact with air.
It has been revealed by the research of the inventors of this application that metallic corrosion of the above-explained metal is accelerated in a specific environment where one side is in contact with air and the other side is in contact with an atmosphere containing hydrogen at high temperature. Further, the electric resistance of the separator required to conduct electricity among the metal components is directly linked to the efficiency of the SOFC or the SOEC, and therefore an increase in resistance due to the corrosion is also a serious problem. To prevent the performance degradation of the cell due to the evaporation of chromium from the separator made of stainless steel and the adhesion of chromium to the cell, a chromium diffusion inhibition coating is often provided on the air electrode side of the separator. The chromium diffusion inhibition coating is applied to the air electrode side of the separator, and it has been revealed by the research of the inventors of this application that the coating also deteriorates from the influence of diffusion of hydrogen present on the rear side.
A metal component for electrochemical stack in an embodiment includes: a metal base material having a first surface exposed to an atmosphere containing hydrogen and a second surface exposed to an atmosphere containing oxygen; and a hydrogen permeation inhibition and protection coating provided on the first surface of the metal base material.
Hereinafter, a metal component for electrochemical stack and an electrochemical stack in embodiments will be explained with reference to the drawings. In each embodiment illustrated below, the same codes are given to substantially the same components to partially omit their explanations in some cases. The drawings are schematically illustrated, in which the relation between a thickness and plane dimensions, a ratio between thicknesses of parts, and the like may differ from actual ones.
The metal component 1 illustrated in
The first electrochemical cell 11 and the second electrochemical cell 12 have the same configuration, and each have a first electrode 14 functioning as a fuel electrode (hydrogen electrode), a second electrode 15 functioning as an air electrode (oxygen electrode), and an electrolyte layer 16 arranged between the electrodes 14 and 15. The first and second electrodes 14 and 15 are each formed of a porous electric conductor. The first electrode 14 is arranged on a porous support body 17. The electrolyte layer 16 is composed of, for example, a dense solid oxide electrolyte, and is an ion conductor which does not conduct electricity. Each of the first and second electrochemical cells 11 and 12 is composed of the first electrode 14, the second electrode 15, the electrolyte layer 16, and the support body 17. Around the first and second electrochemical cells 11 and 12, a gas flow path 18 is provided. More specifically, gas according to the use application of the electrochemical stack 10 is supplied when needed to the first and second electrodes 14 and 15 as a supply gas via a part of the gas flow path 18, and an exhaust gas generated in and exhausted from the first and second electrodes 14 and 15 is exhausted from the cells 11 and 12 via another part of the gas flow path 18.
In the case of using the electrochemical stack 10 as a fuel cell such as the SOFC, hydrogen (H2) is supplied to the first electrode 14 as the fuel electrode (hydrogen electrode), and air (oxygen) is supplied to the second electrode 15 as the air electrode (oxygen electrode). Further, in the case of using the electrochemical stack 10 as an electrolysis cell such as the SOEC employing the high-temperature water vapor electrolysis method, water vapor (H2O) or water vapor (H2O) containing hydrogen (H2) as needed is supplied to the first electrode 14 as the hydrogen electrode.
In the electrochemical cell 11, 12, the atmosphere of the first electrode 14 as the fuel electrode (hydrogen electrode) and the atmosphere of the second electrode 15 as the air electrode (oxygen electrode) are isolated from each other by the dense electrolyte layer 16. Also at the outer peripheral portions of the electrochemical cells 11 and 12 and between the adjacent cells 11 and 12, the atmospheres of the first electrode 14 and the second electrode 15 need to be separated by some dense member. In this embodiment, between the adjacent first electrode 14 and second electrode 15, their atmospheres are separated by the dense separator 13.
Further, a partition plate 19 which partitions atmospheres of the first electrode 14 and the second electrode 15 is provided on the outer peripheral part of the dense electrolyte layer 16 at the outer peripheral portion of one electrochemical cell 11, 12, thereby partitioning the atmospheres of the first electrode 14 and the second electrode 15. At a contact surface between the partition plate 19 and the separator 13, a contact surface between the partition plate 19 and the cell 11, 12, a joint surface in the case where the separator 13 is composed of a plurality of parts, and the like, a sealing member 20A is often used for prevention of gas leakage and, for example, a glass seal, a compressive seal, or the like is used. In the electrochemical stack 10 illustrated in
The metal component 1 illustrated in
In the metal component 1 used as the separator 13 in the electrochemical stack 10 illustrated in
In the case of using the electrochemical stack 10 illustrated in
Further, in the separator 13 which is required to conduct electricity among the metal components, the electric resistance is directly linked to the efficiency of the SOFC, the SOEC, or the like, and therefore an increase in resistance due to corrosion becomes a serious problem. Thus, to prevent the corrosion accelerated by the diffusion of hydrogen of the metal base material 2, it is important to suppress the diffusion of hydrogen in the metal base material 2. It has been revealed by the research of the inventors of this application that in the case of forming the chromium diffusion inhibition coating 4 on the second electrode 15 side as the air electrode of chromium from the separator 13 in order to prevent performance degradation due to the evaporation of chromium from the separator 13 composed of stainless steel or the like and the adhesion of chromium to the cells 11 and 12, the deterioration of the chromium diffusion inhibition coating 4 is also accelerated due to the diffusion of hydrogen on its rear side.
The hydrogen permeation inhibition and protection coating 3 is provided on the first surface 2a exposed to the atmosphere containing hydrogen of the metal base material 2. The hydrogen permeation inhibition and protection coating 3 preferably contains a material low in hydrogen permeability, specifically, at least one selected from a group consisting of aluminum (Al), aluminum oxide (AlO), aluminum-chromium composite oxide (AlCrO), erbium oxide (ErO), silicon-chromium composite oxide (SiCrO), zirconium oxide (ZrO), magnesium phosphate (MgPO4), aluminum phosphate (AlPO4), titanium nitride (TiN), titanium carbide (TiC), and silicon carbide (SiC). Because at least one selected from the above material group is low in hydrogen permeability, the provision of the hydrogen permeation inhibition and protection coating 3 containing the material on the first surface 2a of the metal base material 2 suppresses the diffusion of hydrogen into the metal base material 2 from the atmosphere containing hydrogen present on the first surface 2a side of the metal base material 2. Therefore, it is possible to suppress the corrosion of the metal base material 2 on the second surface 2b side exposed to air or the like due to the diffusion of hydrogen in the metal base material 2.
As illustrated in the cross-sectional SEM image in
For the formation of the hydrogen permeation inhibition and protection coating 3, a thin film forming method such as a plating method, a vapor disposition method, or a sputtering method is applicable, for example, for a metal coating such as Al. A compound coating composed of oxide such as AlO, ZrO, or AlCrO, nitride such as TiN, or carbide such as TiC, SiC or the like can be formed by applying a thin film forming method such as the vapor disposition method, the sputtering method, or the like. In the case of applying the oxide to the hydrogen permeation inhibition and protection coating 3, a metal oxide film may be formed by forming a metal film on the metal base material 2 by the plating method or the like and then firing it in an atmosphere containing oxygen. Further, when the metal base material 2 is composed of an alloy containing Cr in the formation of the hydrogen permeation inhibition and protection coating 3 composed of a composite oxide containing Cr such as AlCrO, SiCrO, or the like, the hydrogen permeation inhibition and protection coating 3 containing AlCrO or SiCrO may be formed by forming a metal Al film or a metal Si film on the metal base material 2 by the plating method and then baking it to diffuse Cr of the metal base material 2 into the metal Al film or the metal Si film. A partial Cr in AlCrO or SiCrO is composed of Cr in the metal base material 2. The formation method of an oxide film is easy to execute and can be reduced in cost, and the oxide such as AlCrO or SiCrO is formed in situ, whereby the adhesiveness of the hydrogen permeation inhibition and protection coating 3 can be enhanced. In the case of applying a coating on the metal base material 2, peeling is a serious problem, and therefore the improvement in adhesiveness is important.
In the case of applying the above metal component 1 to the separator 13 of the electrochemical stack 10, the separator 13 is required to conduct electricity. There is no problem in the case of applying a good conductive material such as metal Al to the hydrogen permeation inhibition and protection coating 3, but in the case of applying a material low in conductivity such as oxide or nitride, the increase in electric resistance due to the formation of the hydrogen permeation inhibition and protection coating 3 needs to be suppressed. In this case, it is preferable to form the hydrogen permeation inhibition and protection coating 3 as thin as possible to suppress the increase in electric resistance due to the hydrogen permeation inhibition and protection coating 3. Specifically, the thickness of the hydrogen permeation inhibition and protection coating 3 is preferably set to 2 μm or more and 30 μm or less. When the thickness of the hydrogen permeation inhibition and protection coating 3 is less than 2 m, the hydrogen diffusion inhibition effect may deteriorate. When the thickness of the hydrogen permeation inhibition and protection coating 3 is more than 30 m, the electric resistance is likely to increase.
Next, a metal component for electrochemical stack according to a second embodiment will be explained with reference to
The metal pipe 21 illustrated in
In the case of applying the electrochemical stack 10 to the SOFC, hydrogen (H2) is supplied from a hydrogen tank 35 through the first supply pipe 31 to the first electrode as the fuel electrode (hydrogen electrode) of the cell 11, and air and oxygen (O2) in air are supplied from a compressor 36 through a second supply pipe 32 to the second electrode as the air electrode (oxygen electrode) as illustrated in
H2+O2-→H2O+2e− (1)
The oxide ion (O2-) generated in this event is sent to the second electrode through an electrolyte layer of the cell 11. The electron (e−) reaches the second electrode through an external circuit. At the first electrode, water (H2O) is generated.
½O2+2e−→O2- (2)
The excessive hydrogen exhausted from the first exhaust pipe 33 is returned to the first supply pipe 31 via a recovery pipe 37. The supply pipes 31, 32 and the exhaust pipes 33, 34 are provided with valves 38 as needed. In the electrochemical stack apparatus 30 including the SOFC, the metal pipe 21 in the second embodiment is used at least for the first supply pipe 31.
In the case of applying the electrochemical stack 10 to the SOEC, water vapor (H2O) containing about 10 vol % of hydrogen is supplied from a heated water vapor generator 39 through the first supply pipe 31 to the first electrode as the hydrogen electrode of the cell 11 as illustrated in
H2O+2e−→H2+O2- (3)
The oxide ion (O2-) generated in this event is sent to the second electrode through the electrolyte layer of the cell 11. At the second electrode, oxygen (O2) is generated by the following reaction of Formula (4).
O2-→½O2+2e− (4)
The hydrogen (H2) generated at the first electrode and excessive water vapor (H2O) are sent through the first exhaust pipe 33 to a separator 40 having a function of cooling and separating hydrogen and water vapor. In the electrochemical stack apparatus 30 having the SOEC, the metal pipe 21 in the second embodiment is used for the first supply pipe 31 and the first exhaust pipe 33. In the case of not adding hydrogen to water vapor to be supplied to the first electrode, the metal pipe 21 may be applied only to the first exhaust pipe 33.
In the metal pipe 21 used as at least part of the supply pipes 31, 32 and the exhaust pipes 33, 34 of each of the electrochemical stack apparatuses 30 illustrated in
In the case of using the electrochemical stack 10 illustrated in
Hence, at least one of the inner surface 22a and the outer surface 22b of the metal tube 22 is provided with a hydrogen permeation inhibition and protection coating 23. For the hydrogen permeation inhibition and protection coating 23, a material low in hydrogen permeability, specifically, at least one selected from a group consisting of aluminum (Al), aluminum oxide (AlO), aluminum-chromium composite oxide (AlCrO), erbium oxide (ErO), silicon-chromium composite oxide (SiCrO), zirconium oxide (ZrO), magnesium phosphate (MgPO4), aluminum phosphate (AlPO4), titanium nitride (TiN), titanium carbide (TiC), and silicon carbide (SiC) is used as in the first embodiment. Because at least one material selected from the above material group is low in hydrogen permeability, the provision of the hydrogen permeation inhibition and protection coating 23 containing the material at least on the inner surface 22a of the inner surface 22a and the outer surface 22b of the metal tube 22 suppresses the diffusion of hydrogen into the metal tube 22 from the atmosphere containing hydrogen present on the inner surface 22a side of the metal tube 22. Therefore, it is possible to suppress the corrosion of the metal tube 22 on the outer surface 22b side exposed to air due to the diffusion of hydrogen in the metal tube 22.
In the metal tube 22 provided with the hydrogen permeation inhibition and protection coating 23 on the inner surface 22a, the decrease in mechanical strength of the metal tube 22 can be suppressed because the hydrogen permeation inhibition and protection coating 23 provided on the inner surface 22a side in contact with an atmosphere containing hydrogen and water vapor suppresses the permeation and diffusion of hydrogen and the occurrence of the corrosion on the outer surface 22b side in contact with air due to the diffusion of hydrogen, as in the results illustrated in
For the formation of the hydrogen permeation inhibition and protection coating 23, a thin film forming method such as a plating method, a vapor disposition method, or a sputtering method is applicable, for example, for a metal coating such as Al, and a thin film forming method such as a vapor disposition method, a sputtering method, or the like is applicable for a compound coating composed of oxide such as AlO, ZrO, or AlCrO, nitride such as TiN, or carbide such as TiC, SiC as in the first embodiment. When applying the oxide to the hydrogen permeation inhibition and protection coating 23, a metal film may be first formed by a plating method or the like on the surface (22a, 22b) of the metal tube 22, and then burned in an atmosphere containing oxygen to form a metal oxide film.
Further, in the formation of the hydrogen permeation inhibition and protection coating 23 composed of a composite oxide containing Cr such as AlCrO, SiCrO, or the like, in the case where the metal tube 22 is composed of an alloy containing Cr, the hydrogen permeation inhibition and protection coating 23 containing AlCr or SiCrO may be formed by forming a metal Al film or a metal Si film on the surface (22a, 22b) of the metal tube 22 by the plating method, then baking it in an atmosphere containing oxygen to diffuse Cr in the metal tube 22 into the metal Al film or metal Si film while oxidizing the metal Al film or the metal Si film. In this case, a material containing Cr does not need to be used in forming a film of the hydrogen permeation inhibition and protection coating 23. The forming method of the oxide film is easy to execute and can be reduced in cost, and the oxide such as AlCrO or SiCrO is formed in situ, whereby the adhesiveness of the hydrogen permeation inhibition and protection coating 23 can be enhanced. In the case of applying a coating on the metal tube 22, peeling is a serious problem, and therefore the improvement in adhesiveness is important.
In the case of applying the above metal pipe 21 to the electrochemical stack apparatus 30, it is not required to conduct electricity through the metal pipe 21, so that the increase in electric resistance due to the formation of the hydrogen permeation inhibition and protection coating 23 does not need to be suppressed unlike the metal component 1 used for the separator in the first embodiment. Therefore, the hydrogen permeation inhibition and protection coating 23 provided on the metal tube 22 may be formed thicker than the hydrogen permeation inhibition and protection coating 3 provided on the metal base material 2. This can enhance the durability, reliability and the like of the hydrogen permeation inhibition and protection coating 23. However, if the thickness of the hydrogen permeation inhibition and protection coating 23 is too large, peeling or the like becomes likely to occur, and therefore the thickness of the hydrogen permeation inhibition and protection coating 23 is preferably set to 100 μm or less. The thickness of the hydrogen permeation inhibition and protection coating 23 is preferably set to 2 μm or more, and more preferably set to 5 μm or more for enhancing the hydrogen diffusion inhibition effect.
The above first and second embodiments illustrate examples in which the electrochemical cell and the electrochemical stack are applied to the fuel cell or the electrolysis cell, but the electrochemical cell and the electrochemical stack are not limited to the above but may be, for example, an electrolysis device for carbon dioxide (CO2) or a co-electrolysis device for a mixed gas of carbon dioxide and water vapor. For example, in the CO2 electrolysis device, the first electrode reduces supplied carbon dioxide (CO2) to generate carbon monoxide (CO) and an oxide ion (O2-). The second electrode generates oxygen from the oxide ion (O2-) sent from the first electrode. The metal component or metal pipe in the embodiment may be applied to the CO2 electrolysis device. The reaction of the first electrode is as following Formula (5) and Formula (6), and only the reaction of Formula (6) occurs in the case of CO2 electrolysis, and the reactions of Formula (5) and Formula (6) occur in the case of co-electrolysis. The reaction of the second electrode is as following Formula (7).
H2O+2e−→H2+O2- (5)
CO2+2e−→CO+O2- (6)
2O2-→O2+4e− (7)
Note that the above-explained configurations of the embodiments are applicable in combinations and part thereof may be replaced. While certain embodiments of the present invention have been explained, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. These embodiments may be embodied in a variety of other forms; furthermore, various omissions, substitutions and changes may be made therein without departing from the spirit of the inventions. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the inventions.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-132001 | Aug 2021 | JP | national |
