This application claims priority to Japanese Patent Application Nos. 2012-085610, filed Apr. 4, 2012 and 2012-087456, filed Apr. 6, 2012, each incorporated herein in its entirety.
The present invention relates to a membrane electrode assembly used for example in a solid polymer electrolyte fuel cell, a fuel cell, a fuel cell stack, and a method for manufacturing a membrane electrode assembly.
As a conventional technique concerning a fuel cell, there is a configuration disclosed in Japanese Patent Application Laid-Open Publication No. 2009-245871. In a fuel cell described in Japanese Patent Application Laid-Open Publication No. 2009-245871, a gas-permeable electrode region MPL is formed with coarse regions formed of conductive particles of a large particle size and dense regions formed of conductive particles of a particle size smaller than those of the coarse regions. The gas-permeable electrode region MPL is in contact with a gas diffusion layer at an upper surface thereof and with a catalyst layer at a lower surface thereof.
The particles used in the dense regions have such a particle size as to make a saturated water vapor pressure in voids, which is determined according to the Kelvin equation, be higher than that in an open space. Thereby, in the fuel cell, the saturated water vapor pressure in the coarse regions is made lower than that in the dense regions so that condensation of water vapor produced at the catalyst layer is suppressed in the dense regions.
In the fuel cell described in Japanese Patent Application Laid-Open Publication No. 2009-245871, the porosity in the dense regions determined according to the Kelvin equation is in nano-order, and if liquid water is condensed in the coarse regions, gas diffusivity drastically decreases.
In view of the above problem, the present invention has an objective of providing a membrane electrode assembly, a fuel cell, and a method for manufacturing a membrane electrode assembly, which can facilitate discharge of liquid water produced upon power generation and improve oxygen transport and consequently the power generation performance.
A membrane electrode assembly according to a first aspect of the present invention is a membrane electrode assembly in which a first porous body is stacked on a surface of a catalyst layer and a second porous body is stacked on the first porous body. In this membrane electrode assembly, the first porous body has a low porosity at portions in contact with solid-phase portions of the second porous body, and has a relatively high porosity at portions facing gas-phase portions of the second porous body.
A fuel cell according to a second aspect of the present invention comprises: a membrane electrode assembly having a structure in which an electrolyte membrane is sandwiched by paired electrode layers; and a separator configured to form a gas flow channel between the separator and the membrane electrode assembly. Each of the electrode layers includes a first porous body and a second porous body which is formed of a metal porous body and which forms an electrode surface, and the first porous body and the second porous body engage with each other such that the first porous body partly digs into voids in the second porous body.
Embodiments of the present invention are described below with reference to the drawings.
With reference to
The fuel cell stack 10 has paired end plates 11 and 12, paired power collection plates 13 and 14 placed between the paired end plates 11 and 12, and multiple cell units (fuel cells) A1 placed between the paired power collection plates 13 and 14. The end plate 12 is provided at one end of the cell units A1 in their stacking direction (an X direction) (at the right end in
As shown in
The plan structure of the cell unit A1 is described with reference to
The manifold portions H at the one side include supply manifold holes H1 to H3. The supply manifold holes H1 to H3 are specifically a manifold hole for supplying oxygen-containing gas (H1), a manifold hole for supplying coolant fluid (H2), and a manifold hole for supplying hydrogen-containing gas (H3), and form flow channels for an oxygen-containing gas, a coolant fluid, and a hydrogen-containing gas, respectively, in the X direction shown in
The manifold portions H at the other side include discharge manifold holes H4 to H6. The discharge manifold holes H4 to H6 are specifically a manifold hole for discharging hydrogen-containing gas (H4), a manifold hole for discharging coolant fluid (H5), and a manifold hole for discharging oxygen-containing gas (H6), and form flow channels for the hydrogen-containing gas, the coolant fluid, and the oxygen-containing gas, respectively, in the X direction shown in
The sectional structure of the cell unit A1 is described with reference to
The cell frame 20 (31 to 33 and 21) is also called a membrane electrode assembly (MEA), and includes a membrane electrode assembly 30 (31 to 33) and the frame 21 having a quadrangular shape in a plan view. The membrane electrode assembly 30 (31 to 33) has: an electrolyte membrane 31 made for example of a solid polymer; and an air electrode 32 and a fuel electrode 33 in contact with respective surfaces of the electrolyte membrane 31.
As shown in
The separators 40 and 41 are each made for example of stainless steel, have a quadrangular shape that matches the frame 21 and the electrolyte membrane 31, and have the supply manifold holes H1 to H3 and the discharge manifold holes H4 to H6 like the frame 21. The separators 40 and 41 form the gas flow channels G by being superimposed on the cell frame 20 (31 to 33 and 21). In this state, the supply manifold holes H1 to H3 and the discharge manifold holes H4 to H6 of the separators 40 and 41 and of the frame 21 communicate with each other in the X direction.
A gas seal 36 is provided between an edge portion of the frame 21 and an edge portion of each of the separators 40 and 41, as well as around each of the supply manifold holes H1 to H3 and the discharge manifold holes H4 to H6. The gas seal 36 is also provided between every adjacent ones of the stacked cell units A1, i.e., between the adjacent separators 40 and 41. This enables the coolant liquid to flow between the adjacent separators 40 and 41. The gas seal 36 forms gas flow channels for the oxygen-containing gas, the hydrogen-containing gas, and the coolant fluid between the layers in an air-tight manner. The gas seal 36 provides an opening to an edge portion of appropriate ones of the supply holes H1 to H3 and the discharge holes H4 to H6 so that a fluid may flow between the layers.
With reference to
The air electrode 32 has a catalyst layer 32A in contact with one of the surfaces of the electrolyte membrane 31 and a gas diffusion layer 32B stacked on a surface of the catalyst layer 32A on the separator 40 side. The gas diffusion layer 32B has a first porous body 32b in contact with the catalyst layer 32A and a second porous body 32a stacked thereon on the separator 40 side.
The second porous body 32a is for example wire mesh formed by weaving metal wire materials (several tens micro meter) alternately, and has solid-phase portions 32a′ where the metal wire material exists and gas-phase portions 32a″ where no metal wire material exists. The first porous body 32b has a low porosity at portions in contact with the solid-phase portions 32a′ of the second porous body 32a, and has a relatively high porosity at portions facing the gas-phase portions 32a″ of the second porous body 32a. Specifically, the first porous body 32b has a lower porosity at the portions in contact with the solid-phase portions 32a′ than at the portions facing the gas-phase portions 32a″.
Further, the first porous body 32b has a large particle size at the portions in contact with the solid-phase portions 32a′ of the second porous body 32a, and has a relatively small particle size at the portions facing the gas-phase portions 32a″ of the second porous body 32a.
The fuel electrode 33 has the same structure as the air electrode 32 described above. To be more specific, the fuel electrode 33 has a catalyst layer 33A in contact with the other surface of the electrolyte membrane 31 and a gas diffusion layer 33B stacked on a surface of the catalyst layer 33A on the separator 41 side. The gas diffusion layer 33B has a first porous body 33b in contact with the catalyst layer 33A and a second porous body 33a stacked thereon on the separator 41 side. The second porous body 33a is for example wire mesh formed by weaving metal wire materials (several tens micro meter) alternately, and has solid-phase portions 33a′ where the metal wire material exists and gas-phase portions 33a″ where no metal wire material exists. The first porous body 33b has a low porosity at the portions in contact with the solid-phase portions 33a′ of the second porous body 33a, and has a relatively high porosity at the portions facing the gas-phase portions 33a″ of the second porous body 33a.
Further, the first porous body 33b has a large particle size at the portions in contact with the solid-phase portions 33a′ of the second porous body 33a, and has a relatively small particle size at the portions facing the gas-phase portions 33a″ of the second porous body 33a.
The structure of the air electrode 32 shown in
The membrane electrode assembly 30 generates power when the hydrogen-containing gas flowing through one of the gas flow channels G flows to and comes into contact with the fuel electrode 33 and also when the oxygen-containing gas flowing through the other one of the gas flow channels G flows to and comes into contact with the air electrode 32. The first porous body 32b (33b) has a low porosity at the portions in contact with the solid-phase portions 32a′ (33a′) of the second porous body 32a (33a), and has a relatively high porosity at the portions facing the gas-phase portions 32a″ (33a″) of the second porous body 32a (33a). For this reason, as shown with arrows EL in
As for the gas-phase portions 32a″ (33a″) of the second porous body 32a (33a), as shown with arrows Ox in
The above-described improvement in the transport of the electrons and of the oxygen-containing gas is related to a “degree of bend.”
With reference to
The degree of bend in the second porous body 32a is represented by L2/L1. Thus, in the second porous body 32a, the smallest value of the degree of bend is “1.” The same applies to the second porous body 33a.
Next, a description is given of a method for manufacturing the membrane electrode assembly 30 according to the first embodiment. A first example of the method for manufacturing the membrane electrode assembly 30 is described with reference to
In the method for manufacturing the membrane electrode assembly 30 according to the first embodiment, the structure of the first porous body 32b (33b) is changed according to the arrangement of the gas-phase portions (voids) 32a″ (33a″) and the solid-phase portions 32a′ (33a′) of the second porous body 32a (33a). Specifically, in the method for manufacturing the membrane electrode assembly 30, the voids in the first porous body 32b (33b) are crushed by part of the second porous body 32a (33a). Thereby, the first porous body 32b (33b) has a low porosity at the portions in contact with the solid-phase portions 32a′ (33a′) of the second porous body 32a (33a), and has a relatively high porosity at the portions facing the gas-phase portions 32a″ (33a″) of the second porous body 32a (33a).
As shown in
The pressing force is not applied to the first porous body 32b (33b) at the portions facing the gas-phase portions (voids) 32a″ (33a″). Hence, voids in the first porous body 32b (33b) at the portions facing the gas-phase portions (voids) 32a″ (33a″) are not crushed, and therefore little structural change occurs. However, carbon particles are often bound with a binder such as polytetrafluoroethylene (PTFE), and they follow the compressed carbon particles as shown with encircling line II in
In the first example shown in
According to the membrane electrode assembly 30 configured as above and the method for manufacturing the membrane electrode assembly 30, the following effects can be attained. Condensation of liquid water in the coarse region is prevented, and thereby decrease in the gas diffusivity can be prevented. Carbon particles are brought into more contact with each other under the solid-phase portions 32a′ (33a′), so that the transport paths for electrons increase. On the other hand, particle contact is relatively low under the gas-phase portions 32a″ (33a″), which allows securement of transport paths for oxygen. In addition, capillary pressure promotes discharge of liquid water from the solid-phase portions 32a′ (33a′) to the gas-phase portions 32a″ (33a″). Thereby, transport of not only electrons but also oxygen can be improved, and consequently the power generation performance can be improved.
In a second embodiment, the cell plate (fuel cell) A1 and the fuel cell stack 10 formed by stacking multiple cell plates A1 are described. In the cell plate A1, the first and second porous bodies 32a and 32b (33a and 33b) engage with each other such that the first porous body 32b (33b) is partly embedded in the gas-phase portions (voids) 32a″ (33a″) of the second porous body 32a (33a).
The overall configuration of the fuel cell stack 10 (
The structure of the air electrode 32 is described with reference to
A height H by which the first porous body 32b and the second porous body 32a engage with each other is equal to or smaller than a depth D of the gas-phase portions 32a″ of the second porous body 32a.
The first porous body 32b is a so-called porous solid, and is made for example of a carbon material. Specifically, the first porous body 32b is formed by binding randomly-stacked fiber with a binder and giving the stack a water-repellent treatment such as PTFE, or by sintering an aggregate of carbon black or the like with a binder such as PTFE.
The second porous body 32a is a metal porous body and is distinct from the first porous body 32b. At least one metal selected from the group consisting of iron, stainless steel, aluminum, aluminum alloys, chromium, chromium alloys, nickel, nickel alloys, magnesium, and magnesium alloys can be used for the second porous body 32a. A specific mode of the metal porous body includes wire mesh, punched metal, etched metal, expanded metal, and the like, and is wire mesh in this embodiment as shown in
The fuel cell stack 10 is formed by stacking multiple cell plates (fuel cells) A1 according to the second embodiment. When an oxygen-containing gas and a hydrogen-containing gas are supplied to the air electrode 32 and the fuel electrode 33, respectively, the cell plate (fuel cell) A1 generates electric energy by electrochemical reaction. In this event, since the first porous body 32b (33b) is partly embedded in the gas-phase portions (voids) 32a″ (33a″) of the second porous body 32a (33a), transport paths for electrons are secured between the first porous body 32b (33b) and the solid-phase portions 32a′ (33a′) of the second porous body 32a, as shown with arrows EL in
Under the gas-phase portions 32a″ (33a″) of the second porous body 32a (33a), as shown with arrows Ox in
As described, with the cell plate (fuel cell) A1 and the fuel cell stack 10 according to the second embodiment, discharge of liquid water from the air electrode 32 and the fuel electrode 33 is facilitated, and at the same time, oxygen transport (gas diffusivity) is improved to consequently improve the power generation performance.
The second porous body 32a (33a) is at least one metal selected from the group consisting of iron, stainless steel, aluminum, aluminum alloys, chromium, chromium alloys, nickel, nickel alloys, magnesium, and magnesium alloys. Thereby, electron transportability can be improved while maintaining high oxygen transportability.
The height H by which the first porous body 32b (33b) and the second porous body 32a (33a) engage with each other is equal to or smaller than the depth D of the gas-phase portions 32a″ (33a″) of the second porous body 32a (33a). Thereby, the first porous body 32b (33b) does not partly protrudes toward the gas flow channel G. This enables the second porous body 32a (33a) having good conductivity to be in contact with the separator 40 (41) without fail, which allows securement of favorable conductive paths with low resistance.
Other embodiments are described with reference to
Under the solid-phase portions 32a′ (33a′) of the second porous body 32a (33a), the first porous body 32b (33b) is compressed to increase contact among carbon particles forming the first porous body 32b (33b). Thus, more electron transport paths (arrows EL in
At the gas-phase portions 32a″ (33a″) of the second porous body 32a (33a), the oxygen transport paths (arrows Ox in
Like the embodiment shown in
In the embodiment shown in
Although the embodiments of the present invention have been described, the invention is not limited to the foregoing embodiments, and various modifications may be made within the scope of the invention.
For example, although the wire mesh is used as an example for the second porous body in the embodiments described above, the present invention is not limited this. For example, punched metal or the like can of course be used instead.
According to the embodiments of the present invention, discharge of liquid water produced upon power generation is facilitated, and at the same time, oxygen transport (gas diffusivity) is improved to consequently improve the power generation performance. Therefore, the present invention is industrially applicable.
Number | Date | Country | Kind |
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2012-085610 | Apr 2012 | JP | national |
2012-087456 | Apr 2012 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2013/002348 | 4/4/2013 | WO | 00 |