This application is a national phase application of International Application No. PCT/JP2013/005799, filed Sep. 30, 2013, and claims the priority of Japanese Application No. 2012-253172, filed Nov. 19, 2012, the content of both of which is incorporated herein by reference.
The present invention relates to a porous layer material used for a fuel cell and a membrane electrode and gas diffusion layer assembly including the porous layer material.
A fuel cell may be configured to have a layer where a large number of small pores are formed (hereinafter referred to as “porous layer”) placed between a catalyst layer and a gas diffusion layer. For example, an available method of forming the porous layer mixes particles including carbon black powder and polytetrafluoroethylene (PTFE) with a dispersed solution of PTFE to form a slurry and applies the slurry on a gas diffusion layer, as described in Patent Literature 1. In another example, as described in Patent Literature 2, another available method first mixes carbon particles with fine powder of PTFE using a blender and additionally adds a processing aid to obtain a mixture. The method subsequently extrudes and rolls the mixture to obtain a film and places the film between a catalyst layer and a gas diffusion layer. As described in Patent Literature 2, another available method adds a precipitating agent to a mixed solution of carbon particles and a dispersed solution of PTFE to coprecipitate carbon and PTFE, subsequently filtrates and dries the coprecipitate and subsequently adds a processing aid to obtain a mixture. The method subsequently extrudes and rolls the mixture to obtain a film and places the film between a catalyst layer and a gas diffusion layer.
PTL1: JP 2008-243767A
PTL2: JP 2006-252948A
The method described in Patent Literature 1, however, causes the slurry to be penetrated in the gas diffusion layer in the course of application of the slurry. In application of the porous layer obtained by this method for a fuel cell, water may be accumulated in an area which the slurry is penetrated in. This may cause deterioration of the water drainage performance of the fuel cell. Penetration of the slurry in the gas diffusion layer may also may reduce the gas diffusion area and cause deterioration of the gas dispersibility.
In the method of mixing carbon particles with PTFE fine power using a blender described in Patent Literature 2, the two different particles (different solid substances) are mixed with each other and the average particle diameter of PTFE particles included in the fine powder is significantly larger than the average particle diameter of the carbon particles, so that there is a difficulty in uniformly dispersing the carbon particles and the PTFE particles. The uneven dispersion the carbon particles and the PTFE particles is likely to cause unevenness in power generation in the fuel cell and deterioration of the power generation performance.
In the method of adding the precipitating agent to the mixed solution of the carbon particles and the dispersed solution of PTFE to coprecipitate carbon and PTFE described in Patent Literature 2, the homogeneity of PTFE in the dispersed solution of PTFE is deteriorated with elapse of time. An upper layer part and a lower layer part of the coprecipitate may accordingly have different compositions. It is thus unlikely to disperse carbon and PTFE uniformly in the coprecipitate. Additionally, this method requires a long time for precipitation and drying and accordingly has the low productivity. Other needs with respect to the conventional method of forming the porous layer include reducing the cost and facilitating the process.
In order to solve at least part of the problems described above, the invention may be implemented by the following aspects.
(1) According to one aspect of the invention, there is provided a production method of a porous layer material for forming a porous layer placed between a gas diffusion layer and a catalyst layer in a fuel cell. The production method comprises the steps of (a) obtaining particles containing carbon and a water-repellent resin by spray drying a mixed solution including the carbon and the water-repellent resin, (b) producing a paste including the particles, and (c) extruding or rolling the paste to obtain the porous layer material in a sheet-like form. The production method of this aspect obtains the porous layer material in the sheet-like form. The porous layer is formed by joining the porous layer material with the gas diffusion layer or the catalyst layer. This suppresses penetration of the porous layer material into the gas diffusion layer and accordingly suppresses deterioration of the water drainage performance and the gas dispersibility in the gas diffusion layer. Additionally, the particles as the base material of the porous layer material are obtained by spray drying the mixed solution including the carbon and the water-repellent resin. This enables the carbon and the water-repellent resin to be substantially uniformly dispersed in the particles. This suppresses uneven distribution of the carbon and the water-repellent resin in the porous layer, thus suppresses the unevenness in water drainage performance in the porous layer. The spray drying technique also enables the particles including the carbon and the water-repellent resin to be produced in a relatively short time period. The sheet-like material is obtained as the porous layer material, so that the step of joining the porous layer material and the step of joining the material for gas diffusion layer may be provided as different steps.
(2) In the production method of the above aspect, the water-repellent resin may comprise polytetrafluoroethylene. The production method of this aspect provides the porous layer with high water repellency.
(3) According to another aspect of the invention, there is provided a production method of a membrane electrode and gas diffusion layer assembly including the porous layer material produced by the production method of the above aspect. The production method of the membrane electrode and gas diffusion layer assembly comprises the steps of (d) joining the porous layer material with a material for catalyst layer under application of a first force, and (e) joining a material for gas diffusion layer with the porous layer material joined with the material for catalyst layer under application of a second force that is smaller than the first force. The production method of this aspect causes the second force applied for joining the porous layer material with the material for gas diffusion layer to be smaller than the first force applied for joining the porous layer material with the material for catalyst layer. This suppresses the material for gas diffusion layer from being stuck through the porous layer, the catalyst layers of both the electrodes and the electrolyte membrane. This accordingly suppresses a short circuit between the electrodes.
(4) The production method of the above aspect may further comprises the steps of (f) providing an electrolyte membrane sheet that includes a carrier film and an electrolyte membrane placed on the carrier film, (g) placing the material for catalyst layer on the electrolyte membrane of the electrolyte membrane sheet, and (h) removing the carrier film from the electrolyte membrane sheet, wherein performing the step (d) after the step (g) to form the porous layer of one electrode, subsequently performing the step (h) and then performing the step (d) to form the porous layer of the other electrode. The production method of this aspect joins the porous layer material on one electrode side, before removing the carrier film from the electrolyte membrane sheet. After removal of the carrier film, the porous layer material serves instead of the carrier film to protect the electrolyte membrane and suppress deformation of the electrolyte membrane.
The invention may be implemented by any of various aspects: for example, a fuel cell including the porous layer material and the membrane electrode and gas diffusion layer assembly, a production method of the fuel cell, and a vehicle equipped with the fuel cell.
A. Embodiment
The procedure spray dries the mixed solution of carbon and PTFE obtained at step S205 to produce PTFE-coated carbon particles (step S210). The procedure adds and mixes a lubricant with the PTFE-coated carbon particles produced at step S210 to produce a paste including the PTFE-coated carbon particles (step S215). The mixed solution of carbon and PTFE is spray dried at step S210, since production of the paste using the particles obtained by spray drying ensures carbon and PTFE to be uniformly dispersed in the paste.
The procedure then extrudes and rolls the paste produced at step S215 to produce the MPL sheet (step S220). For example, the MPL sheet may be produced by extruding the paste produced at step S215 with an extruder to form beads and rolling the beads with a heat rolling mill.
The procedure dries the MPL sheet produced at step S220 to remove the lubricant and subsequently fires the dried MPL sheet to remove the surfactant, so as to complete the MPL sheet (step S225). The completed MPL sheet has a large number of small pores. In application of this MPL sheet to a fuel cell, it is expected that water produced in the course of power generation is discharged to a gas diffusion layer by taking advantage of the capillarity of the small pores. The above procedure may be modified to omit the drying process but perform only the firing process at step S225 in order to remove both the lubricant and the surfactant in the firing process.
Referring back to
The ink for catalyst layer provided at step S110 is applied on an exposed surface (surface of the electrolyte membrane on the side not bonded to the carrier sheet) of the electrolyte membrane sheet provided at step S110 (step S115). This process forms a catalyst layer of one electrode out of catalyst layers of two electrodes.
The electrolyte membrane sheet with the catalyst layer of one electrode formed thereon is joined with the MPL sheet produced at step S105 under application of a first pressure (step S120). At step S120, the MPL sheet is joined with the surface of the electrolyte membrane sheet with the catalyst layer formed thereon by applying the ink for catalyst layer. This process forms an MPL layer of one electrode. According to this embodiment, the term “MPL sheet” denotes a material for forming the MPL layer, and the term “MPL layer” denotes a layer formed by joining the MPL sheet with another layer or a material for forming another layer.
According to this embodiment, a die coater is used at step S115. As shown in
As shown in
Referring back to
The electrolyte membrane sheet with the catalyst layer formed at step S125 is joined with the MPL sheet produced at step S105 under application of a first pressure (step S130). At step S130, the MPL sheet is joined with the surface of the electrolyte membrane sheet with the catalyst layer formed thereon at step S125. This process forms an MPL layer of the other electrode opposite to the electrode of the MPL layer formed at step S120.
The electrolyte membrane sheet with the catalyst layers of both the electrodes and the MPL layers of both the electrodes formed thereon is joined with the GDL materials under application of a second pressure (step S135). At step S135, the GDL materials are joined with both the surfaces (two surfaces with the MPL layers respectively formed thereon) of the electrolyte membrane sheet. This process forms GDL layers of both the electrodes.
The MEGA is completed by hot pressing the electrolyte membrane with the catalyst layers of both the electrode, the MPL layers of both the electrodes and the GDL layers of both the electrodes formed thereon (assembly) (step S140).
As shown in
The feed roller 100 feeds the electrolyte membrane sheet 40 produced at step S120. The removal roller 410 removes the carrier film 11 from the electrolyte membrane sheet 40 and conveys the removed carrier film 11. The windup roller 415 winds up the carrier film 11 removed from the electrolyte membrane sheet 40. The die head 120 applies the ink for catalyst layer on a surface of the electrolyte membrane 12 exposed by removal of the carrier film 11. The conveyance roller 105 conveys an electrolyte membrane sheet 50 with the in, for catalyst layer applied thereon by the die head 120. As shown in
As shown in
As shown in
The second pressure is smaller than the first pressure applied at step S120 and at step S130. This suppresses the occurrence of a short circuit by part of the GDL material (for example, carbon fibers of the carbon paper) stuck through the adjacent catalyst layer, the electrolyte membrane 12 and the catalyst layer of the other electrode in the course of joining the GDL materials.
As shown in
As shown in
The production method of MEGA according to the embodiment described above produces the MPL sheets and joins the MPL sheets with the electrolyte membrane sheet with the catalyst layers formed thereon to form the MPL layers. This suppresses penetration of the component material of the MPL layer into the gas diffusion layer. This accordingly suppresses deterioration of water drainage performance and deterioration of the gas dispersibility caused by penetration of the base material of the MPL layer into the gas diffusion layer.
Additionally, the MPL sheets are used to form the MPL layers. This enables the process of joining the MPL sheets with the electrolyte membrane sheet with the catalyst layers formed thereon (steps S120 and S130) to be separated from the process of joining the GDL materials with the electrolyte membrane sheet with the MPL layers formed thereon (step S135). This enables the pressure applied for joining the electrolyte membrane sheet with the MPL sheet (first pressure) to be different from the pressure applied for joining the electrolyte membrane sheet with the GDL materials (second pressure). Setting a relatively large pressure to the pressure applied for joining the electrolyte membrane sheet with the MPL sheet (first pressure) causes the MPL layer and the catalyst layer to be closely joined with each other. This enhances the drainage performance of water in the catalyst layer. Setting a relatively small pressure to the pressure applied for joining the electrolyte membrane sheet with the GDL materials (second pressure) suppresses the GDL materials from being stuck through the electrolyte membrane and the catalyst layers of both the electrodes. This accordingly suppresses a short circuit of both the electrodes.
The mixture (particles) as the base material of the MPL sheet is produced by spray drying the mixed solution of carbon and PTFE. This enables carbon and PTFE to be uniformly dispersed in the mixture. This accordingly suppresses uneven distribution of carbon and PTFE in the MPL layer. The spray drying technique also enables the mixture of carbon and PTFE to be obtained in a relatively short time period. This improves the production efficiency of the MEGA.
The MPL sheet is joined with the catalyst layer of one electrode at step S120. The joined MPL sheet suppresses deformation of the electrolyte membrane after removal of the carrier film at step S125.
The MPL sheet described above corresponds to the porous layer material of the claims. The MPL layer and PTFE respectively correspond to the porous layer and the water-repellent resin of the claims.
B. Example
B1. Production of MPL Sheet
At step S205, after addition of Triton X as the surfactant to deionized water, the aqueous solution was stirred with a stirrer for 10 minutes. The rotation speed of the stirrer was set to a specified rotation speed producing no bubbles. The amount of Triton X added was determined such that the content of Triton X was approximately 10 wt % in the aqueous solution. Acetylene black (trade name: HS-100 manufactured by DENKI KAGAKU KOGYO KABUSHIKI KAISHA) was subsequently added as the carbon to the aqueous solution. The aqueous solution after addition of acetylene black was stirred with a homo mixer, so that acetylene black was dispersed. A homogeneous mixed solution (carbon black slurry) with little clumping was obtained by setting the stirring time to 1 to 3 hours. Subsequently D-111 (manufactured by DAIKIN INDUSTRIES, LTD.) was added as a fluid dispersion of PTFE to the mixed solution obtained. The amount of the fluid dispersion of PTFE added was determined such that the content of PTFE (solid substance) was approximately 40 wt % in the mixed solution. The mixed solution after addition of the fluid dispersion of PTFE was subsequently stirred for 10 minutes with a planetary mixer.
At step S210, PTFE-coated carbon particles were obtained by spray drying the mixed solution obtained at step S205 with a spray drying machine (manufactured by Fujisaki Electric Co., Ltd.) The conditions of spray drying were the hot air temperature set to 150° C. and the dropping rate of the mixed solution set to 50 cc/min. The particle diameter of the PTFE-coated carbon particles obtained was 3 to 7 μm.
At step S215, a mixture (paste) was produced by adding and mixing ISOPAR M (manufactured by Exxon Mobile Corporation) as the lubricant with the PTFE-coated carbon particles for 1 hour with a ball mill. The produced paste was then left at room temperature (about 25° C.) for 8 hours. The amount of ISOPAR M added (concentration) was determined such that the content was approximately 30 wt % in the mixture.
At step S220, the paste produced at step S215 was extruded to beads using a ram extruder (manufactured by Tabata Industrial Machinery Co., Ltd.) The conditions of extrusion were the bead diameter set to 20 mm, the cylinder temperature set to 50° C. and the extrusion rate set to 10 mm/min. The cylinder temperature may be set to any temperature in the range from room temperature (about 25° C.) to 70° C. The extrusion rate may be set to any rate in the range from 1 mm/min to 20 mm/min. The beads were then rolled to 0.05 mm using a heat rolling machine. The rolling conditions were the roll temperature set to 70° C. and the feed speed set to 0.5 m/min. Rolling was performed in two stages. More specifically, the beads were rolled to a sheet of 0.2 mm in thickness at the first stage, and the sheet of 0.2 mm in thickness was further rolled to a sheet of 0.05 mm in thickness at the second stage.
The drying conditions at step S225 were the drying temperature set to 150° C. and the drying time set to 1 hour. The firing conditions at step S225 were the firing temperature set to 300° C. and the firing time set to 10 minutes.
B2. Production of MEGA
The carbon paper made of the PAN-based carbon fibers was used as the GDL material. The first pressure at step S120 and step S130 was set to 3 MPa, and the second pressure at step S135 was set to 1 MPa.
B3. First Comparative Example
MEGA of a first comparative example was produced. The production method of MEGA of the first comparative example produced PTFE-coated carbon particles by the following process, instead of step S210. The mixed solution obtained at step S205 was subjected to centrifugal separation using a centrifuge, and a precipitate was obtained. The precipitate was dried in a drying furnace set to 150° C., so that the PTFE-coated carbon particles were obtained. The particle diameter of the PTFE-coated carbon particles obtained in the first comparative example was 4 to 7 μm. The other processes (steps S205, S215 to S225 and S110 to S135) were the same as those of the example described above.
B4. Second Comparative Example
MEGA of a second comparative example was produced. The production method of MEGA of the second comparative example mixed acetylene black (HS-100 manufactured by DENKI KAGAKU KOGYO KABUSHIKI KAISHA) with PTFE particles (M-111 manufactured by DAIKIN INDUSTRIES, LTD.) for 30 minutes using a V blender, instead of steps S205 and S210, so as to obtain a mixture of carbon and PTFE. In the mixture, the content of acetylene black was 60 wt %, and the content of the PTFE particles was 40 wt %. The average particle diameter of the PTFE particles was about 30 μm. The other processes (steps S215, S220, S225 and S110 to S135) were the same as those of the example described above.
B5. Third Comparative Example
MEGA of a third comparative example was produced. The mixed solution obtained at step S205 was applied on carbon paper, so that MPL layers were formed on gas diffusion layers. The composition of the mixed solution was controlled to be suitable for application on the carbon paper. More specifically, the dispersed solution of PTFE was added, such that the amount of PTFE (solid substance) in the mixed solution was 20 wt %. An ink for catalyst layer was applied on both surfaces of the electrolyte membrane to form catalyst layers. The MEGA was produced by joining the electrolyte membrane with the catalyst layers formed thereon with the gas diffusion layers with the MPL layers formed thereon.
B6. Evaluation Test
Four different fuel cells were produced using the MEGAs produced in the example, the first comparative example, the second comparative example and the third comparative example described above and were subjected to a power generation test for evaluation of the power generation performance. More specifically, the respective fuel cells were operated under the same conditions, and their voltages at the current density of 1.0 A/cm2 were measured. The power generation performances of these fuel cells were evaluated, based on the measured voltages. The voltages of the respective fuel cells were measured at the fuel cell temperature during operation set to 80° C. and 50° C. The temperature of 80° C. simulates the temperature suitable for power generation, and the temperature of 50° C. simulates the temperature of the fuel cell at the start. Table 1 given below shows the results of the evaluation test.
As shown in Table 1 above, the fuel cell using the MEGA of the example had the higher measured voltages at both 80° C. and 50° C. than the fuel cells using the MEGAs of the respective comparative examples. This means that the fuel cell using the MEGA of the example has the higher power generation performance than those of the fuel cells using the MEGAs of the respective comparative examples. Especially, the differences between the voltage of the fuel cell using the MEGA of the example and the voltages of the fuel cells using the MEGAs of the respective comparative examples at the relatively low fuel cell temperature (at 50° C.) are greater than those at the relatively high fuel cell temperature (at 80° C.).
The first comparative example produces the PTFE-coated carbon particles from the precipitate obtained by centrifugal separation of the mixed solution. Compared with the PTFE-coated carbon particles obtained by spray drying technique like the example, the produced PTFE-coated carbon particles are likely to have the lower dispersibility of carbon and PTFE. It is thus likely to cause the unevenness in water drainage performance in the MPL layers in the resulting fuel cell and provide the lower power generation performance compared with that of the example.
The average particle diameter (about 30 μm) of the PTFE particles used in the second comparative example is significantly larger than the average particle diameter (about 0.3 μm) of PTFE in the dispersed solution of PTFE of the example. This makes the carbon particles and the PTFE particles unlikely to be homogeneously mixed in the mixing process of the carbon particles and the PTFE particles. Additionally, the second comparative example mixes the two different particles and is thus likely to have difficulty in uniform dispersion of carbon and PTFE, compared with the example. Because of these reasons, it is likely to cause the unevenness in water drainage performance in the MPL layers in the resulting fuel cell and provide the lower power generation performance compared with that of the example.
The third comparative example applies the mixed solution of carbon and PTFE on the carbon paper as the base material of the gas diffusion layer. The mixed solution is thus penetrated in the carbon paper. In the resulting fuel cell, this makes water likely to be accumulated in an area of the gas diffusion layer (carbon paper) which the mixed solution is penetrated in and thereby deteriorates the water drainage performance. In close observation of the area of the carbon paper which the mixed solution is penetrated in, part of an area in which the mixed solution is not penetrated in may be placed between the areas which the mixed solution is penetrated in along the thickness direction of the carbon paper. Water is likely to gather and is unlikely to be drained in this part by, for example, capillarity in the area which the mixed solution is penetrated in. Accordingly water is more likely to be accumulated in this part.
Additionally, in the third comparative example, penetration of the mixed solution in the carbon paper reduces the gas diffusion area and deteriorates the gas dispersibility. As a result, the third comparative example has unevenness in water drainage performance in the MPL layers in the resulting fuel cell or interference with the gas dispersibility. It is thus likely to provide the lower power generation performance compared with that of the example.
At the relatively lower fuel cell temperature of 50° C., water is more likely to be aggregated than at the relatively higher fuel cell temperature of 80° C. Accordingly, the differences in water drainage performance between the example and the respective comparative examples more significantly appear as the differences in power generation efficiency (voltage) at the fuel cell temperature of 50° C.
C. Modifications
C1. Modification 1
In the embodiment and its example described above, the MPL layer of one electrode and the MPL layer of the other electrode are formed at different steps (steps S120 and S130). The invention is, however, not limited to this procedure. A modified procedure may form catalyst layers of both the electrodes prior to formation of the MPL layer of ether electrode and then simultaneously join the MPL sheets with the catalyst layers of both the electrodes to simultaneously form the MPL layers of both the electrodes. In the embodiment and its example described above, the GDL layers of both the electrodes are formed simultaneously. Alternatively, the GDL layers of the respective electrodes may be formed at different timings (i.e., at different steps).
C2. Modification 2
In the embodiment and its example described above, the GDL materials are cut by the two cutting machines 530 and 535 and are then joined with the MPL layers. The invention is, however, not limited to this procedure. For example, one modified procedure may join the GDL materials with the MPL layers and subsequently cut the entire membrane electrode assembly to a specified size.
C3. Modification 3
In the embodiment and its example described above, the assembly including the gas diffusion layers is produced as the MEGA. Alternatively, an assembly comprised of the layers other than the gas diffusion layers may be produced. In this modified procedure, the fuel cell is manufactured by joining the completed MEGA with the GDL materials and placing the resulting assembly between separators.
C4. Modification 4
In the embodiment and its example described above, the catalyst layers of both the electrodes are formed by the method of applying the ink for catalyst layer. A modified procedure may prepare catalyst layer sheets in advance like the MPL sheets and join the catalyst layer sheets with the electrolyte membrane to form the catalyst layers of both the electrodes.
C5. Modification 5
In the embodiment and its example described above, the pressure applied for joining the MPL sheets (first pressure) is smaller than the pressure applied for joining the GDL material (second pressure). The invention is, however, not limited to this configuration. The first pressure may be equal to the second pressure or may be larger than the second pressure.
The invention is not limited to any of the embodiment, the examples and the modifications described herein but may be implemented by a diversity of other configurations without departing from the scope of the invention. For example, the technical features of the embodiment, examples or modifications corresponding to the technical features of the respective aspects described in Summary may be replaced or combined appropriately, in order to solve part or all of the problems described above or in order to achieve part or all of the advantageous effects described above. Any of the technical features may be omitted appropriately unless the technical feature is described as essential herein.
Number | Date | Country | Kind |
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2012-253172 | Nov 2012 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2013/005799 | 9/30/2013 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
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WO2014/076863 | 5/22/2014 | WO | A |
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Number | Date | Country | |
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