Patent Application
20090130534
The present invention relates to a fuel cell separator which is produced by performing press molding on a preform that is formed into a plate-like shape, with using a molding die, and also to a method of producing it.
A fuel cell separator has: a role of adequately holding an MEA (Membrane Electrode Assembly) in a cell of a fuel cell (a unit member in which an MEA is interposed between fuel cell separators) and supplying fuel (hydrogen) and air (oxygen) that are necessary in the electrochemical reaction; that of collecting electrons obtained by the electrochemical reaction for functioning as a fuel cell, without a loss; and the like. In order to play these roles, a fuel cell separator is required to have characteristics of 1. mechanical strength, 2. flexibility, 3. electrical conductivity, 4. molding processability, and 5. gas impermeability.
As a material of a fuel cell separator of this kind, conventionally, it is usually that graphite is used as the main raw material from the viewpoint of improving the corrosion resistance, and, in the initial stage of development, a fuel cell separator is produced by cutting sintered carbon. Because of the problem of cost, recently, a technique is employed in which a compound of a thermosetting resin such as a phenol resin or an epoxy resin, and graphite is produced as a molding material, and the compound is compression molded to be formed as a fuel cell separator. Usually, a compound which is used as a molding material is supplied in a powdery state. Therefore, such a compound is once subjected to primary molding for producing a preform at a low temperature at which a resin does not react, and then conveyed to a press molding die which performs secondary molding. As a fuel cell separator in which a preform is once produced by primary molding, and secondary molding is then performed to attain the excellent molding processability, and a method of producing it, known are those disclosed in Patent Reference 1.
On the other hand, as graphite which is to be used as the main raw material of a fuel cell separator, expanded graphite is sometimes used. For example, graphite disclosed in Patent Reference 2 is known. In a fuel cell separator using expanded graphite, expanded graphite is preferable means for effectively using the inherent characteristics of expanded graphite, such as the heat resistance, the corrosion resistance, the electrical property (conductivity), and the thermal conductive characteristics, to exert the predetermined cell performance. Namely, such a separator can be formed so as to have the excellent electrical conductivity. In order to realize a light and compact fuel cell which uses as many as several hundreds to several thousands of separators, and which has a light and compact configuration that is required in the automobile use or the like, it is necessary to reduce the thickness of each separator as far as possible without impairing the required functions.
When a conventional fuel cell separator in which expanded graphite is used as the main raw material is made thin, however, it easily cracks and allows gasses to permeate readily therethrough. Therefore, such a separator has drawbacks in the above-mentioned mechanical strength and gas impermeability.
Therefore, it is an object of the invention to, in order to attain excellent electrical conductivity and molding processability, improve a fuel cell separator that is to be produced by performing press molding on a preform in which expanded graphite is used as the main raw material, so as to produce the preform by a papermaking method, whereby the characteristics of the mechanical strength, the flexibility, and the gas impermeability are improved, and a light and compact configuration that is preferred in the automobile use or the like can be realized.
The invention set forth in claim 1 is a fuel cell separator which is to be produced by performing press molding on a preform 14 that is formed into a plate-like shape, with a molding die, wherein
the preform 14 is configured into a sandwich structure where a first sheet 14A obtained by a papermaking process using a raw material in which a fibrous filler is added to expanded graphite is interposed between a pair of second sheets 14B in which a thermosetting resin is applied to graphite.
The invention set forth in claim 2 is characterized in that, in the fuel cell separator according to claim 1, the first sheet 14A has a thermosetting resin which is impregnated after the papermaking process.
The invention set forth in claim 3 is characterized in that, in the fuel cell separator, the thermosetting resin used in the second sheets according to claim 1 and/or the first sheet according to claim 2 is a phenol resin.
The invention set forth in claim 4 is a method of producing a fuel cell separator, having a secondary molding step of performing press molding on a preform 14 that is formed into a plate-like shape, with using a molding die 15, wherein the preform 14 is produced by a primary step S1 having: a papermaking step a of performing a papermaking process using a raw material in which a fibrous filler is added to expanded graphite; and a stacking step c of stacking a first sheet 14A obtained in the papermaking step a while interposing the first sheet between a pair of second sheets 14B in which a thermosetting resin is applied to graphite.
The invention set forth in claim 5 is characterized in that, in the method producing a fuel cell separator according to claim 4, the primary step S1 has a post-impregnating step b of impregnating a sheet-like member which is paper-made in the papermaking step a, with a thermosetting resin, thereby producing the first sheet 14A.
The invention set forth in claim 6 is characterized in that, in the method producing a fuel cell separator, a phenol resin is used as the thermosetting resin for producing the second sheets 14B according to claim 4 and/or the first sheet 14A according to claim 5.
According to the invention of claim 1, although described in detail in the paragraph of embodiments, the preform has the three-layer sandwich structure where the first sheet obtained by a papermaking process is interposed between the two second sheets in which the graphite and the thermosetting resin are used as the main raw materials, i.e., the configuration where the first sheet which has excellent mechanical and electrical characteristics, which is thin, in which characteristics such as the specific resistance are less dispersed, which can be easily mass-produced, and which is advantageous in production cost is interposed between the pair of second sheets having an excellent moldability. As a result, in order to attain excellent electrical conductivity and molding processability, the fuel cell separator to be produced by performing press molding on a preform in which expanded graphite is used as the main raw material is improved so that the preform has the sandwich structure where a paper-made sheet produced by a papermaking process is interposed, and the second sheets having an excellent moldability are positioned in the surface, and therefore it is possible to provide a fuel cell separator in which, although the characteristics of the mechanical strength, the flexibility, and the gas impermeability are improved, the moldability is excellent, and a light and compact configuration that is preferred in the automobile use or the like can be realized.
According to the invention of claim 2, the first sheet produced by the papermaking process in which expanded graphite is used as the main raw material is later impregnated with the thermosetting resin. In addition to usual functions and effects due to addition of a thermosetting resin, consequently, there is an advantage that the thermosetting resin enters into gaps of the paper-made sheet-like member to fill the gaps, and the gas permeability and the bulk density are advantageously affected, whereby the performance can be further improved. In this case, it is possible to provide a fuel cell separator having a sandwich structure in which, when, as in claim 3, the thermosetting resin used in the first sheet is a phenol resin which is synthesized by condensation polymerization of phenols and aldehydes, further preferable functions and effects that the insulating property, the water resistance, the chemical resistance, and the like are excellent are added, or, when the thermosetting resin used in the second sheets is a phenol resin, both an improvement of the gas permeability coefficient and an excellent moldability can be more efficiently attained. Furthermore, the following means 1. to 5. may be employed.
When 1. the degree of impregnation of the phenol resin is set to a range of 5 to 30%, or 2. the material ratio of the expanded graphite is set to 60 to 90%, the performance target values that the contact resistance is 30 mΩ·cm2 or less, the bending strength is 25 MPa or more, the bending strain is 0.6 to 2.1%, and the gas permeability coefficient is 1×10−8 mol·m/m2·s·MPa or less can be satisfied, and hence it is advantageous (see
The invention of claim 4 is realized by configuring the invention of claim 1 as a method, the invention of claim 5 is realized by configuring the invention of claim 2 as a method, and the invention of claim 6 is realized by configuring the invention of claim 3 as a method. The inventions can provide a method producing a fuel cell separator which can exert functions and effects equivalent to those of the corresponding claim.
Hereinafter, embodiments of the fuel cell separator and method of producing it according to the invention will be described with reference to the drawings.
First, the configuration and operation of a solid polymer electrolyte fuel cell comprising the separator of the invention will be described briefly with reference to
In peripheral portions of the separators 4, as shown in
In the thus configured solid polymer electrolyte fuel cell E, the fuel gas which is supplied from a fuel gas supply apparatus disposed outside to the fuel cell E, and which contains hydrogen is supplied to the fuel gas flow paths 12 of the unit cells 5 through the fuel gas supply manifold to exhibit an electrochemical reaction on the sides of the anodes 2 of the unit cells 5, and, after the reaction, the fuel gas is discharged to the outside through the fuel gas flow paths 12 of the unit cells 5 and the fuel gas discharge manifold. At the same time, the oxidation gas (air) which is supplied from an oxidation gas supply apparatus disposed outside to the fuel cell E, and which contains oxygen is supplied to the oxidation gas flow paths 13 of the unit cells 5 through the oxidation gas supply manifold to exhibit an electrochemical reaction on the sides of the cathodes 3 of the unit cells 5, and, after the reaction, the oxidation gas is discharged to the outside through the oxidation gas flow paths 13 of the unit cells 5 and the oxidation gas discharge manifold.
In accordance with the above-mentioned electrochemical reactions, an electrochemical reaction in the whole fuel cell E advances to directly convert the chemical energy of the fuel to the electric energy, thereby exerting a predetermined cell performance. Because of the property of the electrolyte film 1, the fuel cell E is operated in the temperature range of about 80 to 100° C., and hence the operation involves heat generation. During the operation of the fuel cell E, therefore, cooling water is supplied from a cooling water supply apparatus disposed in the outside, to the fuel cell E, and circulated through the cooling water paths, thereby preventing the temperature in the fuel cell E from being raised.
The cell structure may be that shown in
Next, the manner (production method) of producing the separator 4 will be described. In the production method, the separator 4 is produced by performing press molding a preform that is formed into a plate-like shape, with using a molding die. As shown in
The primary molding step S1 is a step of, as shown in
The papermaking step a is a step of producing the first sheet 14A by a papermaking process using a raw material in which a fibrous filler is added to expanded graphite, and, as shown in
The post-impregnating step b is a step of impregnating the first sheet 14A which is paper-made in the papermaking step a, with a phenol resin, thereby producing the first sheet 14A in a state where it becomes a component of the preform 14. The stacking step c is a step of interposing and integrating the first sheet 14A produced in the papermaking step a and the post-impregnating step b, between a pair of second sheets 14B in which a phenol resin (an example of a thermosetting resin) is applied to graphite (graphite powder or the like), thereby producing the preform 14 configured by, as shown in
The secondary molding step S2 is a step of pressurizing by a press the preform 14 having the three-layer sandwich structure with using the molding die 15 configured by, for example, an upper die 15a and a lower die 15b, thereby producing the separator 4 having the predetermined final shape. Hereinafter, a specific producing method, its example, and the like will be described.
First, the papermaking step a in the primary molding step S1 is performed in the following manner. A fibrous filler in which 3% of carbon fibers, 7% of acrylic fibers, 1% of PET fibers, and 1% of aramid fibers are blended is defiberized with using a domestic mixer to be adjusted so as to have a predetermined pulp density (for example, 1%). To the adjusted pulp slurry, 83% of expanded graphite of, for example, 40 μm is added, and water is further added to readjust the slurry to the solid content concentration of 0.1%. Thereafter, small amounts of other blending materials [aluminum sulfate, a yield improving agent [Hymolock NR11-LH (trade name)]] are added, and a papermaking process is performed while using the slurry as a raw material for papermaking (see Example 1 of
In the post-impregnating step b in the primary molding step S1, impregnation is performed with using a phenol resin solution to obtain the first sheet 14A for the preform 14. The impregnation amount of the phenol resin in Example 1 is set so that the blending ratio after impregnation is 5%. The first sheet 14A produced by the papermaking process is slightly inferior in moldability, for example, hardly bendable, but has excellent mechanical and electrical characteristics.
Although not illustrated, a second-sheet forming step in the primary molding step S1 is a step of coating graphite powder (preferably, having a particle diameter of about 1 to 200 μm) with a phenol resin to produce the second sheet 14B which is resin carbon. The second sheet 14B which is resin carbon is inferior in mechanical characteristics, but excellent in moldability.
Alternatively, the second sheet 14B may be produced in the following manner. The sheet is configured by a thin plate-like molded member in which a carbon-phenol resin molding compound that is prepared by mixing and reacting phenols, aldehydes, and carbon in the presence of a catalyst is molded. The carbon-phenol resin molding compound is obtained as a material in which carbon is thinly and uniformly covered with the phenol resin, by reacting phenols and aldehydes with carbon in the presence of a catalyst while being mixed with carbon. In this case, even when the amount of carbon is increased, a thin plate-like molded member in which carbon particles are surely bonded and the gaps between carbon particles are filled with the phenol resin can be obtained, and it is possible to easily obtain a fuel cell separator which is excellent in mechanical strength and electrical conductivity, and which has a low gas impermeability.
In the secondary molding step S2, the preform 14 having the three-layer sandwich structure which is produced in the primary molding step S1 is subjected to heat and pressure molding during five minutes at a surface pressure of 20 MPa with using a molding die of 170° C. (see
In a bending test (the bending strength and the bending strain), the bending strength and the bending strain are measured by the three-point bending test. The measurement was conducted while setting the distance between fulcrums to 7.8 mm, the cross-head speed to 10 mm/min., and the width of the test pieces to 15 mm. The gas permeability coefficient was measured in accordance with JIS K7126A method (differential pressure method) with using a gas permeability measuring device (BT-1 manufactured by Toyo Seiki Seisaku-sho, Ltd).
In
Example 10 shows data in the case where graphite was applied to the surface of the preform 14, i.e., the surface sides of the second sheets 14B, 14B. In Example 10, namely, an applying step of applying graphite to the surface of the second sheet 14B which is formed by the carbon-phenol resin molding compound was added. In all Examples 1 to 10, the blending ratios (blending amounts) of the carbon fibers, acrylic fibers, PET fibers, and aramid fibers which constitute the fibrous filler are identical.
In
In
As seen from
As described above, the invention is a separator which is to be produced by performing press molding on a preform that is formed into a plate-like shape, with a molding die, wherein the preform is configured into a sandwich structure where the first sheet obtained by the papermaking process using a raw material in which a fibrous filler is added to expanded graphite is interposed between the pair of second sheets in, which a thermosetting resin is applied to graphite. When the thickness is 0.15 mm, therefore, the performance target values that the contact resistance is 30 mΩ·cm2 or less, the bending strength is 25 MPa or more, the bending strain is 0.6 to 2.1%, and the gas permeability coefficient is 1×10−8 mol·m/m2·s·MPa or less can be satisfied. As a result, in order to attain excellent electrical conductivity and molding processability, the fuel cell separator to be produced by performing press molding on a preform in which expanded graphite is used as the main raw material is improved so that the preform has the sandwich structure where the second sheet made of resin carbon is sandwiched between the two first sheets produced by a papermaking process, and therefore it is possible to provide a fuel cell separator in which the characteristics of the mechanical strength, the flexibility, and the gas impermeability are improved, and a light and compact configuration that is preferred in the automobile use or the like can be realized.
The separator has the sandwich structure where the first sheet 14A which is excellent in mechanical strength and electrical characteristics is interposed between the pair of second sheets 14B which are excellent in moldability. In addition that the above-mentioned characteristics are satisfied, therefore, the moldability is improved while the sealing property (gas permeability coefficient) is further improved, with the result that a fuel cell separator having excellent total performance, and a method of producing the fuel cell separator can be realized.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2006-136449 | May 2006 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2007/000407 | 4/13/2007 | WO | 00 | 11/14/2008 |
