JPS5996661A - Electrode substrate for fuel battery - Google Patents

Abstract

PURPOSE:To prevent mixing of reaction gas diffused from the side of electrode through formation of electrode substrate by arranging a graphite sheet extending from the edge of carbon property layer between the porous carbon property layers having a group of tunnels. CONSTITUTION:A graphite sheet 8 having average bulk density of 1.0g/cm<3> or more, gas transmitting degree of 0.2ml/cm.hr.mm.Ag or less is disposed in such a manner as being extending from the edge surface of carbon property layer 7 between the porous carbon property layers 7 having a plurality of tunnels 9 consisting of polyethylene at the center, average bulk density of 0.4-0.8g/cm<3> and gas transmitting degree of 20ml/cm.hr.mm.Ag or more, and these are laminated. A manihold 11 is arranged around the carbon property layer 7 through a sealing material 10. Accordingly, a bending strength can be enhanced, gas diffusion resistance can be made small and mixing of reaction gas leaking from the edge surface can be prevented securely, thereby improving the efficiency.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrode substrate for fuel cells, and more specifically, to
It has a graphite sheet (compressed graphite plate) that functions as a seven-layer sheet, and a porous carbonaceous layer having a group of hollow holes for introducing a reaction gas on both sides.
The present invention relates to an electrode substrate for a carbonaceous fuel cell in which a graphite sheet extends outwardly from a porous carbonaceous layer.

Conventionally, pipo lase using a pipo se/9retar obtained by lip-working an impermeable helium lead IJ'4 thin plate, e
Rake fuel cells are known.

In contrast to this, [2. Monopolar has a structure in which ribs are provided on one surface and a flat electrode surface on the other surface, and the reactive gas diffuses from the ribbed surface to the flat electrode surface. type electrode substrates have been developed.

Conventional mono 7J? - As shown in the attached Figure 1, the L-type cell consists of an electrode substrate 1, a catalyst layer 2, and a matrix 3 in which the electrolyte is made of gold, with a RISO 5 on one side and a flat structure on the other side. and a separator sheet 4,
Reactive gas (oxygen or hydrogen) from the ribbed surface of the electrode substrate 1
is diffused onto the flat electrode surface.

Conventionally, as a method for manufacturing electrode substrates for monopolar fuel cells, there has been a press-forming method based on short flame fibers (4).
¥56-48700), a paper-making method in which carbon fibers are dispersed (Japanese Patent Publication No. 53-18603), and a method of chemical vapor deposition of pyrolytic carbon on a web of carbon fibers (U.S. Patent Nos. 3 and 8).
No. 29,327) has been proposed. The electrode substrates obtained by these conventional manufacturing methods all consist of a single layer with a uniform structure throughout.

When such a homogeneous single-layer electrode substrate has a large bulk density, the gas diffusion coefficient is small, so the limiting current density is small, and the electrolyte retention amount is not sufficient, so the performance deteriorates earlier. In other words, it has the disadvantage of a short lifespan. On the other hand, when the bulk density is low, it has the drawbacks of high electrical resistance, high thermal resistance, and low mechanical strength such as bending strength.

In addition, in the case of an electrode substrate having a rib structure, as shown in FIG. As a result, its overall strength was somewhat unreliable. Therefore, the only way to maintain the strength of the molded plate is to increase the wall thickness of the flat plate part, which allows the reactive gas (oxygen or hydrogen) to diffuse through the entire electrode substrate from the rib side to the electrode surface side. The disadvantage is that the diffusion resistance becomes large when doing so. Moreover, it is difficult to perfect the flatness of the top surface of the rib.
Electrical and thermal contact resistance with the separator becomes so large that it cannot be ignored. In general, these contact resistances are said to reach several times the transmission resistance within the substrate, and the contact resistance of conventional monopolar electrode substrates is large, and therefore the temperature distribution between cells is independent.1 The power generation efficiency is It had the decisive drawback of lowering its performance.

Furthermore, when such electrode substrates are stacked and used as a fuel cell, the reaction gas also diffuses from the end surfaces of the electrode substrate 1, so it diffuses from the end surfaces of the electrode substrates on both sides of the monogrator sheet 4. The disadvantage is that the reactant gases mix on the side of the cell.

An object of the present invention is to provide an electrode substrate for a carbonaceous fuel cell that eliminates the above-mentioned drawbacks.

The electrode substrate of the present invention includes a graphite sheet.

The graphite sheet has a porous carbonaceous layer having hollow holes on both sides thereof, and the graphite sheet extends outward from the porous carbonaceous layer.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

Note that the same reference numerals are used for the middle part of the drawings.

FIG. 2 shows the cell structure of the electrode substrate of the present invention.

The electrode substrate of the present invention has a three-layer laminated structure in which porous carbonaceous layers 7 are integrally molded on both sides of a graphite sheet 8. A hollow hole group consisting of a plurality of hollow holes 9 is provided in the center of the thickness.

This hollow hole path 9 is continuous from one end surface of the electrode substrate (porous carbonaceous layer 7) to the opposite end surface, and each hollow hole path 9 is parallel to each other at tTi, and is parallel to the electrode surface of the electrode substrate. - approximately 'parallel to the side surfaces, and furthermore, both hollow holes 9 sandwiching the graphite sheet 8 are oriented at right angles to each other (see FIG. 2);

The cross-sectional shape of the hollow hole 9 may be arbitrary, and may be circular, for example, as shown in FIG. When the cross section of the hollow hole path 9 is considered circular, the dimension corresponding to the diameter (referred to as the monk diameter) is preferably 0.5 to 3 gates, and this equivalent diameter is 0.5 F.
If , Il+ is smaller than υ, the gas flow resistance becomes too large, and if it is larger than 3, the porous carbonaceous layer becomes too thick, reducing the volumetric efficiency of the cell in which the electrode substrates are laminated.

The porous carbonaceous layer 7 of the electrode substrate of the present invention is composed of a homogeneous porous carbonaceous layer material, and its average bulk density is 0.3.
~1.0 g/l, preferably 0.4-0.8%j, and the gas permeability is 2 kg/hr/m Aq.

It is preferable that it is above. A porous carbonaceous layer having an average bulk density and gas permeability in the above ranges has favorable mechanical strength, such as bending strength, and has favorable gas diffusion resistance. Note that the pores of the porous carbonaceous layer 7 are open holes! l)', and the pores of 60 or more are 10 to 100
Preferably, the diameter is within the range of μ.

The graphite sheet 8 of the electrode substrate of the present invention preferably has an average bulk density of 1.0 rings or more and a gas permeability of 0.2 mehr/mehr.
．． If it is less than 0, the desired density cannot be obtained. Also, since the graphite sheet 8 has a low gas permeability, it can function as a separator sheet (Fig. 1, 4); becomes unable to fulfill its role.

The thickness of the graphite sheet 8 is preferably 1/2 or less of the total thickness of the electrode substrate, and more preferably 01-3.

The carbonaceous electrode substrate having a three-layer structure of the present invention is manufactured as follows.

As the material for the porous carbonaceous layer, filler (short flame fiber 1
For example, 10 to 50% by weight of a binder (phenol resin, epoxy resin, petroleum-based and/or coal-based pitch, etc.) (granular activated carbon, etc.), and 10 to 40% by weight of a pore control material (polyvinyl alcohol, polystyrene, etc.). A mixture prepared by mixing, for example, 20 to 50 pieces of polypropylene, polyvinyl chloride, sugar, etc., is used.

As the hollow holes, polymers such as polyethylene, polypropylene, polystyrene, polyvinyl alcohol, polyvinyl chloride, etc., in the form of cross-like fabrics or lattices, are used.

Molding is carried out by the Sores F-Schiff method. The above-mentioned porous carbonaceous layer mixture is supplied into a press molding die, a mold is placed in the hollow hole λ on top of the mold, the porous carbonaceous layer mixture is supplied, and then a graphite sheet is supplied. After press molding, the mold is released, and the porous carbonaceous layer material, the hollow hole passage material, and the porous carbonaceous layer material are fed into the same mold in this order. The graphite sheet of the previously molded product is placed on top of it with the surface facing downward, and press molding is performed.

The press molding conditions were a mold heating temperature of 70 to 200C.

The molding pressure is appropriately selected from the range of 5 to 100 min and the pressing time of 1 to 60 minutes.

After press molding, the obtained molded product is post-cured for at least 2 hours, and then cured at 1000 to 3000 t:' for about 1
Bake for an hour. At this time, in the low-temperature pyrolysis process, about 7
It is preferable to raise the temperature slowly to 00C to prevent stress generation due to rapid contraction during gasification.

If the temperature is rapidly increased during this low-temperature thermal decomposition process, delamination and cracks may occur.

The electrode substrate of the present invention is manufactured as described above.

It has high mechanical strength, such as bending strength, and can be made into thin pieces, allowing the reaction gas diffusion layer to be made thinner, resulting in lower gas diffusion resistance and higher current density. Furthermore.

The dense carbonaceous layer plays the role of a separator sheet.
7'h, the conventional separator sheet is no longer required, reducing the cost and eliminating contact resistance. As a result, great effects such as a drastic reduction in the overall electrical resistance when laminated are achieved.Furthermore, since the graphite sheet extends outward from the porous carbonaceous layer, The reaction gas leaking from the end face of the porous carbonaceous layer of the battery (11
There is no danger of mixing on the surface, and the electrical board of Kinoi 9'1 can be said to be reasonable from the viewpoint of safety and cell efficiency. By the way.

Compared to the carbon fiber P type A'-type produced by the carbon shading method, l! ! 'lge strong 1 e becomes big and at the same time rib 0 black f) @ is not! We can expect a decrease in the υ1 price of 1 and a further decrease in 11.

FIG. 3 shows a cell structure when the electrode substrate of the present invention is layered and used as a fuel cell.

The substrate of the FJrJ of this invention is parallel to the hollow hole of the porous carbon 19 layer 7 and the 411 tortoise? 4 peripheral seals on the lfa side
The gas manifold 11 with the tubes 12 for supplying the reaction gas to the hollow holes 9r1 group is arranged as shown in Fig. F+1a. This peripheral sealing material 10 has electrical insulation properties and galvanic properties.
f'% of pit resistance to tylinic acid, ttT lk t4
%, for example, Teflon, layered silicone or ceramic itself, or a suitable material coated with Teflon or silicon carbide. Note that the arrows in FIG. 3 indicate the direction of flow of the reaction gas.

In a fuel cell using the cell of the present invention as shown in Fig. 3, there is no risk of reaction gas leaking from the end faces of the upper and lower porous carbonaceous layers mixing on the side surface of the substrate, which improves safety and cell efficiency. It has a remarkable effect on the surface as well.

Further, a more favorable result can be obtained by providing a graphite sheet for peripheral sealing in order to prevent leakage of the reaction gas from the end face of the porous carbonaceous layer 7 in contact with the peripheral sealing material 10. In this case, a material having the same physical properties as the graphite sheet 8 is used for the graphite sheet for the peripheral seal. Although it is sufficient that the peripheral sealing graphite sheet can cover the end surface of the porous carbonaceous layer 7 that is in contact with the peripheral sealing material 10, it is preferable that the peripheral sealing graphite sheet be integrated with the graphite sheet. That is, as shown in FIG. 4, a peripheral sealing graphite sheet 13 having a concave cross section is preferably used. in this case.

The graphite sheets 13 for peripheral sealing are used in combination at right angles as shown in FIG.
A three-layer structure will be established. The electrode substrate of the present invention shown in FIG. 4 can be manufactured in the same manner as the electrode substrate described above, as will be clear from Example 2 described later. Note that the glassite sheet 13 for peripheral sealing may extend outward from the porous carbonaceous layer 7.

The present invention will be explained in more detail below using examples.

The present invention is not limited to the following examples.

(Left below) Example 1 Short flame fiber (Kenbetsu Kagaku, M 104S) 40wt
%, phenolic resin (K, manufactured by Asahi Yukizai) 30
A mixture (mixture for porous carbonaceous layer) consisting of 30 wt % of polyvinyl alcohol particles (Japan Synthetic Chemical Industry Co., Ltd.) was supplied to a press molding die. Subsequently, a hollow hole material (a polyethylene molded product in the form of a lattice structure) was supplied, and then the above-mentioned mixture for a porous carbonaceous layer was supplied. Thereafter, a large graphite sheet with a thickness of 0.6 m+n and a total inner diameter of about 50 mm (25 mm on each side) was supplied. After that, 140℃, 40kl? /d for 20 minutes.

After the molding was completed, the mold was released, and the porous carbonaceous layer mixture, the hollow hole material, and the porous carbonaceous layer mixture were fed into the same mold in this order. On this.

The molded product was placed on a mold with the graphite sheet side facing downward, and press-molded at 140″G and 40 kg/crI for 20 minutes. The molded product was cured for about 2 hours.

The temperature is slowly raised to 700℃ at a rate of 100℃/hour, and then
It was baked at 00°C for 1 hour.

The obtained electrode substrate had a three-layer structure with a sealing part as shown in FIG. 2, and the hollow hole had a cross section of t'! , was circular and had a diameter of about 0.8 mm+. Table 1 shows the physical properties of this electrode substrate.

Table 1 Note 1) Excluding the hollow hole path part.

2) The value when the porous carbonaceous layer 7 and the phytosheet 8 in FIG. 2 are integrated.

Example 2 Graphite seam with a thickness of 0.3 mm in a press molding mold)
(Graph oil made by UCC) is placed as shown in Figure 5 (
15) in Figure 5), the mixture for porous carbonaceous material of Example 1 (16 in the diagram), the hollow hole material (17 in the diagram), and the mixture for porous carbonaceous material (16 in the diagram) were further supplied thereon. . In addition, in FIG. 5, 18 indicates the middle frame of the mold, and 19 indicates the lower plate of the mold.

Thereafter, it was press-molded at 140° C. and 4 ok/aft for 20 minutes. Furthermore, another identical molded article was manufactured using the same method. After applying carbon adhesive (phenolic resin) to the graph oil surface of these two molded bodies, the thickness is 0.3 mm, which is 50 m in total (approximately 25 tones on one side) larger than the outer shape of the molded bodies.
It was laminated to mm graph oil so that the directions of the hollow holes crossed.

After that, the molded product was cured for about 2 hours, and then heated to 100°C/
Slowly raise the temperature to 700°C, then further to 2000°C
Baked for 1 hour.

The obtained electrode substrate had the structure shown in FIG. 4 with a rigid seal portion, and the hollow hole had a nearly circular cross section and a diameter of about 0.8 mm. Table 2 shows the physical properties of this electrode substrate.

Table 2 Note 1) Excludes hollow hole passages.

2) Value that combines the porous carbonaceous layer 7, peripheral sealing Darafite sheet 13, and second graphite sheet 14 shown in FIG. 4.

3) Value including peripheral sealing graphite sheet 13 and second graphite sheet 14i.

[Brief explanation of the drawing]

FIG. 1 is a perspective view showing a conventional monopolar fuel cell structure, FIG. 2 is a perspective view of the electrode substrate of the present invention, and FIG. 3 is a cell when using the electrode substrate of the present invention shown in FIG. A perspective view showing the structure, FIG. 4 is a perspective view of another electrode substrate of the present invention,
Figure 5 is. 5 is a schematic diagram showing a method of manufacturing the electrode substrate of the present invention shown in FIG. 4. FIG. 7... Porous carbon 1Iji layer, 8... Graphite sheet, 9... Hollow hole path, 10... Peripheral sealing material. 11...Gas manifold F, 1a...Graphite sheet for peripheral seal, 14...Second graphite sheet. Agent 7 FI 1 Shimamuramoto Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Procedure Tani 1) jF F? Showa 59 Kin 12/] 22 + 1 1, display of 11 cases of Snake Showa Ei 7 ;I 1'!
7 ;Tganryoku 205628132, Komei name Fuel cell electric 41i base plate 3, ? 11i i1', relationship with master 1'1 1°1. ;11 names in 1 entry
(110) Prefectural industrialization (λ, j℃kai 7) 4
Agent Shinjuku 1-1-14, Shinjuku-ku, Tokyo
Mountain [(, 1 building (zip code 816 (+) phone (03)
354-8623ε3. Contents of the amendment The entire specification is amended as shown in the attached sheet. Description 1, Name of the invention Fuel cell electrode substrate 2, Claims (1) Consisting of two porous carbonaceous layers and a graphite sheet sandwiched between them, the porous carbonaceous layer having hollow holes] Y
1. An electrode substrate for a carbonaceous fuel cell, characterized in that the graphite sheet extends outward from the porous carbonaceous layer. (2) The electrode substrate according to claim 1, further comprising a peripheral sealing graphite sheet on an end face parallel to the hollow pores of the porous carbonaceous layer. O) The electrode substrate according to claim 2, wherein the graph eye 1 sheet for peripheral sealing is integrated with the graph eye sheet. (4) The porous carbonaceous layer has a peripheral seal on the end face parallel to the hollow holes, and the end face perpendicular to the hollow holes has a gas manifold. (The electrode substrate according to any one of claims 1 to 3. 3. Detailed Description of the Invention The present invention relates to an electrode substrate for a fuel cell, and more specifically relates to a separator sheet. Fulfills its function as Kori Craft I
A1-sheet (compressed graphite plate), both sides of A have a porous carbonaceous layer having a group of hollow holes for receiving a reaction mixture, and the graphite sheet1- has a porous carbonaceous layer J: This invention relates to an electrode substrate for a carbonaceous fuel cell that extends outward. Conventionally, there is a bipolar lever type fuel cell using a bipolar hibernate obtained by ribbing both sides of an impermeable graphite thin plate. The monopolar electrode substrate has a structure in which ribs are installed on one surface and the other surface is a flat electrode surface, and the reactant gas diffuses from the ribbed surface to the flat electrode surface. As shown in the attached Figure 1, a conventional monopolar cell has a rib 5 on one side and a flat structure on the other side.
Electrode substrate 1. Catalyst layer 2. Electrolysis Ga. Matrix 3 and separator sheet 4 impregnated with
The reactant gas (1'l!i element or hydrogen) diffuses from the ribbed surface of the electrode substrate 1 to the flat electrode surface. Conventionally, methods for producing electrode substrates for monopolar fuel cells include a press-forming method based on short-flame fibers (Japanese Patent Publication No. 57-166354), and a paper-forming method using dispersed carbon fibers (Japanese Patent Publication No. 18603-1983). , a method of chemically vapor depositing pyrolytic carbon onto a web of carbon fibers (U.S. Pat. No. 3,
No. 829,327) has been proposed. The porous carbonaceous electrode substrates obtained by these conventional manufacturing methods all consist of a single layer with an entirely uniform structure. When such a homogeneous single-layer electrode substrate has a low bulk density, the gas diffusion coefficient is small, so the limiting current density is small, and the electrolyte retention amount is not sufficient, so the performance deteriorates quickly. In other words, the drawback is that it has a short lifespan. On the other hand, when the bulk density of () is small, the electrical resistance and thermal resistance have the disadvantage that the bending strength and the mounting surface strength are similar. White, as shown in Figure 1, the section modulus is small because one side is not flat;
For example, stress concentration occurred at the sharp edge portion 6 at the base of the rib 5, making the overall strength unreliable. Therefore, in order to maintain the strength of the molded plate, the wall thickness of the flat plate part is not thickened, and reaction scum (oxygen) passes through the thin thickness of the electrode substrate from the rib side to the electrode side. There is a drawback that the diffusion resistance becomes large when diffusion of hydrogen (or hydrogen) occurs. Moreover, it is difficult to perfect the flatness of the planar part of the rib believer11,
Electrical and thermal contact resistance with the lever becomes so large that it cannot be ignored. In general, it is said that these contact resistances reach several times the transmission resistance within the root, and the contact resistance of conventional monopolar electric 4FI substrates is large, and therefore the non-uniformity of the hot stone distribution between cells, 'ff , C- had a decisive drawback of reduced electrical efficiency. Furthermore, when such electrode substrates are used as a fuel cell by stacking them on a car, the reaction gas also diffuses from the side end surfaces of the electrode substrate 1. The drawback is that the reactant gases that come in are mixed on the side of the battery. An object of the present invention is to provide an electrode substrate for a carbonaceous fuel cell that eliminates the above-mentioned drawbacks. The electrode substrate of the present invention has a graphite sheet 1~ and a porous carbonaceous layer having hollow hole groups on both sides thereof, and the graphite sheet 1~ has a porous carbonaceous layer on the outside than the porous T/I carbonaceous layer. Distraction C. Hereinafter, the present invention will be described in detail with reference to the accompanying drawings (1), in which the same reference numerals are used for the middle portion of the drawings. A tentative structure of electrode J1 of the present invention is shown in FIG. The electronic substrate of the present invention is a three-layer (I'
The porous carbonaceous layer 7 has a hollow hole group consisting of a plurality of hollow holes 9, preferably at approximately the center of its thickness. This hollow hole path 9 is continuous from one end surface of the porous carbonaceous material F17 to the opposite end surface, and each hollow hole i69 is approximately parallel to the U and is approximately parallel to the electrode surface and the negative side surface of the electrode substrate. In addition, the hollow pore groups 9 of both porous carbonaceous layers across the graph 1-1 sheet 8 are parallel to each other, and the hollow pore groups 9 of both porous carbonaceous layers are oriented at right angles to each other.
(See Figure 2). The cross-sectional shape of the hollow hole 9 may be arbitrary, for example, it may be circular as shown in FIG. When the cross-sectional area of this hollow hole path 9 is converted into the cross-sectional area of a circle, it corresponds to the diameter of the circle ~ J method (
The equivalent diameter (referred to as the equivalent diameter) is preferably 0.5 to 3IllI11. If this equivalent diameter is smaller than 0.5111 m, the electrode substrate area becomes large and the length of the hollow hole path becomes long, and the gas flow resistance becomes large. If the thickness is too large and exceeds 3 mm, the porous carbonaceous layer becomes too thick and the volumetric efficiency of the layer on which the electrode substrates are laminated decreases. The porous carbonaceous layer 7 of the electrode substrate of the present invention is composed of homogeneous porous carbon 7j rice grains, and its average bulk density is 0.3.
~1.0<1/ci, preferably 0.4~o, gg
/ cri 'C: Yes, 1 gas permeability IJ, 207
/ cm · hr - mmAq, preferably 2. A porous carbonaceous layer having an average high density and gas permeability of 95 or less preferably has a surface strength such as bending strength, and has a preferable scum diffusion resistance. J3, the porous carbonaceous layer 7 has every 1 pore C', and 6()% or more of the pores in A-11J<10-1
Preferably, the value is within the range of 00μ. Kionai Meiden (Kuranoa I1-C1-8 on the board is 1
, the average bulk density on OQ y' ci IX and 0.2i
/ cm -hr -111...△q, preferably having a dregs permeability of 1. If the average high density is less than 1.0 (J/ci), the desired durability cannot be obtained.Furano Eye 1-Sheet 8 has low gas permeability, so it is transferred to Separator Sea 1 (Fig. 1, 4).
(It can be used, but the gas permeability is 0.2ml!/
cm・old゛・mmAq, cl: 1.The role of C cannot be fulfilled. The thickness of Graphite 1 to Graphite 1 to 8 is 1/2 of the total thickness of the electrode substrate.
It is preferably less than or equal to 0.1 to 3 mm, and more preferably 0.1 to 3 mm. The carbonaceous electrode substrate having the three-layer structure of the present invention is manufactured as follows. As the material for the porous carbonaceous layer, the filling side (short leg elementary fiber 1
For example, 10 to 50% of the combined IJ (granular activated carbon, etc.)
For example, 20 to 40 wt. ) is used, for example, by mixing 20 to 50% by weight. The short-legged elementary fibers used as the filling side preferably have a fiber diameter of 5 to 30 μm and a pAN length of about 0.05 to 2 mm. If the fiber length exceeds 2 mm, one culm that is formed becomes entangled with the soybean beans and becomes pill-like, making it impossible to obtain the desired high density and pore size distribution. Na, 13.0.05
mmJ: Riff, if it is 0, the required strength cannot be obtained. Further, when the short flame fiber is fired at 2000°C, the carbonization line shrinkage rate is in the range of 0.1 to 3.0%. If the linear shrinkage rate is too high, there is a risk that this will be one of the causes of cracks during firing. The use of such short-flame fibers and silk makes it especially possible to manufacture large-sized electrode substrates. The binder used in water serves as a carbon buying binder after carbonization to bond between carbon fibers, and in order to achieve the desired high density, the carbonization yield must be 30 to 75%. l·1 fat in the range of m% is preferred. Possible examples of such a binder include phenolic resin, petroleum and/or coal-based pitch, furfuryl alcohol resin, etc. 1.1, powdered phenolic resin. It has been found that L, alone or in a mixture with powder pitch, is most preferable during dry mixing and has excellent characteristics of the obtained substrate.The mixed matrix of the binder resin is 10 to 50% by weight, preferably 20% by weight.
~40 weight Φ% is used, and if there is less than 10 weight % J, the strength of the electric TFI board to be applied will be lower due to the lack of C hills, and if there is more than 50 weight % J, The desired pore size and high density cannot be obtained. The pore control material used in the present invention is an important material that defines the pores of a molded article. In the present invention, in order to adjust the high density and pore size, 70% or more of the particles are 30 to 300
Organic particulate materials with particle sizes in the μ range are used. As the organic particulate material, one that does not volatilize or exhibit melt flow at at least 100° C. is used. That is, the organic particulate material is formed at a molding temperature of d3 J: and a pressure of
Thermal deformation is permitted, but volatilization or melt flow is prohibited. For the above reasons, preferred pore control materials include polyvinyl alcohol, polyvinyl chloride, polyethylene, polypropylene, borisdylene, sugar, etc., or mixtures thereof, which have a carbonization yield of 300 weight or more. If the carbonization yield is lower than A'4, it may be difficult to adjust the bulk density and pore diameter.
4I is selected from the range of U3O-500 weight depending on the 1L tentative bulk density and pore size. In addition, when mixing, when expressed as /Z weight %, where A is the filling material, B is the binder, and C is the pore regulating material, (Δl-C) 7/[3-10,'+~4
,0) f41! i1 After adjusting the 8 components, good J,
You can get better results. Outside this range, it is not possible to satisfy the requirements for high density 1σ1 bending strength, sword penetration, and electrical resistance. In the present invention, (, charge jv Δ is 10, 5 (
) It is preferable that the binding material B is selected from the range of 20 to 40% by weight for the pore control material C in the range of 20 to 50% by weight. As the hollow holes, polymers such as polyethylene, polypyrene, polyvinylalcohol, polyvinyl chloride, etc., such as cloth-like fabrics and sugre lattices, are used. In order to cover the equivalent diameter of the hollow holes in a preferable range of 171+1, the cos-like fabric C is made of a single yarn or +1 with a shoulder diameter of 0.5 to 3.3 ml made of the polymeric substance.
A plurality of convergent yarns are converged in the gas flow direction 1. :
``I' row single yarn or convergent yarn spacing 1.5-・5 ml
l, the distance between single yarns or convergent yarns in the direction perpendicular to the waste flow is 1
．． 5 to 50 Illnl etc. (2 J, Use sea urchin woven mold. Also, extrude the sudare lattice molded product (J, extrude the above polymer material in a molten state into a mold 1), The lattice of the Sudare lattice...1 is circular, rectangular, square, or star-shaped. It can be expressed as any shape, such as [Ji surface cutting].
．． 5-3mm J, sea urchin) about 1 foot long. Streak 1 {
Meiryo's waste flow is flat on 6 sides? -1'c; 1st call during completion
The spacing of 1.5-・5 n1m and (the spacing of the fence in the yj direction perpendicular to the Hanonos flow is 1.j]-50mm 9・i2
1111 /J White,) L1 (from 42) fi IJ Reru 1 These cross-repellent objects or sudare lattice moldings (J
During the formation of the porous 41 carbon layer in the mold, the porous bone char' If you put it in 1 of the L-composite, J, (, Pressure molding after A, [I prefer the upper stage of history) - (, Excluding the part that is carbonized by carbonization firing,
Most of it is caused by thermal decomposition.1. y l Porous F1
Hollow pores are formed within the transparent layer. In general, when forming such a hollow hole, after firing, it is heated to room temperature or cold. It has been confirmed that the diameter of the hollow hole ) 01'' becomes smaller by 3.~7% i'i, -7J, so this convergence t* 'a'
lIl'A L/ T, A ￥'J MA The fiber diameter or equivalent diameter of the object or molded body) It can be adjusted to The molding is done using a press molding method.
L ijj, feed the fr5-containing material for the first layer of Y'1 into a press molding container, insert 4 hollow holes in it, and further supply the mixed mixture for the porous V'1 layer, After that, the gelatin film sheet 1- is supplied.After press molding, the mold is released.
, the above-mentioned porous charcoal cap 7゛ (for the layer o'≧1, the above-mentioned hollow hole passage material, and the above-mentioned porous (<1 for the carbonaceous layer 14 M'! Provide I in this order G-vr
-ru. The graphite sheet 1 of the molded product previously molded was placed on the surface of the molded article U with the 1-side facing downward, and the molded product was press-molded and covered. At this time, two molded products for the porous carbonaceous layer described in "-" may be molded, and then these may be bonded to both sides of the C. graphite 1 to C. 1 by using an adhesive. Press molding conditions are mold heating 'IFA a' to 2
00''C1 Molding pressure 5 to 100 kg/crA, pressure holding time 1 to GO minutes as appropriate. After being 1-re(υ) for 1 hour, it was heated to 1000℃ under an inert atmosphere.
Inter-fired Jru. At this time, low-temperature heat')) In the FJ'i overculm, the temperature is about 700℃, for example, 100±! l
O"C/ Il'l 'c 'l'? Heating and gasification 1
1. 'l's grudge if! It is preferable to prevent stress generation due to severe contraction. This low-temperature thermal decomposition process C causes delamination N1 and crack generation if the temperature is rapidly increased. I-1 J, Wood 57H Mei no Den (Φ31N) manufactured by Uni
The board has regional strength 1! Iile is that the bending force is too strong, and
119. When the layer is made thinner, the gas diffusion resistance becomes smaller and the current becomes larger. plays a role in lever resistance 1. Therefore, the conventional separator sea j-t, J is unnecessary, 1Illi is reduced, etc.] 1"I] Σ;mi resistance becomes 14 As a result, the electrical resistance of the stacked platform as a whole is drastically reduced, which is a great effect.
- By extending the sheet outward from the porous carbonaceous layer, there is no risk of reaction gas leaking from the end faces of the upper and lower porous carbonaceous layers mixing on the side of the cell, improving safety and cell efficiency. The electrode substrate of the present invention can be said to be an ideal type. Incidentally, compared to the carbon fiber assembly vapor type made by the carbon fiber papermaking method, the C1 bending strength is improved, but at the same time, the reso (q graphite plate is no longer required), the price is expected to decrease, and the electrical resistance is also expected to decrease. Fig. 3 does not show the 1z layer structure when the electrode substrate is used as a fuel cell with v1 layers. A peripheral seal plate 10 is pasted to the top by a suitable means such as a tack, and a gas mer-hold 11 with a tube 12 for supplying a reactive gas to the hollow hole 1 and fj P=Y is attached. The surrounding sealing material 10 is arranged as shown in Fig. 3.This peripheral sealing material 10 has electrical insulation properties and a 6.1 heat IJ1 and υ・10 (1%
Corrosion resistance f1 against phosphoric acid is good. J]-No1-'', use one inked with ionic carbide]-7-1. Note that the arrow in No. 3I71 corresponds to the direction of the flow of waste. ) In an i-size battery using the rail of the present invention, there is no risk of reaction residue leaking from the end surfaces of the upper and lower porous carbonaceous layers and mixing with the soil on the side surface of the substrate. , in terms of safety and efficiency?'''t) It has a remarkable effect. In addition, gelatin for the peripheral seal is used to prevent leakage of reaction residue from the end face of the peripheral seal 4Δ10 of the porous carbonaceous layer 7.・As shown in Fig. 4, the sheet is placed in row 1 (row t-0). Crannon・
A monthly rate with similar physical properties to sheet sheet 8 is used. This graph I sheet 1-13 for peripheral sealing is porous (2+ carbon "if it can cover the end surface in contact with the peripheral sealing material 10 of the iJt layer 7"-minute, but from graph eye 1 to sea 1 14 In other words, as shown in FIG.
In this case, the peripheral sealing graphon sheet 1-13 is placed at right angles as shown in Figure 4, or the second peripheral sealing granon sheet 1-13 is placed between the two peripheral sealing granon sheets 1 and 1-13.
A graphite sheet 14 is installed to create a two-layer drawing. The electrode substrate of the present invention as shown in FIG. 4 can be manufactured in the same manner as the above-mentioned electrode substrate.
It can also be preferably produced in this way. Incidentally, the peripheral sealing graph eyes 1 to 13 may extend outward from the porous carbonaceous layer 7J in the direction of the hollow hole. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. Example 1), 0 carbon content eyebrow 1 (Tsu 1 Hagaku Kagaku, M10/13.''-
1j Uniform shoulder 1fiO, 45mm, instep uniform #lI diameter 12t
s) 40wt%, fuconol resin (Kawaishi (Δ1
30wt% and polyheal alcohol particles (M1 made by Synthetic Chemical Co., Ltd., average particle diameter 180%) 301Y
19 (uniform from + to 4) [Breath molding metal that molds the compound (mixture for porous carbon 71 layer) into a predetermined shape! 1゛! 1 was compatible with 2, pile C1 hollow hole through shrine (Sugure (・8
Child-like poly-1-rylene molded product, 1-tree lattice is equivalent to 100 1 reservation 0
．． A 8 mm round Igi surface was supplied, and the porous carbonaceous layer mixture was further supplied, and then,
Thickness 0.6mm [TEJ] Clasp 1 inner shape J, ri all! i
Approximately 0 mm (approximately 25 mm on one side) Graph/-r1 ~ sheet (Graph Oil manufactured by UCC) with large p noise was supplied. After that, 140℃, 40J/cta T'
Pressed for 20 minutes. After molding is completed, the mold is released and the same inner shape is placed in the right mold -1-
The mixture for the porous carbon layer Y1, the hollow hole material described above, and the mixture for the porous carbonaceous layer were supplied in this order. On top of this, place the molded product on the -C mold with the graphite 1 to sea 1 side facing downward, and place the molded product at 140°C and 40k (1/C
Press molding was performed using IA for 20 minutes. The molded product was heated to 140℃, 0
．． After curing for about 2 hours at 5kg/crj, 100
'C/hour 7 (+ (11'), slowly warm the stomach at ℃,
Further, it was fired at 2000"C for 5 minutes. The electrode substrate thus prepared was placed in a three-B molded structure with a seal as shown in Fig. 2, and the hollow hole had an approximately circular cross section and a diameter of was approximately 0.8 mm. The physical properties of this electrode substrate are shown in Table 1. Notes to Table 1 1) Hollow hole path portions are excluded. 2) Pore 1j1 carbon buying layer 7 and graph eye in Figure 2 1~
1 shift that combines shi-8. Example 2 Grapheye 1 with a thickness of 0.3111 m in a press molding mold
-Sea 1- (Graph Oil manufactured by UCC) was placed as shown in Fig. 5 (15 in Fig. 5), and on top of it, the mixture for porous carbonaceous layer of Example 1 (16 in the figure), hollow hole material. (17 in the diagram
), and also supplied a porous carbonaceous layer mixture. Furthermore, the fifth
In the figure, 18 indicates the middle frame of the mold, and 19 indicates the lower plate of the mold = l-. Thereafter, press molding was carried out at 140°C and 40k (110+f) for 20 minutes.Furthermore, another identical molded body was manufactured using the same method.Carbon adhesive (phenolic resin) was applied to the graph oil surface of these two molded bodies. After coating, it is pasted onto graph oil with a thickness of 0.3 ml, which is about 50 mm in total (approximately 25 mm on each side) smaller than the outer shape of the molded object, so that the directions of the hollow holes cross. After post-curing at 140°C and 0.5k (J/ctA) for about 2 hours, it was slowly warmed to 700°C at 100°C/hour and further baked at 2000°C for 1 hour. The electrode substrate had a structure with a seal part as shown in Fig. 4, and the hollow hole jυ had a nearly circular cross section and a diameter of about 0.8n+m. The material f'l liii'i is shown in Table 2.Table 2 2) The granofoils 1 to 13 for sealing around the porous carbonaceous layer 7 shown in Fig. ff14 and the second graph 11 to 14 are integrated. 3) Value obtained by combining graphs 1-13 and 2nd graphs 1-1-14 for peripheral seals. 4. Brief explanation of the drawings Figure 1 shows the conventional monopolar type fuel cell. Battery (-A perspective view showing a chill structure; FIG. 2 is a perspective view of one plate of the electrode sheet of the present invention; FIG. 3 is a perspective view showing the cell structure when the electrode plate of the present invention shown in FIG. 2 is used) 4 is a perspective view of another electrode J1 plate of the present invention, and FIG. 5 is a schematic diagram showing a method of manufacturing the electrode curtain plate of the present invention shown in FIG. 4. 7. ...Porous 1 (11 stain elemental layers, 8...
・・・・・・Graph Eye 1 to Sea 1, 9・・・・・・
...Hollow hole road, 10......Peripheral seal shrine, 11...Cast manifold, 13.
・・・・・・Graph Eye 1 to Sea 1 for peripheral seals
114......Second Graphite Sea 1~. 293-

Claims (1)

[Claims] (A porous carbonaceous layer is provided on both sides of the 11gra 7ite sheet, and the porous carbonaceous layer has a group of hollow holes,
An electrode substrate for a carbonaceous fuel cell, characterized in that a graphite sheet extends outward from a porous carbonaceous layer. (2) The electrode substrate according to claim 1, further comprising a peripheral sealing graphite sheet on an end face parallel to the hollow pore groups of the porous carbonaceous layer. (3) The electrode substrate according to claim 2, wherein the graphite sheet for peripheral sealing is integrated with the graphite sheet by laminating them together. (4) A patent claim characterized in that the porous carbonaceous layer has a peripheral sealing material on the end face parallel to the hollow holes, and a gas manifold on the end face perpendicular to the hollow holes. The electrode substrate according to any one of the first to third terms.