JP2015096464A - Porous carbon electrode base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a porous carbon electrode base material having suppressed formation of open holes.SOLUTION: There is provided a sheet shape porous carbon electrode base material having the number of open holes having length of a major axis of 1 mm or more of 0.2 or less per 1 m. The porous carbon electrode base material has a thickness of 0.05 to 0.4 mm, bulk density of 0.3 to 0.8 g/cm, flexural strength of 30 MPa or more, flexural deflection of 1.5 mm or more and area of 15 mor more, and is wound by paper tube having length of 50 m or more and outer diameter of 180 mm, the porous carbon electrode base material is constituted by carbon short fiber and carbide derived from a thermosetting resin binding the fiber short fibers to each other, the content of the carbide derived from the thermosetting resin is 20 to 60 mass%.

Description

  The present invention relates to a porous carbon electrode substrate used for a polymer electrolyte fuel cell and a method for producing the same.

  A porous carbon electrode base material used for a polymer electrolyte fuel cell is required to have characteristics such as diffusibility of a substance involved in electrode reaction and high conductivity. Moreover, in order to improve the workability of an electrode member in addition to these functions, a porous carbon electrode substrate in the form of a long roll is required. As a method for producing such a porous carbon electrode substrate, Patent Documents 1 and 2 describe that carbon fiber paper mainly composed of carbon short fibers is impregnated with a thermosetting resin, and the obtained resin-impregnated paper is continuously used. Discloses a method of heat press molding and firing.

International Publication No. 01/056103 Pamphlet International Publication No. 02/006032 Pamphlet

  However, when a porous carbon electrode substrate is manufactured by the manufacturing methods disclosed in Patent Documents 1 and 2, through holes are formed in the porous carbon electrode substrate in the firing step. The porous carbon electrode base material including such through-holes has a problem that spots are formed by post-processing such as water repellent treatment. Furthermore, when a porous carbon electrode substrate including through holes is incorporated in a fuel cell, non-uniform power generation occurs in the plane. In-plane non-uniform power generation promotes deterioration of the electrolyte membrane, and thus adversely affects the durability of the fuel cell. In other words, it is inevitable to use the portion where the through hole exists as a porous carbon electrode base material for a fuel cell. However, if the manufactured porous carbon electrode base material has a large number of through holes, the yield is increased. descend.

  An object of the present invention is to provide a porous carbon electrode base material in which formation of through holes is suppressed and a method for producing the same.

The present invention includes (a) a step of obtaining carbon fiber paper containing 10 to 50% by mass of a pulp-like material as an organic polymer compound from short carbon fibers;
(B) impregnating the carbon fiber paper with a thermosetting resin to obtain a resin-impregnated paper;
(C) heat press molding the resin-impregnated paper to obtain a resin-cured sheet;
(D) running the resin-cured sheet into a firing furnace under an inert atmosphere and firing the resin-cured sheet while exhausting at a lower portion of the firing furnace, and with respect to the width of the firing furnace Porous carbon electrode in which at least two resin cured sheets having a width ratio (sheet width ratio) of 90% or less and a sheet width ratio of 45% or less are arranged and run in the firing furnace. It is a manufacturing method of a base material.

The present invention is a sheet-like porous carbon electrode substrate, wherein the number of through-holes having a major axis of 1 mm or more is 0.2 or less per m ² .

  ADVANTAGE OF THE INVENTION According to this invention, the porous carbon electrode base material with which formation of the through-hole was suppressed and its manufacturing method are provided. This porous carbon electrode base material contributes to improving battery power generation characteristics and post-processing productivity.

<Method for producing porous carbon electrode substrate>
In the present invention, a porous carbon electrode substrate is produced by a method having the following steps. At this time, the ratio of the width of the cured resin sheet to the width of the firing furnace (sheet width ratio) is 90% or less. Is essential.
Step (a): Carbon fiber paper is obtained from carbon short fibers.
Step (b): The carbon fiber paper is impregnated with a thermosetting resin to obtain a resin-impregnated paper.
Step (c): The resin-impregnated paper is hot press-molded to obtain a cured resin sheet.
Step (d): The cured resin sheet is fired by running the cured resin sheet in a firing furnace under an inert atmosphere.

(Process (a): Production of carbon fiber paper)
As a method for producing carbon fiber paper in the step (a), a wet method in which carbon short fibers are dispersed in a liquid medium and paper making, or a dry method in which carbon short fibers are dispersed in air and applied are applied. Among them, the wet method is preferable. Step (a) is performed continuously.

  The short carbon fibers contained in the carbon fiber paper may be any of polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, rayon-based carbon fibers, etc., but polyacrylonitrile-based carbon fibers having relatively high mechanical strength are preferred. The polyacrylonitrile-based carbon fiber is produced using a polymer mainly composed of acrylonitrile as a raw material. Specifically, a spinning process for spinning acrylonitrile fibers; a flameproofing process in which acrylonitrile fibers are heated and fired in an air atmosphere at 200 to 400 ° C. to convert them into oxidized fibers; an inert atmosphere such as nitrogen, argon, or helium It is a carbon fiber obtained through a carbonization step in which it is further heated to 300 to 2500 ° C. and carbonized, and can be suitably used as a composite material reinforcing fiber. Therefore, it is possible to form a carbon fiber paper that has higher strength and higher mechanical strength than other carbon fibers. From the viewpoint of maintaining the mechanical properties of the porous carbon electrode substrate, the polyacrylonitrile-based carbon fiber is preferably contained in the carbon fiber paper by 50% by mass or more, and more preferably by 70% by mass or more. In particular, it is preferable that the carbon single fiber to be used is only a polyacrylonitrile-based carbon fiber.

  The average fiber length of the short carbon fibers is preferably 2 to 18 mm, more preferably 2 to 10 mm, and more preferably 3 to 6 mm from the viewpoint of the strength and uniform dispersibility of the porous carbon electrode substrate. More preferably. By setting the average fiber length of the short carbon fibers to 2 mm or more, the short carbon fibers are entangled with each other, and the strength of the porous carbon electrode base material is increased. Moreover, the dispersibility in the dispersion medium of a carbon short fiber becomes favorable because the average fiber length of a carbon short fiber shall be 18 mm or less, and the dispersion spot in carbon fiber paper decreases.

  The liquid medium in which the short carbon fibers are dispersed is preferably water that can be used industrially at low cost.

  The short carbon fiber to carbon fiber paper preferably contains an organic polymer compound as a binder. Examples of the organic polymer compound include polyvinyl alcohol (PVA), polyvinyl acetate, polyester, polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, acrylic resin, polyurethane resin, and other thermoplastic resins, phenol resins, epoxy resins, Thermosetting resins such as melamine resin, urea resin, alkyd resin, unsaturated polyester resin, acrylic resin, polyurethane resin, thermoplastic elastomer, butadiene / styrene copolymer (SBR), butadiene / acrylonitrile copolymer (NBR) Elastomer such as rubber, rubber, cellulose and the like can be used. One organic polymer compound may be used alone, or two or more organic polymer compounds may be used in combination.

  As the form of the organic polymer compound, pulp-like materials and short fibers are suitable. The pulp-like material referred to here is a structure in which a large number of fibrils having a diameter of several μm or less are branched from a fibrous trunk, and in the sheet-like material using this pulp-like material, the entanglement of fibers is efficiently formed. Even if it is a thin sheet-like product, it has a feature that it is excellent in handleability. The short fiber is obtained by cutting fiber yarns or fiber tows into a predetermined length. The length of the short fiber is preferably 2 to 12 mm from the viewpoint of binding properties and dispersibility as a binder.

  The organic polymer compound is preferably a polyvinyl alcohol, polyethylene, polyacrylonitrile, cellulose or polyvinyl acetate pulp or short fiber. Since these organic polymer compounds are excellent in binding power in the papermaking process, the use of these organic polymer compounds reduces the loss of short carbon fibers. In addition, most of these organic polymer compounds are decomposed and volatilized in the final carbonization process for producing the porous carbon electrode substrate to form pores. The presence of these pores improves water and gas permeability.

  The content of the organic polymer compound in the carbon fiber paper is preferably 5 to 60% by mass, and more preferably 10 to 50% by mass. In order to lower the electrical resistance of the porous carbon electrode substrate obtained by impregnating the carbon fiber paper with a thermosetting resin described later and firing, it is better that the content of the organic polymer compound is smaller, The content of the organic polymer compound in the carbon fiber paper is preferably 60% by mass or less. From the viewpoint of maintaining the strength and shape of the carbon fiber paper, the content of the organic polymer compound in the carbon fiber paper is preferably 5% by mass or more.

(Process (b): Impregnation)
The thermosetting resin impregnated into the carbon fiber paper is preferably a resin that exhibits adhesiveness or fluidity at room temperature and remains as a conductive material even after carbonization, and a phenol resin, a furan resin, or the like is used. it can. As the phenol resin, a resol-type phenol resin obtained by a reaction between phenols and aldehydes in the presence of an alkali catalyst can be used. In addition, a novolac type phenolic resin which shows a solid heat-fusible property and is produced by the reaction of phenols and aldehydes under an acidic catalyst by a known method can be dissolved and mixed in the resol type flowable phenolic resin. . However, in this case, it is preferable to use a self-crosslinking type containing, for example, hexamethylenediamine as a curing agent. A commercially available product can be used as the phenol resin. As phenols, for example, phenol, resorcin, cresol, xylol and the like are used. As aldehydes, for example, formalin, paraformaldehyde, furfural and the like are used. Moreover, these can be used as a mixture.

  The content of the thermosetting resin in the resin-impregnated paper obtained by impregnating the carbon fiber paper with the thermosetting resin is preferably 30 to 70% by mass. By setting the content of the thermosetting resin to 30% by mass or more, the structure of the obtained porous carbon electrode substrate becomes dense and the strength becomes high. Moreover, the porosity and gas permeability of the obtained porous carbon electrode base material can be kept favorable by making the content rate of a thermosetting resin into 70 mass% or less. The resin-impregnated paper refers to a paper obtained by impregnating a carbon fiber paper with a thermosetting resin before heating and pressurization, but when the solvent is used at the time of resin impregnation, it means a paper from which the solvent is removed.

  Carbon fiber paper may be impregnated with a mixture of a thermosetting resin and a conductive material. Examples of the conductive material include carbonaceous milled fiber, carbon black, acetylene black, and isotropic graphite powder. The mixing amount of the conductive substance is preferably 1 to 10% by mass with respect to the thermosetting resin. By setting the mixing amount of the conductive substance to 1% by mass or more, the effect of improving the conductivity becomes sufficient. Moreover, since the effect of improving the conductivity tends to be saturated even if the mixing amount of the conductive material exceeds 10% by mass, the increase in cost can be suppressed by setting the mixing amount of the conductive material to 10% by mass or less. Can do.

  As a method for impregnating carbon fiber paper with a solution containing a thermosetting resin and optionally a conductive material, a method using a squeezing device or a method of superimposing a separately prepared thermosetting resin film on carbon fiber paper is preferable. In the method using the squeezing device, the impregnation solution is impregnated with carbon fiber paper so that the intake liquid is uniformly applied to the entire carbon fiber paper with the squeezing device, and the liquid amount is adjusted by changing the roll interval of the squeezing device. Is the method. When the viscosity of the solution is relatively low, a spray method or the like can be used. In the method of superposing a thermosetting resin film on carbon fiber paper, first, a release paper is coated with a solution containing a thermosetting resin and optionally a conductive substance to obtain a thermosetting resin film. Thereafter, a thermosetting resin film is laminated on the carbon fiber paper, a heat and pressure treatment is performed, and the carbon fiber paper is impregnated with the thermosetting resin.

(Process (c): Heat press molding)
Step (c) is an important step of curing the thermosetting resin in the resin-impregnated paper and controlling the sheet thickness. Step (c) is continuously performed from the viewpoint of productivity.

  As a press apparatus to be used, it is preferable to use a continuous heating roll press apparatus or a continuous heating press apparatus (double belt press apparatus) provided with a pair of endless belts. In the heated roll press apparatus, one set or two or more sets of multi-stage presses can be adopted. In the double belt press machine, when the thermosetting resin is softened in the preheating stage, the resin-impregnated paper can be transported by a belt with almost no tension. Excellent in properties. Therefore, it is more preferable to use a double belt press apparatus.

  It is preferable to perform a preheat treatment before the hot pressing. By applying heat to the resin-impregnated paper before the heat pressing to soften the thermosetting resin, the thermosetting resin can be well adapted to the carbon fiber paper. When heated and pressed, the short carbon fibers are effectively bound to each other, and a porous carbon electrode substrate having excellent mechanical properties and high handling properties can be produced. The heating means employed in the preheat treatment may be any one of heat transfer heating such as a heating roll, convection heating provided with a heating region, radiation heating such as far infrared rays, or a combination thereof, from the viewpoint of reducing heat loss. Heat transfer heating using a heating roll or the like is preferable.

  It is preferable to heat press-mold a resin-impregnated paper laminate in which two resin-impregnated papers are laminated. As the number of resin-impregnated papers to be laminated increases, the basis weight of one carbon fiber paper can be reduced, and the surface state of the carbon fiber paper becomes better. However, when three or more resin-impregnated papers are laminated, not only the productivity of carbon fiber paper is lowered, but also press errors may be increased.

  The resulting cured resin sheet preferably has a silicon content of 300 ppm or less, and more preferably 100 ppm or less. By setting the silicon content of the resin cured sheet to 300 ppm or less, it is possible to suppress the silicon compound from adhering to the firing furnace wall when the cured resin sheet is run in the firing furnace in the next step. In addition, when a silicon compound adheres to the firing furnace wall, the silicon compound falls on the traveling resin cured sheet, and is further processed at a high temperature to react with carbon short fibers in the resin cured sheet to form through holes. Is done. Therefore, in order to suppress the formation of through holes, it is effective to reduce the amount of silicon compound brought into the firing furnace.

(Process (d): Firing)
In the step (d), the resin cured sheet is fired. Specifically, the resin cured sheet is run in a firing furnace under an inert atmosphere. Step (d) is performed continuously.

  From the viewpoint of mechanical properties and conductivity of the finally obtained porous carbon electrode base material, the step (d) is a step of performing a heat treatment (preliminary carbonization) having a maximum temperature of at least 600 ° C (preferably 700 ° C or more). Step) and a heat treatment step (carbonization step) in which the maximum temperature is at least 1500 ° C. or higher (preferably 1600 ° C. or higher).

  In the step (d), it is essential that the ratio of the width of the cured resin sheet to the width of the firing furnace (sheet width ratio) is 90% or less. This is because the inert gas in the firing furnace needs to be exhausted smoothly without stagnation. When the sheet width ratio exceeds 90%, the circulation of the inert gas on the upper and lower sides across the resin cured sheet is hindered, and impurities such as silicon-containing compounds floating in the firing furnace are exhausted. It will concentrate without becoming a factor that a through hole is formed.

  More preferably, at least two resin cured sheets having a sheet width ratio of 45% or less are arranged side by side and run in a firing furnace. With this method, the inert gas in the baking furnace does not stay on the upper side or the lower side of the cured resin sheet, and the inert gas is smoothly replaced, thereby suppressing the floating of the silicon-containing compound. Can do.

  In the step (d), a cover sheet made of a carbon material is disposed above the sheet traveling path in the firing furnace, and the resin-cured sheet continuously travels under the cover sheet and fired. Is preferred. As the carbon material, for example, a separately prepared porous carbon electrode substrate can be used. By covering the traveling resin cured sheet with the cover sheet, adhesion of the silicon-containing compound can be prevented, and formation of through holes can be suppressed.

  In the step (d), it is preferable that the exhaust of the carbonization furnace is a lower exhaust. In the upper exhaust, solid content and organic matter adhere to the exhaust gas duct, which may drop onto the resin cured sheet, thereby forming a through hole.

  The obtained porous carbon electrode base material can be used by slitting to a desired width. In that case, it is preferable to slit the resin-cured sheet after the hot press molding step or the porous carbon electrode base material after the firing step to a desired width. A method of cutting the sheet by cooperation of a receiving blade provided on the rotating roller and a disk-shaped slit blade is preferable. Furthermore, it is preferable to suck and remove chips generated immediately after the slit.

<Porous carbon electrode substrate>
(About through holes)
The porous carbon electrode substrate of the present invention is a continuous sheet, and it is essential that the number of through holes having a major axis of 1 mm or more is 0.2 or less per 1 m ² . In the present invention, it is important that the sheet is a continuous sheet having an area of 15 m ² or more so that it can be continuously processed by post-processing.

The porous carbon electrode base material including the through holes has a problem that spots are formed by post-processing such as water repellent treatment. Furthermore, when a porous carbon electrode substrate including through holes is incorporated in a fuel cell, non-uniform power generation occurs in the plane. In-plane non-uniform power generation promotes deterioration of the electrolyte membrane, and thus adversely affects the durability of the fuel cell. Therefore, it is inevitable to use the portion where the through hole exists as a porous carbon electrode substrate for a fuel cell. However, if the number of through-holes exceeds 0.2 / m ² on average, the yield of the porous carbon electrode substrate for fuel cells is lowered. Therefore, it is essential that the number of through-holes having a major axis of 1 mm or more is 0.2 / m ² or less on average, and preferably 0.1 / m ² or less on average.

(About bending strength and bending deflection)
The thickness of the porous carbon electrode substrate of the present invention is preferably 0.05 to 0.4 mm, more preferably 0.1 to 0.3 mm, from the viewpoint of resistance value. By setting the thickness of the porous carbon electrode base material to 0.05 mm or more, the strength in the thickness direction becomes high, and the handling when the cell stack is assembled can be made. Moreover, by setting the thickness of the porous carbon electrode base material to 0.4 mm or less, the electrical resistance is lowered, and the total thickness when stacks are stacked is reduced.

The bulk density of the porous carbon electrode substrate of the present invention is preferably from 0.3 to 0.8 g / cm ^3, more preferably 0.4 to 0.7 g / cm ^3. By setting the bulk density of the porous carbon electrode substrate to 0.3 g / cm ³ or more, the electric resistance is lowered and satisfactory flexibility can be obtained. Moreover, gas permeability becomes favorable and the performance of a fuel cell improves because the bulk density of a porous carbon electrode base material shall be 0.8 g / cm < ³ > or less.

  The bending strength of the porous carbon electrode substrate of the present invention is preferably 30 MPa or more, and more preferably 40 MPa or more, under the conditions of a strain rate of 10 mm / min, a fulcrum distance of 2 cm, and a test piece width of 1 cm. By making the bending strength of the porous carbon electrode substrate 30 MPa or more, handling becomes easy, for example, not only is it difficult to break when wound on a roll, but cracks are also generated when the porous carbon electrode substrate is bent. It may not occur.

  The bending deflection of the porous carbon electrode substrate of the present invention is preferably 1.5 mm or more, and more preferably 2.0 mm or more under the same conditions as the bending strength. When the bending deflection of the porous carbon electrode substrate is 1.5 mm or more, it is difficult to break when continuously wound on a roll, and it becomes easy to produce and handle a long porous carbon electrode substrate. .

(About paper tube diameter)
The porous carbon electrode substrate of the present invention is preferably wound around a paper tube having a length of 50 m or more and an outer diameter not exceeding 180 mm. If the porous carbon electrode substrate is long and can be wound in a roll shape, not only the productivity will be increased, but also the subsequent MEA (Membrane / Electrode Assembly) production will be performed continuously. Can greatly contribute to cost reduction of the fuel cell. For this reason, it is preferable that the outer diameter is flexible enough to be wound around a paper tube not exceeding 180 mm. Furthermore, if it can be wound on a paper tube whose outer diameter does not exceed 180 mm, the product form as the porous carbon electrode substrate can be made compact, which is advantageous in terms of packaging and transportation costs.

(About the content of carbide derived from thermosetting resin)
The porous carbon electrode base material of the present invention is composed of short carbon fibers and carbides derived from thermosetting resins, and the carbon short fibers are bound together by carbides derived from thermosetting resins. Preferably there is. The carbide is derived from a thermosetting resin, but the ratio of the remaining carbon as a carbide on the porous carbon electrode base material varies depending on the type of thermosetting resin and the amount of carbon fiber paper impregnated. When the porous carbon electrode base material is 100% by mass, the content of the carbide derived from the thermosetting resin excluding the short carbon fiber content is the binding of carbon short fibers in the porous carbon electrode base material or the porous material. It is preferable that it is 20-60 mass% from a viewpoint of carbon electrode base-material flexibility expression.

  Hereinafter, the present invention will be described more specifically with reference to examples. The evaluation / inspection methods performed in the examples are as follows.

1) Number of through-holes in porous carbon electrode base material The porous carbon electrode base material is passed through a position 150 mm above the light source (Kyoto Denki Co., Ltd., trade name: LST-40), and visually observed from the transmitted light. A through hole was confirmed. And the size of the confirmed through-hole was measured with the ruler, and the through-hole whose longest diameter (major axis) is 1 mm or more was counted.

2) Silicon content of porous carbon electrode base material 0.2 g of Na ₂ CO ₃ powder was added to a crucible charged with 2-3 g of the porous electrode base material and melted with a gas burner. And after visually confirming that the melting had spread throughout, it was heated for at least 5 minutes. Next, 10 ml of pure water (without Si) was added and dissolved, and then transferred to a 50 ml poly flask several times, and the volume was adjusted to 50 ml with a poly volumetric flask. Then, silicon analysis was performed by ICP emission analysis.

3) Thickness Using a micrometer (trade name: MDC-25MJ, manufactured by Mitutoyo Corporation), five points were measured in the width direction, and the average thickness was calculated.

4) Bulk density Five 200 mm × 300 mm samples were cut out and weighed with an electronic balance. And the bulk density was computed using the average thickness measured by 3).

5) Bending strength of porous carbon electrode substrate It measured using the bending strength test apparatus. Apply a load to a 10 mm wide sample at a fulcrum distance of 2 cm and a strain rate of 10 mm / min, and measure the breaking load of the pressure wedge when the test piece breaks from the point where the load began to be applied. Asked.

P = break load (N), L = distance between fulcrums (mm), W = sample width (mm), h = sample thickness (mm)
In addition, about the continuous sample, the value of the longitudinal direction was measured.

6) Bending Deflection of Porous Carbon Electrode Base Material It was measured using a bending strength test apparatus. A load is applied to a 10 mm wide sample at a fulcrum distance of 2 cm and a strain rate of 10 mm / min, and the moving distance of the pressure wedge when the test piece breaks from the point where the load starts to be applied is measured. It was bent and bent.

7) Content of carbide derived from thermosetting resin The content of carbide derived from thermosetting resin excluding the carbon fiber content when the porous carbon electrode base material is 100% by mass, and is calculated by the following formula. did.

Ｃ：多孔質炭素電極基材中の熱硬化性樹脂由来の炭化物の含有率（質量％）
Ｇｗ：多孔質炭素電極基材の目付（ｇ／ｍ²）
Ｐｗ：炭素繊維紙の目付（ｇ／ｍ²）
Ｆ：炭素繊維紙中の炭素繊維の割合（質量％）

C: Content (% by mass) of carbide derived from the thermosetting resin in the porous carbon electrode substrate
Gw: basis weight of porous carbon electrode substrate (g / m ² )
Pw: basis weight of carbon fiber paper (g / m ² )
F: Ratio of carbon fiber in carbon fiber paper (mass%)

[Example 1]
Polyacrylonitrile carbon short fibers cut to an average fiber length of 3 mm (Mitsubishi Rayon Co., Ltd., trade name: Pyrofil TR50S, average single fiber diameter: 7 μm), polyvinyl alcohol (PVA) short fibers (Kuraray Co., Ltd., trade name: VBP105-1, fiber length 3 mm) and polyethylene pulp (trade name: SWP, manufactured by Mitsui Chemicals, Inc.) were prepared. Polyacrylonitrile-based short carbon fibers are uniformly dispersed and defibrated in water in a slurry tank of a wet short net continuous paper making machine, and when sufficiently dispersed, PVA short fibers and polyethylene pulp are uniformly dispersed so as to have the composition shown in Table 1. And sent out. The fed web was passed through a short mesh plate, and after drying the dryer, a carbon fiber paper in the form of a roll having a width of 1000 mm and a basis weight of 43 g / m ² was obtained.

Next, the carbon fiber paper is immersed in a methanol solution of phenol resin (manufactured by DIC Corporation, trade name: Phenolite J-325), 53 parts by mass are attached to 100 parts by mass of the carbon fiber paper, and further slit to a width of 850 mm. Thus, a resin-impregnated paper having a phenol resin attached thereto was obtained. This resin-impregnated paper was press-molded using a double belt press apparatus. As the conditions at that time, the preheating conditions were a hot air temperature of 150 ° C., a preheating roll temperature of 230 ° C., a press roll temperature of 260 ° C., and a linear pressure of 8 × 10 ⁴ N / m. As a result, a cured resin sheet having a width of 850 mm and a length of 100 m was obtained.

  The obtained cured resin sheet was run in a firing furnace (width: 1 m) in a nitrogen gas atmosphere, and heat-treated at a maximum temperature of 800 ° C. under a temperature increase rate of 140 ° C./min. Then, it was further run in a firing furnace under a nitrogen gas atmosphere, and heat treatment was performed at a maximum temperature of 2000 ° C. The sheet width ratio of the resin cured sheet was 85%. The porous carbon electrode substrate having a length of 100 m thus obtained was slit into a width of 400 mm and then wound on a paper tube having an outer diameter of 172 mm. The inspection results of the obtained porous carbon electrode substrate are shown in Tables 1 and 2. Moreover, the content rate of the carbide | carbonized_material derived from the thermosetting resin contained in a porous carbon electrode base material was 31 mass%.

[Example 2]
In the same manner as in Example 1, a carbon fiber paper in the form of a roll having a width of 1000 mm and a basis weight of 34 g / m 2 was obtained.

Next, carbon fiber paper is immersed in a methanol solution of phenol resin (manufactured by DIC Corporation, trade name: Phenolite J-325), and 53 parts by mass are attached to 100 parts by mass of carbon fiber paper, and further slit to a width of 650 mm. Thus, a resin-impregnated paper having a phenol resin attached thereto was obtained. This resin-impregnated paper was pressed using a double belt press. The preheating conditions were as follows: the hot air temperature was 150 ° C., the preheating roll temperature was 230 ° C., the press roll temperature was 260 ° C., and the linear pressure was 8 × 10 ⁴ N / m. As a result, a cured resin sheet having a width of 650 mm and a length of 100 m was obtained.

  The obtained cured resin sheet was run in a firing furnace (width: 1 m) in a nitrogen gas atmosphere, and heat-treated at a maximum temperature of 800 ° C. under a temperature increase rate of 140 ° C./min. Then, it was further run in a firing furnace under a nitrogen gas atmosphere, and heat treatment was performed at a maximum temperature of 2000 ° C. The sheet width ratio of the cured resin sheet was 65%. The porous carbon electrode substrate having a length of 100 m thus obtained was slit to a width of 300 mm and then wound on a paper tube having an outer diameter of 172 mm. The inspection results of the obtained porous carbon electrode substrate are shown in Table 2. Moreover, the content rate of the carbide | carbonized_material derived from the thermosetting resin contained in a porous carbon electrode base material was 45 mass%.

[Comparative Example 1]
In the same manner as in Example 1, a 1000 mm wide carbon fiber paper having a roll shape with a basis weight of 43 g / m ² was obtained.

Next, the carbon fiber paper is immersed in a methanol solution of a phenol resin (manufactured by DIC Corporation, trade name Phenolite J-325), and 53 parts by mass is attached to 100 parts by mass of the carbon fiber paper, and further slit to a width of 950 mm. Thus, a resin-impregnated paper having a phenol resin attached thereto was obtained. This resin-impregnated paper was pressed using a double belt press. The preheating conditions were as follows: the hot air temperature was 150 ° C., the preheating roll temperature was 230 ° C., the press roll temperature was 260 ° C., and the linear pressure was 8 × 10 ⁴ N / m. As a result, a cured resin sheet having a width of 950 mm and a length of 100 m was obtained.

  The obtained cured resin sheet was run in a firing furnace (width: 1 m) in a nitrogen gas atmosphere, and heat-treated at a maximum temperature of 800 ° C. under a temperature increase rate of 140 ° C./min. Then, it was further run in a firing furnace under a nitrogen gas atmosphere, and heat treatment was performed at a maximum temperature of 2000 ° C. The sheet width ratio of the resin cured sheet was 95%. The porous carbon electrode substrate having a length of 100 m thus obtained was slit into a width of 400 mm and then wound on a paper tube having an outer diameter of 172 mm. The inspection results of the obtained porous carbon electrode substrate are shown in Table 2. Moreover, the content rate of the carbide | carbonized_material derived from the thermosetting resin contained in a porous carbon electrode base material was 32 mass%.

Claims (5)

A porous carbon electrode substrate, which is a sheet-like porous carbon electrode substrate, wherein the number of through-holes having a major axis of 1 mm or more is 0.2 or less per 1 m ² . The thickness is 0.05 to 0.4 mm, the bulk density is 0.3 to 0.8 g / cm ³ , the bending strength is 30 MPa or more, and the bending deflection is 1.5 mm or more. Porous carbon electrode substrate. The porous carbon electrode substrate according to claim 1 or 2, having an area of 15 m ² or more.   The porous carbon electrode substrate according to any one of claims 1 to 3, wherein the porous carbon electrode substrate is wound around a paper tube having a length of 50 m or more and an outer diameter not exceeding 180 mm.   It is comprised from the carbon short fiber and the carbide | carbonized_material derived from the thermosetting resin which has bound the said carbon short fiber, The content rate of the carbide | carbonized_material derived from the said thermosetting resin is 20-60 mass%. The porous carbon electrode substrate according to any one of claims 1 to 4.