JP4965832B2 - Manufacturing method of fuel cell separator and fuel cell separator - Google Patents

Description

  The present invention relates to a prepreg for a fuel cell separator, a method for producing a fuel cell separator, and a fuel cell separator.

  In general, a fuel cell is composed of a cell stack in which several tens to several hundreds of unit cells are stacked in series, thereby obtaining a predetermined voltage.

  The most basic structure of the unit cell has a configuration of “fuel cell separator / fuel electrode (anode) / electrolyte / oxidant electrode (cathode) / fuel cell separator”. In this unit cell, the chemical energy of the reaction is obtained by oxidizing the fuel by electrochemical reaction by supplying fuel to the fuel electrode and supplying the oxidant to the oxidant electrode of the pair of electrodes facing each other through the electrolyte. Direct conversion to electrochemical energy.

  Such fuel cells are classified into several types depending on the type of electrolyte. Recently, solid polymer fuel cells using a solid polymer electrolyte membrane as an electrolyte have attracted attention as fuel cells that can provide high output. Has been.

  As an example of such a polymer electrolyte fuel cell, a polymer electrolyte membrane and a gas diffusion electrode are provided between two fuel cell separators having a plurality of convex portions (ribs) formed on both left and right side surfaces. A unit cell (unit cell) is formed by interposing (fuel electrode and oxidant electrode), and several tens to hundreds of unit cells are arranged in parallel to form a battery body (cell stack). is there. The convex portion forms a groove-shaped concave portion between adjacent convex portions, and in this concave portion, a gas supply / discharge groove which is a flow path for hydrogen gas as a fuel and oxygen gas as an oxidant is formed. Constitute.

  Such a cell stack can be composed of, for example, 50 to 100 unit cells in a stationary type for home use, and can be composed of 400 to 500 unit cells for automobile loading.

In this polymer electrolyte fuel cell, hydrogen gas, which is a fluid, is supplied to a fuel electrode, and oxygen gas, which is a fluid, is supplied to an oxidizer electrode, thereby extracting current from an external circuit. In the reaction, the reaction shown in the following formula occurs.
Fuel electrode reaction: H ₂ → 2H ⁺ + 2e ⁻ (1)
Oxidant electrode reaction: 2H ⁺ + 2e ⁻ + 1 / 2O ₂ → H ₂ O (2)
Overall reaction: H ₂ + 1 / 2O ₂ → H ₂ O
That is, hydrogen (H ₂ ) becomes proton (H ⁺ ) on the fuel electrode, and this proton moves through the solid polymer electrolyte membrane to the oxidant electrode and reacts with oxygen (O ₂ ) on the oxidant electrode. To produce water (H ₂ O). Therefore, for the operation of the polymer electrolyte fuel cell, it is necessary to supply and discharge the reactive gas and to take out the current.

  In addition, the polymer electrolyte fuel cell is normally assumed to operate in a humid atmosphere in the range of room temperature to 120 ° C., and therefore water is often handled in a liquid state. It is necessary to manage the replenishment of liquid water and discharge the liquid water from the oxidizer electrode.

  Among the components constituting such a fuel cell, the fuel cell separator has a unique shape having a plurality of gas supply / discharge grooves on one or both sides of a thin plate-like body, It has the function of separating the flowing fuel gas, oxidant gas and cooling water so that they do not mix, and also transmits the electric energy generated by the fuel cell to the outside, or dissipates the heat generated in the fuel cell to the outside. It plays an important role.

  As such a fuel cell separator, various thermoplastic resins such as phenol resin and epoxy resin which are advantageous in terms of productivity and cost, or a resin composition mainly composed of thermosetting resin and graphite particles are used. A method of molding by compression molding, injection molding, transfer molding, or the like is known (see, for example, Patent Documents 1 and 2).

  In addition, since such fuel cell separators are required to be thin and lightweight, a resin composition is formed into a sheet by a roll molding method or an extrusion molding method, and this is compression molded or hot-press molded. Attempts have also been made to obtain a fuel cell separator by further molding by the above method.

However, when the fuel cell separator is made thin as described above, the mechanical strength is lowered, and particularly when used for a fuel cell for a vehicle, a crack occurs during use, which is practically satisfactory. There was a problem that strength characteristics could not be obtained.
JP 2001-216976 A JP 2002-114572 A

  The present invention has been made in view of the above points, and enables sheet molding to reduce the thickness and weight of the fuel cell separator, and also provides good conductivity of the obtained fuel cell separator. And a fuel cell separator prepreg capable of ensuring mechanical strength, a fuel cell separator manufacturing method using the fuel cell separator prepreg, and a fuel cell separator formed using the fuel cell separator prepreg It is intended to do.

  A prepreg for a fuel cell separator according to the present invention is obtained by impregnating and semi-curing a conductive substrate with a resin composition containing graphite particles having an average particle diameter of 5 to 35 μm, a thermosetting resin, and a wax. It is what. When the fuel cell separator prepreg is molded and cured to form the fuel cell separator 1, a high mold releasability is imparted by the wax, so that the fuel cell separator 1 having a desired shape can be easily formed by molding. The fuel cell separator 1 is provided with high mechanical strength by the conductive base material and maintains excellent conductivity, and the graphite particles are uniformly dispersed and the graphite particles are dispersed in the fuel cell separator 1. A stable conductive path is formed.

  The resin composition contains an epoxy resin as a thermosetting resin and a curing catalyst thereof, and the content of the graphite particles with respect to the solid content of the resin composition is 65 to 90% by mass, and the epoxy resin is contained. The amount may be 9 to 30% by mass, the wax content may be 0.1 to 3% by mass, and the content of the curing catalyst with respect to the epoxy resin may be 0.5 to 5% by mass. By doing so, the resin composition and the prepreg for the fuel cell separator have excellent storage stability, and exhibit excellent moldability in forming the fuel cell separator 1 by molding the fuel cell separator 1, A fuel cell separator 1 having high conductivity can be obtained.

Moreover, it is preferable that the basic weight of the said electroconductive base material is the range of 20-210 g / m < ² > . In this way, the impregnating property of the resin composition into the conductive base material is enhanced, and further excellent conductivity is exhibited, and an increase in the thickness of the fuel cell separator 1 is suppressed, thereby further reducing the thickness and weight of the fuel cell separator 1. Obtainable.

  It is also preferable that the viscosity of the resin composition measured with a B-type viscometer be in the range of 300 to 1000 cP, thereby maintaining good impregnation of the resin composition into the conductive substrate. In addition, the fuel cell separator 1 can be provided with further excellent strength and conductivity, and can prevent precipitation of graphite particles due to a decrease in viscosity, so that the required amount of graphite can be sufficiently adhered to the conductive substrate. It is.

  In addition, it is preferable to use carbon fiber paper as the conductive substrate. In this case, the impregnation property of the resin composition to the conductive substrate can be further improved, and the fuel cell separator 1 is further improved. In addition to being able to impart electrical conductivity, it also has excellent sulfuric acid resistance, chemical resistance, and methanol resistance.

  In addition, the prepreg for a fuel cell separator preferably has a volatile content of 0.5% by mass or less, thereby preventing generation of voids when the fuel cell separator 1 is formed. It is possible to prevent the occurrence of gas leak and to prevent the decrease in conductivity.

  Moreover, the manufacturing method of the fuel cell separator 1 according to the present invention is characterized in that the prepreg for a fuel cell separator as described above is subjected to heat compression molding using a molding die.

  The fuel cell separator 1 according to the present invention is characterized in that the prepreg for a fuel cell separator as described above is heat compression molded with a molding die.

  As a result, since the high releasability is imparted by the wax, the fuel cell separator 1 having a desired shape can be easily formed. The resulting fuel cell separator 1 has higher mechanical strength due to the conductive substrate. In addition to being imparted with excellent conductivity, the graphite particles are uniformly dispersed, and a stable conductive path is formed in the fuel cell separator 1 by the graphite particles.

  In addition, the fuel cell separator 1 can be formed to have a corrugated shape, thereby reducing the thickness and weight of the fuel cell separator 1 and forming gas passages and the like required for the fuel cell. It can be done at the same time.

  According to the present invention, when forming a fuel cell separator, the fuel cell separator can be easily formed into a desired shape with good moldability and can be reduced in thickness and weight. And mechanical strength can be imparted, and the fuel cell can be reduced in size and weight.

  Hereinafter, the best mode for carrying out the present invention will be described.

  A prepreg for a fuel cell separator is formed of a resin composition containing graphite particles, a thermosetting resin and a wax, and a conductive substrate.

  Appropriate particles can be used as the graphite particles in the resin composition, which may be naturally produced or purified, or may be artificially produced. Moreover, the particle shape may be various shapes such as a scale shape, a needle shape, and a spherical shape. The average particle diameter of such graphite particles is in the range of 5 to 35 μm. When the average particle size is less than 5 μm, it is difficult to form a conductive path in the fuel cell separator 1 formed, which is disadvantageous in terms of conductivity, and is necessary for obtaining sufficient conductivity. There is a possibility that the amount of graphite particles added increases and the moldability deteriorates. Further, if the average particle size exceeds 35 μm, precipitation of graphite particles tends to occur in the resin composition, which may lead to non-uniformity of the resin composition. The prepreg for battery separators may also become non-uniform and its conductivity may become unstable.

  The content of the graphite particles in the resin composition is preferably in the range of 65 to 90% by weight, more preferably 70 to 85% by weight with respect to the solid content of the resin composition. The solid content is a component that constitutes a cured product when the resin composition is molded and cured. When the solvent is contained in the resin composition, the solid content is a component that excludes the solvent. If the proportion of the graphite particles is too small, sufficient conductivity required for the fuel cell separator 1 cannot be obtained, and if it is excessive, the gas permeability and moldability required for the fuel cell separator 1 are sufficient. May not be obtained.

  Moreover, as a thermosetting resin, various things, such as a phenol resin, an epoxy resin, unsaturated polyester resin, a melamine resin, a urea resin, can be illustrated, and it is especially using the mixture containing an epoxy resin or an epoxy resin. preferable. Further, an appropriate thermoplastic resin may be used in combination with such a thermosetting resin.

  The content of the thermosetting resin in the resin composition is appropriately adjusted, but when using an epoxy resin, the epoxy resin is preferably in the range of 9 to 30% by mass relative to the solid content in the resin composition. Preferably it is made to contain in 15-30 mass%.

  When using an epoxy resin, a curing agent is blended as necessary. As the curing agent, it is preferable to use a non-amine compound. When an amine compound is used, it is difficult to maintain the electric conductivity of the obtained fuel cell separator 1 at a high level, and the fuel cell There is also a risk of poisoning the catalyst. In addition, it is preferable not to use an acid anhydride compound as the curing agent. An acid anhydride compound may be hydrolyzed in an acid-resistant environment such as a sulfuric acid acid environment, resulting in a decrease in electrical conductivity or an increase in impurity elution. As a curing agent satisfying such conditions, it is particularly preferable to use a phenol-based compound. In this case, the properties of the cured product are excellent.

  The content of such a curing agent is appropriately set, but it is preferable that the stoichiometric equivalent ratio of the curing agent to the epoxy resin is 1 to 1.12.

  Moreover, as a curing catalyst (curing accelerator) used when using an epoxy resin, an appropriate one can be used, but it is preferable to use a non-amine compound for the same reason as in the case of a curing agent. . For example, amine-based diaminodiphenylmethane is not preferable because the residue may poison the fuel cell catalyst.

  As such an epoxy resin curing catalyst, a phosphorus compound can be preferably used, and triphenylphosphine can be mentioned as an example. In this case, elution of chlorine ions from the fuel cell separator 1 can be suppressed.

  The content of such a curing catalyst is appropriately adjusted, but is preferably in the range of 0.5 to 5% by mass with respect to the epoxy resin in the resin composition. If this content is less than 0.5% by mass, the time required for curing and molding the prepreg for the fuel cell separator will be prolonged and the production efficiency will deteriorate, and if this exceeds 5% by mass, the fuel cell separator 1 will be used. When the material is stored, the resin component may be cured and storage stability may be lowered.

  Moreover, it is preferable that the content of the chlorine ion which is an ionic impurity, and the content of a sodium ion are 5 ppm or less in a mass ratio, respectively. In this case, elution of ionic impurities from the fuel cell separator 1 which is a molded product can be further suppressed, and when each content exceeds 5 ppm, the amount of elution of impurities increases and the characteristics as a fuel cell are obtained. Decrease may occur.

  Moreover, a coupling agent can also be contained in the resin composition. Any appropriate coupling agent may be used, but it is preferable not to use aminosilane since it is preferable not to include a primary amine and a secondary amine in the resin composition. When aminosilane is used, the catalyst of the fuel cell may be poisoned, which is not preferable. Further, it is preferable not to use mercaptosilane as a coupling agent. The use of this mercaptosilane is also not preferable because it may similarly poison the fuel cell catalyst. Examples of preferable coupling agents include silicon-based silane compounds, titanate-based, aluminum-based ones. For example, epoxy silane is suitable as an epoxy-based silane coupling agent.

  The coupling agent is preferably attached to the surface of the graphite particles by spraying or the like in advance. The addition amount is appropriately set, and it is necessary to consider the coating area per unit mass of the coupling agent to be used as compared with the specific surface area of the graphite particles. The total amount is in the range of 0.5 to 2 times the total surface area of the graphite particles. When this value increases, it is not preferable because it bleeds on the surface of the molded product and contaminates the mold surface.

  The wax (release agent) to be contained in the resin composition is appropriately selected from high purity, but it is particularly preferable to use natural carnauba wax. The content of the wax is appropriately set, but is preferably in the range of 0.1 to 3% by mass with respect to the solid content in the resin composition. Sufficient releasability cannot be obtained at the time of molding, and if it exceeds 3% by mass, sufficient wettability with water required for the fuel cell separator 1 may not be obtained.

  Moreover, also in such a wax, it is preferable that the content of chlorine ions, which are ionic impurities, and the content of sodium ions are both 5 ppm or less in terms of mass. If the content of each ionic impurity exceeds 5 ppm, when the fuel cell separator 1 is used for a fuel cell, the impurities may be eluted and the characteristics may be deteriorated.

  Further, when impregnating the conductive composition with the resin composition, a solvent is further added to the resin composition to prepare the resin composition as a liquid resin varnish, and the conductive base material is impregnated with the resin varnish. You can also. As this solvent, it is preferable to use a non-amine solvent. When an amine solvent is used, it becomes difficult to maintain the electric conductivity of the obtained fuel cell separator 1 in a high state, and the catalyst of the fuel cell is used. There is a risk of poisoning. As such a solvent, an appropriate one can be used. Examples of a solvent that facilitates the formation of a sheet by casting the resin composition and that can achieve a predetermined effect include, for example, methyl ethyl ketone, methoxypropanol, toluene, xylene A polar solvent such as can be used. Thus, when preparing a resin composition as a resin varnish, content of the component (solid content) except the solvent in a resin composition becomes like this. Preferably it is 30-80 mass%, More preferably, it is 40-70 mass%. Try to be in range. In addition, what is necessary is just to mix | blend a solvent as needed, and when using liquid resin etc., a solvent is not mix | blended or the addition amount of a solvent can be reduced.

  Moreover, it is preferable that the viscosity measured with a B-type viscometer of the resin composition is in the range of 300 to 1000 cP (cps), and when the solvent is blended, the viscosity of the resin composition is in the above range. It is preferable to mix. When the resin composition is prepared in such a viscosity range, it is possible to maintain good impregnation of the resin composition into the conductive substrate and to impart further excellent conductivity to the fuel cell separator 1. Further, if the viscosity is too low, precipitation of graphite particles occurs in the resin composition, and it is difficult to attach a necessary amount of graphite particles to the conductive substrate when impregnating the resin composition into the conductive substrate. However, when the viscosity is 300 cP or more, the required amount of graphite particles can be sufficiently adhered, and the bending strength is improved.

  Moreover, it is preferable that the resin composition has a TOC (total organic carbon) of a molded article formed from the resin composition of 100 ppm or less.

Here, TOC is a numerical value measured using an aqueous solution after processing a molded article having a specific surface area of 20 cm ² / g at 90 ° C. for 50 hours. Such a TOC can be measured by, for example, a total organic carbon analyzer “TOC-50” manufactured by Shimadzu Corporation based on JIS K0102. In the measurement method, the concentration of carbon in the sample is quantified by measuring the CO ₂ concentration generated by burning the sample by a non-dispersive infrared gas analysis method. By measuring the carbon concentration, the concentration of organic substances contained indirectly can be measured, the inorganic carbon (IC) and total carbon (TC) in the sample are measured, and the difference between the total carbon and inorganic carbon (TC− IC) to measure total organic carbon (TOC).

  If the above TOC exceeds 100 ppm, there is a risk that the characteristics of the fuel cell will deteriorate, and if it is 100 ppm or less, such characteristics deterioration can be suppressed.

  Here, in the present invention, the TOC value can be reduced and adjusted by selecting a high-purity raw material, adjusting the equivalent ratio of the resin, or performing post-curing treatment.

  In addition, the resin composition preferably has a low content of ionic impurities. If the content of ionic impurities is high, the solid polymer membrane may be deteriorated when the fuel cell separator 1 is incorporated into a fuel cell. In other words, the characteristics as a fuel cell may be significantly impaired.

  Specifically, the content of chlorine ions and sodium ions, which are water-soluble ions, in the entire resin composition is preferably 5 ppm or less by mass ratio with respect to the total amount of the resin composition. If this value exceeds 5 ppm, the elution of impurities from the molded fuel cell separator 1 may cause deterioration in characteristics of the fuel cell such as a decrease in starting voltage, and this value should be 5 ppm or less. Thus, it is possible to prevent such characteristic deterioration from occurring.

The content of the above-mentioned chlorine ion and sodium ion is obtained by extracting water-soluble ions from a molded product obtained by molding and curing the resin composition, and evaluating and measuring this by ion chromatography. It can derive | lead-out by converting based on mass. Extraction of water-soluble ions at this time is performed by immersing the molded product having a specific surface area of 20 cm ² / g in 100 mL of ion-exchanged water with respect to 10 g of the molded product and immersing the molded product in ion-exchanged water and treating at 90 ° C. for 50 hours. This can be done by extracting ions in ion-exchanged water.

On the other hand, as the conductive base material, an appropriate porous sheet-like material formed of a conductive material can be used. At this time, the conductive substrate preferably has a volume resistivity of 10 ⁻² Ωcm or less in order to ensure good conductivity of the fuel cell separator 1. Examples of such a conductive substrate include woven fabrics and papers preferably made of carbon fibers. Carbon fibers include bread and pitch, and any may be used. In particular, carbon fiber paper (carbon paper) is excellent in the impregnation property of the resin composition, and also excellent in sulfuric acid resistance, chemical resistance, and methanol resistance. When using such a carbon fiber paper, it is preferable that the average length of the carbon fiber which comprises this paper is the range of 3-15 mm. If this average length is shorter than 3 mm, sufficient strength may not be obtained in the conductive substrate, and if it exceeds 15 mm, the resin composition may not be sufficiently impregnated into the conductive substrate. is there.

The basis weight of the conductive substrate is appropriately set according to the desired dimensions of the fuel cell separator 1, but in order to obtain a thin and light fuel cell separator 1 with a thickness of 0.3 mm or less, 20 to 20 A range of 210 g / m ² is preferred. If this basis weight is too small, it will be difficult to obtain sufficient impregnation of the resin composition, the number of sheets required to form the fuel cell separator 1 having a predetermined thickness will increase, and the basis weight will be excessive. As a result, the thickness of the fuel cell separator 1 increases.

The conductive substrate preferably has a tensile strength retention rate (acetone strength retention rate) of 60% or more after immersion in acetone. As shown in the following formula (1), the acetone strength retention rate R (%) is obtained by immersing the conductive substrate in acetone for 5 minutes with respect to the tensile strength S ₀ of the conductive substrate before immersion in acetone. The ratio of the tensile strength S of the thing immediately after is shown as a percentage. Here, when the tensile strength is 50 mm wide and 270 mm long, and a tensile stress is applied with a crosshead speed (tensile speed) of 100 mm / min, the tensile stress at the time when the fracture occurs. It is evaluated by.

R (%) = 100 × (S / S ₀ ) (1)
By setting the acetone strength within the above range, the toughness and strength of the fuel cell separator 1 can be further improved. Here, when the acetone strength retention is less than 60%, the conductive base material may be cut when the prepreg for a fuel cell separator is produced, or the strength of the fuel cell separator 1 may be sufficiently improved. There is a risk of disappearing.

  The prepreg for a fuel cell separator is obtained as a prepreg by impregnating the above-mentioned conductive substrate with the resin composition and then semi-curing the resin composition by heating.

  The amount of the resin composition impregnated into the conductive substrate is adjusted as appropriate, but the resin impregnation amount is preferably in the range of 50 to 150% by weight.

  Moreover, although the heating conditions after impregnation are suitably adjusted according to the desired hardening state of the resin composition in the prepreg for fuel cell separators, heating is preferably performed at a heating temperature of 100 to 170 ° C. If the heating temperature is less than 100 ° C., the solvent may remain and an internal void may be generated in the fuel cell separator 1 obtained by the prepreg for fuel cell separator. There is a possibility that the outer diameter shape becomes non-uniform and causes non-uniform conductivity.

Moreover, it is preferable that content of the volatile matter in the prepreg for fuel cell separators obtained in this way is 0.5 mass% or less. This volatile content C (mass%) is based on the mass W ₀ before heating the fuel cell separator prepreg and the mass W after heating when the fuel cell separator prepreg is heated at 163 ° C. for 15 minutes. Is derived from the following equation (2).

C (mass%) = 100 × {(S−S ₀ ) / S} (2)
In this way, by setting the volatile content to 0.5% by mass or less, generation of voids at the time of forming the fuel cell separator 1 is prevented, and gas leakage is prevented from occurring in the obtained fuel cell separator 1 and conductivity is lowered. There are things that can also be prevented.

  Thus, it is preferable to hold | maintain the prepreg for fuel cell separators obtained by impregnating and semi-hardening a resin composition to an electroconductive base material at the temperature of 10 degrees C or less after that. In this way, the progress of the curing reaction of the resin component in the prepreg for the fuel cell separator is suppressed, and it can be stored for a long period of time, at least half a year, without any change in curability.

  In producing the fuel cell separator 1 using such a prepreg for a fuel cell separator, the fuel cell separator prepreg is cut, punched, etc. according to the desired shape of the fuel cell separator 1, and formed into a predetermined shape. A single prepreg for a fuel cell separator is used according to the desired thickness dimension of the fuel cell separator 1, or a laminate of a plurality of the prepregs is used, and this is subjected to heat compression molding.

  In this heat compression molding, for example, in order to obtain a fuel cell separator 1 having a plurality of convex portions 2 as shown in FIG. Used. On this lower mold, a prepreg for a fuel cell separator which is a pressure body is laminated by laminating a predetermined number of sheets, then the upper mold is set, and the mold is clamped and heated and compressed.

  The molding conditions depend on the composition of the resin composition used to prepare the prepreg for the fuel cell separator, the degree of cure of the resin composition in the prepreg for the fuel cell separator, the area, thickness, shape, etc. of the formed fuel cell separator 1 For example, heat compression molding can be performed in the range of a temperature of 120 to 200 ° C. and a pressure of 1 to 100 MPa. In particular, if the molding is performed at a high temperature, the molding cycle can be shortened, so that the production can be efficiently performed.

  The surface roughness Ra (arithmetic mean roughness; JIS B 0601-2001) of the fuel cell separator 1 thus formed is preferably 0.8 to 1.8 μm, more preferably 0.9 to 1.6 μm. Try to be in range. The surface roughness Ra can be adjusted, for example, by removing the resin layer (skin layer) on the surface layer of the fuel cell separator 1 by blasting or the like. When the surface of the fuel cell separator 1 is thus roughened, the contact resistance between the fuel cell separator 1 and the electrode of the fuel cell adjacent thereto is reduced, and the fuel cell separators 1 are adjacent to each other. The contact resistance between the fuel cell separators 1 can be reduced.

  That is, since the electrode of the fuel cell is generally flexible, roughening the fuel cell separator 1 as described above causes the electrode to deform along the rough surface, so that the contact area between the two is reduced. It can be increased to reduce the contact resistance. In addition, when the fuel cell separators 1 are brought into contact with each other, the rough surfaces of the fuel cell separators 1 are engaged with each other to increase the contact area and reduce the contact resistance. Further, the contact resistance can be further reduced by removing the insulating skin layer on the surface layer of the fuel cell separator 1 as described above.

  Here, if the surface roughness Ra is less than 0.9 μm, the slight warpage and thickness accuracy of the fuel cell separator 1 are affected and the contact portion is reduced, so that the contact resistance cannot be sufficiently reduced, On the other hand, when the thickness exceeds 1.8 μm, the area of the contact portion with the electrode and the contact portion with the other adjacent fuel cell separator 1 is reduced, and the contact resistance increases, and the seal portion seals this contact portion. There is also a risk of gas leakage.

  The thickness of the fuel cell separator 1 formed in this way is not particularly limited, but a particularly thin and light fuel cell separator 1 can be obtained by forming the fuel cell separator 1 to have a thickness of 0.3 mm or less. At this time, a part having a thickness exceeding 0.3 mm may exist in a part of the fuel cell separator 1 due to design reasons and the like. The lower limit of the thickness of the fuel cell separator 1 is not particularly limited, and is appropriately set so that the strength required for the fuel cell separator 1 can be maintained.

  In addition, the fuel cell separator 1 can be reduced in thickness and weight as described above, and since it includes a conductive base material, it has sufficient strength and exhibits excellent conductivity.

  The fuel cell separator 1 includes, for example, a plurality of convex portions 2 (ribs) formed on both surfaces, and a hydrogen gas as a fuel and an oxidant by a concave portion 3 formed between the adjacent convex portions 2. A gas supply / discharge groove which is a flow path of oxygen gas is formed, and a solid polymer electrolyte membrane and a gas diffusion electrode (fuel electrode and oxidant electrode) are interposed between the two fuel cell separators 1. Thus, a single battery (unit cell) can be formed, and several tens to several hundreds of unit cells can be arranged side by side to form a battery body (cell stack).

  In forming the fuel cell separator 1 in this manner, the fuel cell separator 1 is formed into a corrugated plate shape as shown in FIG. Even a thin fuel cell separator 1 can form a gas flow path and the like required for the fuel cell separator 1. The fuel cell back separator shown in FIG. 1 is formed in a flat plate shape as a whole, and a plurality of rib-like convex portions 2 are formed on one surface in a predetermined region inside thereof, and between adjacent convex portions 2. A groove-shaped recess 3 is formed in the recess 3, and a gas supply / discharge groove which is a flow path of hydrogen gas as a fuel or oxygen gas as an oxidant is formed in the recess 3. Further, on the other surface of the fuel cell separator 1, a concave portion 3 is formed on the back side of the convex portion 2 on the one surface, and a convex portion 2 is formed on the back side of the concave portion 3 on the one surface. Grooves are formed, or cooling water passages through which cooling water flows are formed. In this way, the thickness of the formation position of the convex portion 2 in the fuel cell separator 1 does not increase, so that the fuel cell separator 1 can be reduced in thickness and weight. In the illustrated example, the convex portions 2 are formed on both sides at the edge of the region where the convex portions 2 and the concave portions 3 are formed so that the convex portions 2 are formed on both sides of all the concave portions 3. However, this portion is thinned as a whole except for this portion, so that it can be sufficiently thinned and lightened.

  Hereinafter, the present invention will be described in detail based on examples.

(Examples 1-19, Comparative Examples 1-5)
Each raw material was blended under the conditions shown in Tables 1 and 2, and the viscosity was adjusted by further blending a solvent (methyl ethyl ketone). The obtained resin composition was impregnated into the conductive substrate shown in Tables 1 and 2, and 150 By heating under the conditions of 5 ° C. for 5 minutes, the prepreg for a fuel cell separator having the resin adhesion amount shown in Tables 1 and 2 was obtained.

  The obtained prepregs for fuel cell separators are laminated as shown in Tables 1 and 2 and subjected to heat compression molding for 2 minutes under the conditions of a heating temperature of 175 ° C. and a pressing force of 35.3 MPa using a molding die. The pressure was reduced with the mold closed, and the mold was opened after being held for 30 seconds to form a fuel cell separator 1 having the corrugated plate shape shown in FIG. 1 and the dimensions of 200 mm × 250 mm × 0.2 mm. .

  In addition, the compounding quantity of each component in Table 1, 2 is shown by the mass part.

(Comparative Example 6)
As a stirring mixer, use a “5XDMV-rr type” manufactured by Dalton. Put the raw materials into the container so as to have the composition shown in Table 2, and rotate the stirrer in a planetary state with the container heated to 90 ° C. with hot water. After stirring for 5 minutes, a solvent (isopropanol: IPA) was added. Stirring was continued for another 10 minutes after the addition of the solvent. Next, the solvent was completely removed by drying under reduced pressure at 90 ° C. using a vacuum pump. The obtained kneaded material was pulverized to a particle size of 500 μm or less with a granulator.

The obtained pulverized product was molded under the conditions of a temperature of 175 ° C. and a pressure of 34.3 MPa (350 kg / cm ² ) for 20 minutes, and demolded to have the same shape as in Examples 1-19 and Comparative Examples 1-5. A fuel cell separator 1 was formed.

(Evaluation of resin composition)
-Viscosity: About the resin composition obtained by each Example and the comparative example, the viscosity in 25 degreeC was measured with the B-type viscosity meter.

  -Sedimentability: Immediately after stirring the resin composition obtained in each Example and Comparative Example, the varnish viscosity was measured in the same manner as described above, and after 10 minutes, the varnish viscosity was measured again in the same manner. The change in varnish viscosity caused by the precipitation of graphite particles was measured. And the thing whose fall of varnish viscosity was less than 10% was evaluated as "(circle)", and the thing whose change was 10% or more was evaluated as "*".

  Change with time: Immediately after stirring the resin composition obtained in each Example and Comparative Example, the varnish viscosity was measured in the same manner as described above, and after 168 hours in an atmosphere at 25 ° C., the varnish viscosity was measured again in the same manner. The viscosity change resulting from the progress of the curing reaction of the resin composition was measured. And the thing whose increase / decrease rate of a viscosity is less than 10% was evaluated as "(circle)", and this change 10% or more was evaluated as "x".

(Evaluation of prepreg for fuel cell separator)
Appearance evaluation: The appearance of the prepreg for a fuel cell separator obtained in each of the examples and comparative examples was visually observed. “○” indicates that no streak was observed, and “×” indicates that it was recognized. ".

  -Volatile content: The prepreg for a fuel cell separator obtained in each of Examples and Comparative Examples was heated at 163 ° C for 15 minutes, and derived based on the mass change before and after that.

(Evaluation of fuel cell separator)
Formability: For each of the examples and comparative examples, a plurality of samples having a thickness of 0.2 mm at the thinnest part were produced under the same conditions for producing the fuel cell separator 1, and the surface of the thinnest part was optically formed. Observation with a microscope confirmed the presence or absence of poor filling. And it evaluated by the number of samples which the filling defect with respect to the total sample number generate | occur | produced.

  Volume resistivity: By using the prepreg for fuel cell separator obtained in each of the examples and comparative examples, heat compression molding for 2 minutes under the conditions of a heating temperature of 175 ° C. and a pressure of 20 MPa, a plane size of 100 mm × 100 mm, A flat plate having a thickness of 0.2 mm was prepared, a sample having a plane size of 50 mm × 50 mm was cut out from the flat plate, and the volume resistivity was measured in accordance with JIS K 7194.

  Contact resistance: Carbon paper was placed above and below the sample formed in the same manner as in volume resistivity measurement, a copper plate was further placed above and below it, and a surface pressure of 1 MPa was applied in the vertical direction. The voltage between the two carbon papers was read with a voltmeter, and at the same time, the current between the two copper plates was read with an ammeter, and the resistance (average value) was calculated. The carbon paper used is TGP-HM series (090M: thickness 0.28 mm, 120M: thickness 0.38 mm) manufactured by Toray Industries, Inc.

  ・ Releasability: The surface of the upper mold and the lower mold after molding was visually observed, and the case where there was no deposit on the mold surface was evaluated as “◯”, and the case where there was an deposit was evaluated as “x”. .

  -Bending strength: The prepreg for fuel cell separators in each Example and Comparative Examples 1 to 5 was laminated and heat compression molded at 175 ° C. and 20 MPa for 3 minutes. Moreover, the pulverized material in Comparative Example 6 was subjected to heat compression molding at 175 ° C. and 20 MPa for 3 minutes. And the sample of the dimension of 50 mm x 10 mm x 0.2 mm was cut out from the part without the groove | channel of each obtained molded object. The bending strength of this sample was measured according to JIS K6911 under the conditions of a distance between fulcrums of 25 mm and a crosshead speed of 1 mm / min.

FIG. 1 shows an example of an embodiment of the present invention, where (a) is a plan view and (b) is a partial format.

Explanation of symbols

1 Fuel cell separator

Claims (8)

An electrically conductive base material is impregnated and semi-cured with a resin composition containing graphite particles having an average particle size of 5 to 35 μm, a cresol novolak type epoxy resin , and a wax to form a prepreg for a fuel cell separator. fuel cell separators method for producing and forming a corrugated shape by heating compression molding the prepreg in the molding die. The resin composition contains a curing catalyst of cresol novolac type epoxy resin, and the content is 65 to 90 mass% of the graphite particles relative to the solid content of the resin composition, the content of cresol novolac type epoxy resin 9 2. The fuel according to claim 1, wherein the fuel content is 30% by mass, the wax content is 0.1 to 3% by mass, and the curing catalyst content with respect to the cresol novolac epoxy resin is 0.5 to 5% by mass. method for producing a battery separators. Fuel cell separators method according to claim 1 or 2, wherein the basis weight of the conductive substrate is 20~210 g / m ^2. Fuel cell separators method according to any one of claims 1 to 3, wherein the viscosity measured at a B type viscometer of the resin composition is in the range of 300～1000CP. Fuel cell separators method according to any one of claims 1 to 4, wherein said conductive substrate is a carbon fiber paper. Fuel cell separators method according to any one of claims 1 to 5, wherein the content of volatile matter of the prepreg for a fuel cell separator is not more than 0.5 mass%. A fuel cell separator produced by the method for producing a fuel cell separator according to claim 1. The fuel cell separator according to claim 7 , wherein the thickness is 0.3 mm or less.

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