TWI267216B - Separator for fuel cell - Google Patents

Abstract

The present invention provides a fuel cell separator provided with resin conducting layer formed by mixing resins and conducting filler at least on one side of the surfaces of the metal substrate thereof. The resin conducting layer includes: (a) a first resin layer with volume resistance below 1.0 Omega.cm; and (b) at least one of layers selecting from a second resin layer and a third resin layer wherein the second resin layer with volume resistance lower than the first resin layer comprises the surface of the resin conducting layer and the third resin layer with volume resistance lower than the first resin layer is provided between the first resin layer and the metal substrate. Therefore, the separator for fuel cell, especially for solid polymer electrolyte type fuel cell, has excellent power collecting and formation properties, strength, and corrosion resistance.

Description

1267216 V. INSTRUCTION DESCRIPTION (1) [Technical jaw region to which the invention belongs] The present invention relates to a fuel cell crucible partitioning member, and more particularly to a fuel cell constructed by laminating a plurality of unit cells. In addition to the fuel cell passage and the oxidizing gas passing between the electrodes and the electrodes, the fuel cell and the oxidizing gas are separated by a fuel cell, and the fuel cell is excellent in formability, strength, and corrosion resistance. ~ t prior art] component preparation; material battery 'particularly solid polymer fuel cell separation for the configuration and contact between the electrodes on both sides of the solid electrolyte membrane, the road, = Ϊ Ϊ the fuel between the electrodes The supply gas passage such as a gas or an oxidizing gas: 面 ^ The surface 1 facing the electrode has a projection, a groove, and the like formed to form a gas passage. Several: L ί ? The initial power of the battery is less than 1 v. It usually consists of a stack of electrical:::it pieces. Because of A, the partition member is negative. The task of the electrode must have good current collection and good density. The battery partition member is made of a metal material such as _ (sus), chin, or y, which is made of a strength or a conductive material as a substrate. Although the electrical conductivity is very brittle, that is, J length: two: graphite The material of the partition member, '7 H. It can maintain the high current collecting performance of the table 1267216 for the partition member. 5. Description of the invention (2) Machining of machining such as cutting. _ ^. Responsible for making orders, there are difficulties in S production

On the other hand, in comparison with the graphite of H and H, the partition member s composed of s strength and the plurality of dense projections and grooves are formed in order to form a gas passage. However, even if 2 private:: with stamping processing, there is easy to mass-produce the battery, in 70~9 0 t: the temperature and sound temperature of the solid polymer fuel metal material of the partition member, and repeat the production of saturated The water vapor is used as a result of the oxide film formed by the use of electricity and oxidation, and an oxide film is easily formed, and the current collecting performance is lowered. The electric resistance is increased, and the partition member is produced. Here, the surface material of the metal material which is excellent in the separation structure is used. However, due to the high price of such materials, the price of precious metals such as gold is problematic. In order to solve these problems, there is a lack of extensive applicability. The resin layer of the conductive filler is:::, is a substrate surface = special opening 2m-1 575〇) Japanese open-ended: high, high current collection performance, formability: = '* excellent electrical conductivity. Strength and corrosion resistance [Invention] The present invention is to improve performance, as well as formability, strength and corrosion resistance Narrative ϋ = 寸 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足

1267216 V. INSTRUCTIONS OF THE INVENTION (3) Means for Solving the Problems The present invention relates to the following matters. A fuel cell partitioning member provided with a resin conductive layer mixed with a resin and a conductive filler on at least one side of a metal substrate, wherein the resin conductive layer comprises: (a) a volume resistance value of 1 · Ο Ω · a first resin layer below cm; (b) a second resin layer constituting the surface of the resin conductive layer and having a smaller volume resistance than the first resin layer, and a ratio of volume resistance values at the interface between the first resin layer and the metal substrate At least one of the third resin layers having a small first resin layer. 2. The separator for a fuel cell according to the above item 1, wherein the second resin layer and the third resin layer respectively have a volume content ratio of the conductive filler in the resin layer, and are more conductive than the first resin layer The volumetric content of the filler is large. 3. The separator for a fuel cell according to the above item 1, wherein the second resin layer and the third resin layer each have a volume resistance value of 0. 5 Ω · c m or less. 4. The separator for a fuel cell according to the above item 1, wherein the first resin layer contains 5 to 40% by volume of a conductive filler, the second resin layer and the third resin. The layers each contain 20 to 90% by volume of a conductive filler. 5. The separator for a fuel cell according to the above item 4, wherein the first resin layer contains 8 to 15% by volume of a conductive filler.

1267216 V. INSTRUCTIONS (4) 6. In the fuel cell nickel according to the above item or item 2, the material of the metal substrate is selected from the group consisting of stainless steel, titanium knives, and steel. . "S, steel 7, the fuel cell of any one of the above-mentioned items, wherein the surface of the metal substrate has at least one selected from the group consisting of nickel, tin, and "plumbing" in which platinum, silver, and palladium are formed. A layer of tantalum titanium, gold, and a layer. Electroplating of the constitutive structure 8. The partition member for a fuel cell according to the above-mentioned item (beta), wherein the surface of the substrate is roughened. /, 'This gold 9. In the fuel cell of the above item i or item 2, the conductive filler is selected from the group consisting of carbon materials, materials, metal oxides, metal nitrides and metals. The ethnic group reversal 1 〇, such as the fuel cell of any of the above items g. The conductive filler is selected from the group consisting of carbon black and a blade. And a fine carbon fiber structure according to the first or second aspect of the invention, wherein the second conductive layer of the second resin layer and the third resin layer contains the fine carbon fibers. 9 匕έ月曰 1 2. The fuel cell partitioning member according to item 11 above, the fine carbon fiber of the agricultural product, the fiber diameter of which is 0. 〇 〇丨 〇 八 中 ’ 该 该 该 该 该 该 该. The separator for a fuel cell according to the above item 9, wherein the conductive filler contained in the first resin layer contains carbon black. Eight, the 14, as mentioned above! Item or item 2 of the fuel cell;

1267216 V. In the invention description (5), the resin is selected from the group consisting of a fluororesin, a fluororubber, and a polyolefin resin. The separator for a fuel cell according to the above item 1, wherein the first resin layer has a thickness of 5 to 3 Å, and the second tree, the lipid layer, and the third resin layer are each The thickness is in the range of 〇•卜2〇. The separator for a fuel cell according to the above item 1, wherein the resin conductive layer is provided with the first resin layer and the second resin layer. The fuel cell partitioning member according to the above item or the second aspect, wherein the resin conductive layer is provided with the first resin layer and the third file, as in the first item Or a separator for a fuel cell according to the second aspect, wherein the conductive layer of the present invention is provided with the first resin layer, the first resin layer, and the third resin layer. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; The agent is mixed with the substrate having the resin conductive layer, and the step of processing the protrusions and the grooves of the gas passage is performed. In the manufacturing method of the fuel cell partition member according to the above-mentioned item 9, the step "i" of forming the protrusion portion and the groove portion by press working further includes a heat annealing step. 21. The separator for a fuel cell according to any one of the above items 1 to 18.

1267216 V. INSTRUCTION OF THE INVENTION (6) Manufacturing method 'The resin-based conductive layer coated with a metal base is coated with a protective protrusion and a protrusion from the step of forming the resin protective film. 22. The above method, wherein after the step of borrowing the ditch portion, the above method, wherein, after the step, the manufacturing method of the above-mentioned parts is more than 150% or more, and the manufacturing method of the above-mentioned parts includes the following steps. : a step of laminating at least one side of the board with a resin and a conductive filler; a surface of the outermost layer of the metal substrate of the conductive layer, covering the substrate of the film, and forming a step of forming the gas passage by press working In the substrate of the starting portion and the groove portion, the step of peeling off the protective film, the manufacturing of the fuel cell partitioning member of the second aspect, the forming of the protruding portion constituting the gas passage by press working, and further including a heating annealing step. In the production of the separator for a fuel cell according to the second aspect, the projection and the groove are formed on the substrate, and the peeling protective film includes a heat annealing step. The separator for a fuel cell according to any one of the items 2 to 2, wherein the protective film has a tensile elongation at break ratio, and the fuel cell partition structure according to any one of the items 2 to 2 &lt; wherein the thickness of the protective film is 5 to 1 〇〇 # m. [Embodiment] Fig. 1 is an enlarged model diagram showing the vicinity of a partition member of a laminated fuel cell in which a plurality of unit cells are stacked. The single battery 1 a and the single battery 丨 b have respectively

Page 12 1267216 V. INSTRUCTION DESCRIPTION (7) The solid molecular electrolyte membranes 2a, 2b, the electrodes 3a, 3b sandwiching them, the cells 1a and the cells 1b are separated by a partition member 1 〇, and the electrodes are connected at the same time. 3 a forms a gas passage 4a on the side of the unit cell la, and further, the connection electrode 3b forms a gas passage 4b on the side of the unit cell 1b. In the partition member 该 of this aspect, the resin conductive layer 12 is provided on both surfaces of the metal substrate π, and the unit cell 1a and the unit cell 1b are connected in series by the connection electrode 3a and the electrode 3b. In this example, a resin conductive layer is provided on both surfaces of a metal substrate. When the partition member is used for a single cell at the end, since only one side of the metal substrate is provided with a resin conductive layer, the following figures only show the layer of one side of the metal substrate. structure. {The resin conductive layer of the present invention has, as described above, (a) a first resin layer having a volume resistivity of 1 · Ο Ω · cm or less; (b) constituting a surface of the resin conductive layer and having a volume resistance value smaller than that of the first resin layer The second resin layer and the at least one resin layer disposed in the third resin layer having an interface with the metal substrate and having a smaller volume resistance than the first resin layer. An example of the layer structure of the partition member is shown in Fig. 2'. In this aspect, the surface of the metal substrate 11 is provided with a resin conductive layer 12, and is composed of two layers of the first resin layer 13 and the second resin layer 14. The first and second resin layers forming the surface layer of the resin conductive layer have a smaller volume resistance value than the first resin layer. In the present invention, since the second resin layer constituting the surface layer is excellent in electrical conductivity, the contact resistance with the electrodes 3a and 3b as shown in Fig. 1 can be made small. On the other hand, the first resin layer provided on the side of the metal substrate has a volume resistance value of 1 Ο Ω · cm or less, and sufficient conductivity is not required, and it is not required to have the same conductivity as the second resin layer. Therefore 'in the first resin layer, by adding resin into

I267216

V. DESCRIPTION OF THE INVENTION (8) The classification can constitute a layer having reworkability and imparting shape, strength, and corrosion resistance. That is, the volume resistivity is changed between the first resin and the second resin. The function of the resin conductive layer is shared by the first resin layer and the second resin layer while satisfying the current collecting performance as well as the formability, strength, and corrosion resistance. Moreover, FIG. 3 shows an example of a different layer structure of the partition member. This example is a structure in which the third resin layer i 5 is further provided between the first resin layer 3 and the metal substrate. The third resin layer has a smaller volume resistance value than the first resin layer, and the contact resistance between the metal substrate and the resin conductive layer can be lowered. In other words, the third resin layer is used to reduce the contact resistance with the electrode. On the other hand, the first resin layer constitutes a layer that emphasizes formability, imparts shape, strength, and sachet resistance. A partition member that satisfies both current collecting properties and formability: strength and corrosion resistance is obtained. The volume resistivity of the third resin layer may be the same as or different from the volume resistivity of the second resin layer. #作ί ^ The aspect of the partition member is a structure in which the second resin layer 丨 5 is disposed between the first resin layer and the metal substrate, that is, the second resin layer t is not provided in the aspect of FIG. 3: according to the aspect By the third resin layer, the contact resistance at the interface between the metal substrate and the resin conductive layer can be reduced. In the above three modes, the lipid layer and the third resin layer are combined to each other, and the second resin layer is simultaneously provided in the first resin layer. From the viewpoint of reducing the contact resistance, the material is more specifically described below and the materials of the respective layers are indicated. .榼Indium: Γ月? As the metal substrate used for the partition member, a thin plate made of no steel, nickel or steel can be suitably used. The thickness is expected to be 0. 0 3

1267216

V. INSTRUCTIONS (9) The range of mm~1. 5 mm is special in the range of 〇·:1~0·3 mm. The surface of the soil is also used as it is, surface treatment or setting #M '..., for various purposes, can be connected to the κ π fly and set the surface layer. For example, in order to improve the adhesion to the conductive layer of the resin, it is possible to improve the bonding property of the resin. The surface of the substrate is grounded with a decane bond or the like. By the bottom layer and/or the adhesive layer, there is a metal whose blood-suppressing resin leads the thunder and smashes it. In the case of the problem of an increase in the resistance of the human body, it is preferable not to provide such a metal substrate and a resin conductive layer. Further, the metal 2^2 is roughened to improve the bonding between the metal substrate and the resin conductive layer. The average roughness Ra of the center line is 0. 05~5. ι/ =:/0 · Bu 1 · 〇 #m is better. When the surface roughness is too small, the bonding with the resin V ^ g is insufficient, and on the other hand, the fine rough surface having a large unevenness is formed, which takes a long time and is inferior in productivity. The surface is roughened and an etching method can be used. For example, mechanical etching using an abrasive, chemical etching using a chemical, electrolytic etching using an electric energy by an anode, or the like is determined depending on the type of the metal substrate. Further, the present invention is preferably provided with a plating layer on the surface of the metal substrate. When an oxide film is formed on the surface of the genus and the contact resistance is increased, a plating layer of a metal which is difficult to form an oxide film is formed on the surface of the substrate, whereby the contact resistance between the metal substrate and the resin conductive layer can be made small. The metal constituting the plating layer is preferably nickel, tin, copper, titanium, gold, platinum, silver or palladium. Particularly preferred are nickel, tin, copper and titanium. Moreover, the stainless steel, stainless steel, steel, and steel are provided for such a battery layer. a resin mixed with a conductive layer of a resin, from the viewpoint of resistance, with a fluorine tree

1267216 V. INSTRUCTIONS (ίο) ------ - Luna, t-fluorene, polyolefin resin and polyolefin elastomer are preferred. As the fluororesin and the fluororubber, specifically, for example, pTFE (polytetrafluoroethylene), PFA &lt; (tetrafluoroethylene to perfluoroalkyl vinyl ether copolymer), FEp (tetrafluoro-6 hexafluorene); propylene copolymer ), EPE (tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer), ETFE (tetrafluoroethylene-ethylene copolymer), PCTFE (polychlorotrifluoroethylene), ECtFE (chlorotrifluoroethylene-ethylene Copolymer), PVDF (polyvinylidene fluoride), pVF (polyvinyl fluoride), THV (tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer) three VDF-HFP/vinylidene fluoride-hexafluoro A propylene copolymer), a TFE-p (fluorinated vinylene-propylene copolymer), a fluorine-containing oxime rubber, a fluorine-containing vinyl ether rubber, a fluorine-containing phosphorus-nitrogen rubber, and a fluorine-containing thermoplastic elastomer. These fluororesins or fluororubbers may be used alone or in combination of two or more. 〆 In particular, from the viewpoint of moldability, PVDF, THV, VDF-HFP, and TFE-P containing vinylidene fluoride are preferred. Specific examples of the polyolefin resin and the polyolefin elastomer include, for example, polyethylene, polypropylene, polybutylene, poly-4-methyl+pentene, polyhexene, polyoctene, hydrogenated=ethylene butadiene rubber. , EpM, EpM, EM. These may be used alone or in combination of two or more.

Among these resins, heat resistance, # y ethylene, polypropylene, and EPDM are suitable. The shape of the view, especially the poly, in addition, the conductive filler, to guide. For example, carbon-based materials, metal=high, and excellent corrosion resistance are more suitable for nitrides and metals, such as conductive ceramics, metal oxides, powders or fibers of metals.

1267216 V. INSTRUCTIONS (11) Suitable carbon fiber inks and natural graphite fine carbon fibers are 001~0.5 Μ m 'better, 1 stone anti-fiber, that is, tube, including carbon tube double tube type, and one end The sealed opening is made of -, carbon, etc., such as indium and nitrogen, and I is preferably used as zinc or silver fiber, for example, and closed, and the other is *metallized titanium or powder. At the end, it is used for metallization, and tantalum nitride is metal, group, and stainless electrical chargeable. The material 'as a powder may be, for example, graphite (artificial stone), carbon black, expanded graphite or the like. The fibrous ones may be, for example, micro and carbon fibers. Further, fine carbon fibers have a fiber diameter of 〇. '0·0 03 to 0·2 // ηι is preferable, and the fiber length is 1 to; [00 # 〜3 0 # m is preferable from the viewpoint of conductivity. Fine with carbon nanotubes and carbon fiber. The carbon tube having a single carbon tube structure as a single tube and the carbon tube structure having a double tube is a multi-tube type having a triple or more structure, and further includes a nano-horn type (nan〇h〇rn) opened at one end of the tube, one end &lt; A pattern of a cup type having a large opening. The carbides may be, for example, tungsten carbide, carbonized sharp, molybdenum carbide, or carbonized. Among them, tungsten carbide or titanium carbide fibers are preferred. Examples of the nitrides include powders such as chromium nitride aluminum nitride, titanium nitride, and gallium nitride, and fibers. Among them, carbonized, carbonized chromium carbide and carbonized carbide, chromium carbide aluminum nitride, tantalum nitride nitride, nitrided to chromium nitride, nitride, powders such as titanium, nickel, tin, copper, aluminum, As the powder of the affinity, the fiber may, for example, be an iron fiber or a copper steel fiber. Only one type of the filler may be used, and two or more types may be used in combination. Mixed carbon nanotubes and/or nano carbon fibers, and

Page 17 I267216

V. Description of the invention His carbon-based materials. Among the w conductive fillers of 7 〇 to 90, in particular, the conductive filler is high, and even if it is preferable, the degree of removal is close to saturated steam, and the resistance change is small, and the material &amp; The material is preferred. Specifically, it is particularly preferred that the carbon black is a mixture of either or both of the fibers. (In the case of a powder, in the case of a powder, it is usually measured by a weight average particle diameter of 1 〇 2), preferably 20 or less, preferably 15 or less. In addition, it is usually 0.01 or more, 0·03 //Π1 is the above, Α ', if it is fibrous, the fine carbon fiber is as good as the above, and when the material is fiber, the fiber diameter is 50 //m. Below, 20 / 1 in 1 ~ ^ (^), usually above 1 / / D1, 5 is better, fiber length Ben Su / 111, from the point of view of conductivity in 5 ~ 1 0 0 / zm good. a filler, a person 1 resin conductive layer, is a mixture of the above resin and a conductive charge resistance value in the &quot;&amp;, the volume of the first resin layer on the surface of the metal substrate is connected, regarding the first - CD1 I According to JIS K7194, the volume resistivity of the first-tree resin layer and the third resin layer may be appropriately adjusted so as to be smaller than the volume resistance of the first: r Μ, and may be appropriately formulated. The second resin layer also accumulates the resistance value, which is better at °.5 Ω._, and the special volume resistance value is extremely high! ί:: The situation under ί. Ω. (10) of the first to third resin layers is slightly smaller than t, and there is a practical limit, usually 0.00 0 1 ω.cm or more = in °·° 0 () 1 Ω, or more ' Typical is in. . . . 1 The present invention can be used to form a second resin layer and a third resin layer (division/layer), which is a conductive filler in the respective layers.

Page 18 1267216 V. Description of invention (13) Volumetric content rate, high rate. Specifically, the amount is a volume ratio of 5 to 40, and the amount of the filler of the following conductivity-filling filler is higher than the content of the filler in the first layer of the resin layer. In the case where the three resin layers are appropriately changed, the carbon black is preferably used, and the second conductive material is contained. The conductivity of the first conductive layer is 5 to 300 //m 2 resin layer for each tree. Preferably, the conductive filler in the first resin layer is 1% of the conductive filler in the first resin layer, and the conductive filler in the first resin layer is the same (where the '% by volume of the filler is the same) The volume content of the second resin layer and the first agent is preferably from 20 to 90% by volume, and is more preferably in the second resin layer and the lipid layer. Further, it is preferably from 8 to 15% by volume, and on the other hand, from 2 to 90% by volume in the second. These contents, 体积 volume resistance value of at least 1·0 Ω·cm, are preferably selected as appropriate. Both the second resin layer and the third resin layer may be of the second or different type and amount of the conductive filler. In the aspect, the conductive resin layer and the third resin layer are contained in the first resin layer (the filler is a fine carbon fiber, respectively. However, the second resin layer and the third resin layer together have a filler as a fine carbon fiber, In the case where the filler is carbon black. The thickness of the lipid layer is first, preferably, the first resin layer is 10 15 〇V m , and the volume of the third resin layer is usually 01 to 20 in a volume of 10 to 10 〇. The volume of the three-body resin layer containing the resin layer, the conductive three-resin layer in the case where the first resin 1 and the third resin are electrically charged and charged, and the case of the electric resin filling agent Particularly preferably, the thickness of the resin layer is usually preferably / / m. //m to

Page 19 (14) 1267216 Five inventions show that the effect of all tree rot is small, if D ^ thick ^ : ^ thin, the resistance to the metal substrate becomes larger, test; 4 ϋ ί thick makes the fuel into a stack a ¥ Electrical properties, formability, strength, etc., the normal range of the product *~ 4 = is preferred. Therefore, usually at 51: the above (four) is better, and the better is 15~! The manufacturing method of the partition member of Fan Maoming of 5〇 and 2, the helmet, the resin layer, the second tree wax layer, the third resin layer, for example, the first roll forming method, such as the roll forming method, is formed in advance. On the second == surface, the third resin layer (if one side of the soil plate or the rain grease layer is hot-processed to make it integrated, the conditions of rolling::: layer, second tree 4, may also be Heating temperature, y force. (3〇kgf/cm2~100 "&quot;-π2) degree and especially with regard to the second and third resin layer filling: 'Because it is difficult to form with self Retentive; conductive at this time pre-formed on a suitable transcription substrate to form a thin 'layer can be laminated. Shaped on the transcription substrate;: heat = dry filler on the transcription substrate dissolved in a suitable solvent 'coated on the burning: A gas passage such as an oxidizing gas must be formed between the battery's partition member and the electrode. On the surface of the partition member, a plurality of protrusions and a groove portion must be provided for the two-body passage'. Open:::; Forming a resin conductive reed set on a metal substrate: Press working is formed, the projection and groove 201,267,216 page portion

V. DESCRIPTION OF THE INVENTION (15) The method of the partition 2 is preferable from the viewpoint of productivity. According to the conditions at the time of press processing, the surface layer of the bamboo shoots in the resin layer. Here, in order to prevent this, a method of applying a protective film to the surface of the resin and then performing press working is preferred. ♦ 罨 layer as the protective film, the tensile elongation at break of the film is preferably 15 〇 / ° or more, and when the tensile elongation at break is less than 150%, the extension of the film is less, if stamping is formed The resin layer of the conductive filler is more likely to be cut off or cracked, and the thickness of the protective film is preferably in the range of 5 to 100 /zm, and is thick. No, the film becomes too thin to be used, and the strength is insufficient, and the rupture at the time of ς $ has a tendency to hardly exhibit the function of the protective film. Further, when the thickness exceeds 111, the film becomes too thick, and the interval between the plurality of projections and the groove portion forming the gas passage is narrowed, and it is difficult to form a deep gas passage. As the material of the protective film, a thermoplastic resin, a rubber, a bismuth elastomer, or the like can be used. Specifically, as a thermoplastic resin, for example, polyene 2, polyvinyl acetate, polyvinyl chloride, polyglycolized vinylene, polyurethane, fluororesin, polyamine, polyacetate, polyamidoxime At least one or more thermoplastic resins of a group consisting of amines and the like. X Also, as rubber, for example, natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, chloroprene rubber, nitro At least one type of rubber composed of rubber, acrylate rubber, epichlorohydrin rubber, chlorinated polyethylene, ruthenium rubber, fluororubber rubber, fluororubber, polysulfide rubber, urethane rubber or the like.

Page 21 1267216

V. INSTRUCTIONS (16) As thermoplastic elastomers, for example, styrene-based oxime, urethane, vinegar, sulfonate, chloroethylene, at least one thermoplastic elastomer tensile fracture The polyolefin having a large elongation and the rubber containing ethylene can be suitably used as a plant such as a diene system or a stellite system, a gas system, and a copolymer. Among these, the olefin-vinyl acetate copolymer thermoplastic elastomer is relatively inexpensive. Here, the coating method of the film is not particularly limited. After forming a dog-like portion or a crotch portion by press working, the protective film must be peeled off, and the bonding strength between the protective film and the metal substrate coated with the conductive resin layer is in the case of the heat fusion method. The temperature is adjusted, and the pressure at the time of bonding is adjusted in the adhesive method, and the appropriate joint strength which can be peeled off is appropriately determined. ^, and annealing treatment after "stamping" is preferred. The annealing treatment is a treatment for eliminating fine cracks or deformation in the conductive layer of the resin, and heating is performed to the extent that the resin mixed in the resin conductive layer is softened. The annealing treatment i can also be carried out after the press working without using the protective film, and after the press working using the protective film or after peeling off the protective film, it is preferable to perform annealing treatment. Therefore, the occurrence of the defective portion is suppressed, and even if it is used for a long period of time, the increase in the resistance value and the elution of the metal component from the metal substrate can be prevented. The temperature at which the annealing treatment is carried out is preferably carried out at a temperature different from the melting point or softening point of the resin depending on the kind of the resin to be mixed. When the resin of the resin conductive layer is a fluororesin or a fluororubber, the annealing temperature is in the range of 150 to 300 ° C, preferably 20 minutes. Especially

Page 22 1267216, invention description (17) In the case of using PVDF or THV as the fluororesin, it is preferably in the range of 150 to 2,000, and 5 to 1 minute. Further, the case of the polyolefin resin and the polyolefin elastomer is in the range of 110 to 200 ° C; [~ 20 minutes is preferable. In particular, in the case of using a polyolefin elastomer containing propylene, it is preferably in the range of 180 to 2 〇〇 〇 c for 5 1 minute. EXAMPLES Hereinafter, examples are described, but the present invention is not limited to the above-described embodiments. <Measurement of Volume Resistance Value>

The volume resistivity of the conductive film was measured in accordance with J I S K 7 1 CU ^ . Ii94, performed by 1. measuring device

Loresta HP (Mitsubishi Chemical Co., Ltd.) 2. Measurement method Four-terminal four-point probe (ASP type probe)

3 · Current applied during measurement 10 0mA <Measurement of area resistance>

The evaluation of the area resistance was carried out in the following manner: 1. Measuring device / J. Naka Nakajima Co., Ltd. (Kawasaki Seiki Research Institute, Ltd.) (area 1 square centimeter, mirror resistance meter: YMR~3 type (loading device: YSR) -8 type electrode: yellow steel plate 2 2. Measurement conditions

1267216 V. INSTRUCTIONS (18) Method: Four-terminal application of current: Appearance surface pressure of open terminal ·· 3. Measurement method The resistance is measured by four-terminal method from both sides by yellow as shown in Fig. 2 . <Example 1> Fluorine resin (%, with a specific gravity of 1 as the conductivity of EC6 00 JD 1 The above-mentioned mixed 5 〇 / / m conductivity value of 0. 8 Ω cm metal substrate nickel plating layer 0. 8 ("GE Toshiba nickname Bar coater coating method 10 mA (AC '287 Hz) Voltage: 20 mV peak or less 90. 90 xl〇5 Pa 1.8 xl 〇5 Pa 4. 5 χ1〇5 Pa 9· 0 xl〇5 Pa 18 xl〇5 In the measurement device shown in the above, the partitioning member 23 is sandwiched between the carbon paper and copper electrodes 21, and a predetermined load is applied thereto, and the voltage at the time of applying a predetermined current is applied to obtain a contact electric power. )) 1'11¥4156 specific gravity 2) 88-volume tantalum carbon black ("Keeenblack" manufactured by Lion Co., Ltd.) 1 2 vol% was mixed in a biaxial extruder. 240 t ) A thick fluororesin sheet is produced. The volumetric electric resistance of the conductive fluororesin is formed on the surface of the main _ 7 of SUS3 04 (thickness 〇·3 mm) as a metal plate as a bottom layer. TSL833 1) 0.3% ethanol soluble i 2 = ι〇 cloth on both sides of SUS304 forming a plating layer, recognized 1Λ ^ at 10〇

1267216 V. Inventive Note (19) Drying at °C for 10 minutes, loading in the order of conductive fluororesin sheet/SUS3 04/conductive fluororesin sheet, and laminating the laminate on a metal substrate by hot pressing. The first resin layer is formed on both sides. The conditions of hot pressing are carried out at a temperature of 2 〇 0, 1 〇 minutes, a pressure of 3 · 5 χ 〇 6 Pa (36 kgf/cm 2 ). On the other hand, 'for the formation of the second resin layer, 'the solid content is 10% by weight in MEK (2-butanone), and the fluororesin ("THV2 2 0G specific gravity 2 by Sumitomo 3% Co., Ltd.") The fine carbon fiber ("PVCF" of the Showa Denko Co., Ltd.) has a volume ratio of 3 0 / 70 to prepare a coating. The coating material was applied to a substrate film (polyethylene terephthalate, manufactured by Mitsubishi Chemical Co., Ltd., thickness: 2 5 β m) at 80 in a bar coater ("Shovel Co., Ltd." No. 24). The solvent was dried at ° C to obtain a transcription sheet of a transcription layer having a thickness of 10 # m. Two pieces of the obtained transcription sheet were used, and the resin surface was overlapped with the first resin layer on both sides of the metal substrate, and after hot pressing at a temperature of 2 Torr, 10 minutes, and a pressure of 3·5χ1〇6 Pa (36 kgf/cm 2 ). The transcription substrate is peeled off to form a second resin layer. Further, the volume resistivity of the second resin layer was measured, and it was 35 cm. The total thickness of the obtained composite panel 1 was Q . 4 2 m m. <Example 2> A fluororesin sheet (first resin layer, thickness 50 μm) and two transcription sheets (transcription layer, thickness 1 〇匕, transcription substrate (PET sheet) were placed on the outer side in the same manner as in Example 1 , loaded in the order of transcription sheet/fluororesin sheet/transcription sheet, at temperature, generation, 1 minute,

1267216

After hot pressing, two transcripts were made into the second and third resin layers. The pressure of 3·5xl06 Pa (36 kgf/cm2) was peeled off, and the total thickness of the sheet formed on both sides of the first resin layer was 170 kg. In the same manner as in the example, the nickel-plated layer 〇·8 was formed on the surface of the SUS304 as a metal plate, and the conductive sheet/SUS30 4/conductive sheet was loaded in the order of 2 Å. 〇°C : 10 minutes, pressure 3·5xl06 Pa (36 kgf/cm2 ) for hot pressing, integrating the layers, forming a second resin layer/first resin layer/third from the outside on both sides of the metal substrate Resin layer.

The resulting composite panel 2 has a total thickness of 〇, 44 mm. <Example 3> Manufactured by 131% of the "Lion Co., Ltd.", a polyolefin-based elastomer ("Ishigaki Kogyo Co., Ltd. 〇·88"), which is a conductive agent, is used as a conductive agent. 5克厘米。 (Forming temperature 26 (TC) is made strictly. The carbon black (Kejenblack EC600JD specific gravity 1·5) 15 vol% and 0. The conductive mixture of the above mixture is formed into a shape of 50 μm. Acoustic sheet. The conductivity is thankful and the volume of the resin is electrically charged. On the other hand, as the second resin layer is formed, the solid content in the cyclohexane is 10% by weight. ("Asahi Kasuga-Make") Tuftec H1041 specific gravity 91·91) Mixed with fine carbon fiber, "Gas-grain carbon fiber <VGCF> specific gravity (manufactured by Kudo Electric Co., Ltd.) 2) . -Babi Paint the above coating with a bar coater ("Songo Industry _ 笙9, Clothing" No. 24)

1267216

On the substrate film (polyethylene terephthalate, Mitsubishi Chemical Co., Ltd., thickness 25 #m), the solvent was dried at 80 ° C to obtain a transcription sheet having a thickness of 10 0 m of the transcription layer. A polyolefin resin sheet (first resin layer, thickness 5 Å) and a transcription sheet (transcription layer, thickness 1 〇 _) were placed on the outside, according to the transcription sheet/polyolefin resin sheet. / The transcription sheets are sequentially loaded, and after hot pressing at a temperature of 20 (rc, 1 minute, pressure 3 5χ1〇6 pa (36 kgf/cm2), the two transcription substrates are peeled off on both sides of the first resin layer. The second and third resin layers were formed. The total thickness of the obtained sheet was 70 μm, and two sheets of the conductive sheet obtained above were formed on the surface of SUS3 04 (thickness 〇·3 _) in the same manner as in Example 2 The nickel plating layer 0.8 is loaded as a metal plate in the order of the conductive sheet/SUS30 4/conductive sheet, and is hot-pressed at a temperature of 2 0 0 ° C, 1 minute, and a pressure of 3.5×10 6 Pa (36 kgf/cm 2 ). The laminate is integrated to form a resin layer/first resin layer/third resin layer from the outside on both sides of the metal substrate. The total thickness of the obtained composite sheet 3 is 44. 44 mm. <Example 4> Abrasive material for aluminum (Sakurandam R#150, manufactured by Carlit丨 Co., Ltd., Japan) Scribe grinder, roughening the surface of SUS304 (center line average roughness Ra = 0 · 3 β m ), and then forming a nickel plating layer of 0 · 8 // m as a metal plate, and the embodiment 2 In the same manner, composite plate 4 was produced. <Measurement of area resistance value of Examples 1 to 4>

Page 27 I267216

V. INSTRUCTION OF THE INVENTION (22) The measurement of the area resistance value of the persons obtained in Examples 1 to 4, '&gt;, and 5 sheets 1 to 4 is not shown in Fig. 5.彳隹# »_l 4·, only 疋 结 ’ is shown in Figure 5. For the comparison of 鲈 _ 八 ^ i 〇, W is the measurement of the electrical value; lipid injection graphite G347B.仃Comparatively, the tree made by Tokai Carbon Co., Ltd. is also evaluated. As shown in Fig. 5, the area resistance value of the first, 笫2 to 4 area is particularly /^/three resin laminated layers. People have the same degree of the same as in the case of graphite. Example 5 The composite film formed in Example 4 is a polyethylene film #63128, thickness 5 () V m ), which is affixed with a hand roller.螬胜^ + 予 and ί) 护 Protective film, made into a composite film 41 film. Furthermore, on the other side, a protective film of ##/f = and one pair is attached, and the measurement is performed according to JIS Κ7127. 1 右右吉士士 I, , ,,° in the direction of the pancreas (MD) The direction is 550% and is 6〇〇% in the right angle direction (TD direction). <Results of Pressing Process> The shape of the gas passage after the composite plate 41 obtained by the above method and the composite sheet 4 without the protective film are wave-shaped, and a shapeable gas passage = 3 nun 'wave-like recessed portion is used. The mold was tested at room temperature by a press (manufactured by Amada Co., Ltd. "Torque pex press" at a press speed of 45 spm). After the press-formed composite sheet 4 and the composite sheet 4 were peeled off from the protective film, the wavy convex portions were observed with a microscope ("Digital HD microscope VH-70" manufactured by Keyence Corporation). As a result, in the composite sheet 4' without the protective film, the resin conductive layer is cut and cracked, and the protective film is attached.

Page 28

1267216 V. INSTRUCTIONS (23) The composite panel 4 1 is completely free of cracks. INDUSTRIAL APPLICABILITY According to the present invention, a fuel cell which satisfies both current collecting performance, formability, strength, and corrosion resistance, particularly a partition member for a solid polymer electrolyte fuel cell, is provided. Therefore, it is highly usable as a fuel cell that operates for a long time.

Page 29 1267216 Brief description of the diagram V. [Simple description of the drawing] Fig. 1 is a model diagram showing the vicinity of the partition member of the fuel cell. Fig. 2 shows an example of the layer structure of the partition member of the present invention. Fig. 3 shows an example of the layer structure of the partition member of the present invention. Fig. 4 shows a method of measuring the area resistance. Fig. 5 is a graph showing the relationship between the applied surface pressure and the area resistance value. Description of the component symbols: 1 a : Single cell I b : Single cell 2a : Solid polymer electrolyte membrane 2b : Solid polymer electrolyte membrane 3 a : Electrode 3b : Electrode 4 a : Gas passage 4 b : Gas passage 10 : Separation member II : Metal substrate 12: resin conductive layer 13: first resin layer 14: second resin layer 15: third resin layer 21: brass electrode 2 2: broke paper

Page 30 1267216 Schematic description of the diagram 2 3 · Separator ( ( page 31

II

Claims (1)

1267216 VI. Patent application scope 1. A separator for a fuel cell, wherein at least one side of the metal substrate is provided with a resin conductive layer formed by mixing a resin and a conductive filler, wherein the resin conductive layer comprises: a first resin layer having a volume resistance value of 1 Ο Ω · cm or less; and (b) a second resin layer constituting a surface of the resin conductive layer and having a smaller volume resistance than the first resin layer, and a volume resistance ratio The first resin layer is at least one resin layer selected from a group consisting of a third resin layer at the interface between the first resin layer and the metal substrate. 2. The separator for a fuel cell according to claim 1, wherein the second resin layer and the third resin layer have a volume content ratio of the conductive filler in each of the resin layers, The conductive filler in a resin layer has a large volume content ratio. The singularity of the second resin layer and the third resin layer is 0. 5 Ω · cm or less, as described in the above. 4. The separator for a fuel cell according to claim 1 or 2, wherein the first resin layer contains 5 to 40% by volume of a conductive filler, and the second resin layer and the third The resin layer contains 20 to 90% by volume of a conductive filler, respectively. 5. The separator for a fuel cell according to claim 4, wherein the first resin layer contains 8 to 15% by volume of a conductive filler. 6. The fuel cell separation member according to claim 1 or 2, wherein the material of the metal substrate is selected from the group consisting of stainless steel, titanium, aluminum, Page 32 1267216 VI. Scope of application for patents The group consisting of copper, nickel and steel. 7. If the patent application scope is the surface of the metal substrate and! A separator for a fuel cell, in which a self-recording of tin, steel, gold, gold, and white is composed of gold, silver, and |bar. A shovel composed of at least one type of metal in the group of the aging group. For example, the partition member for a fuel cell of the sixth aspect of the patent range, A* The surface of the metal substrate is subjected to roughening treatment. 9. The fuel cell component according to claim 1 or 2, wherein the conductive filler is selected from the group consisting of carbonaceous materials, carbides, metal oxides, metal nitrides, and A family of metals: a separator for a fuel cell according to claim 9 of the patent application, and a white filler material selected from the group consisting of carbon black and fine carbon fibers. The fuel cell member according to Item 1 or 2, wherein the second conductive resin and the third resin layer each contain a lipid conductive filler, and the fine carbon is included. In the fuel cell separator according to Item 1, the fine carbon fiber has a fiber diameter of 〇· 〇 (Π 〇 〇 5 5 及 及 及 及 及 及 及 及 及 及 及 及 m m m m m m m m m m m m m m m m m m m m m m m Its // m to The separator for a fuel cell according to claim 9, wherein the conductive filler contained in the first resin layer contains carbon black. In the fuel cell separator according to the first or second aspect of the invention, the resin is selected from the group consisting of fluororesin, fluororubber, and polyolefin resin. The invention relates to a fuel cell partitioning member according to claim 1 or 2, wherein the thickness of the first resin layer is in the range of 5~3 0 0 // m, the first The thickness of each of the two resin layers and the third resin layer is in the range of 0.1 to 2 0 /zm. The separator for a fuel cell according to claim 1 or 2, wherein the resin conductive layer is provided with the first resin layer and the second resin layer. The fuel cell separator according to claim 1 or 2, wherein the resin conductive layer is provided with the first resin layer and the third resin layer. The separator for a fuel cell according to claim 1 or 2, wherein the resin conductive layer is provided with the first resin layer, the second resin layer, and the third resin layer. A method for producing a fuel cell partition member, comprising the fuel cell partition member according to any one of claims 1 to 18, comprising the steps of: mixing at least one side of the metal substrate a step of forming a resin conductive layer of a resin and a conductive filler; and forming a protrusion and a groove constituting the gas passage by press working on the substrate having the resin conductive layer. The method for producing a fuel cell partition member according to claim 19, wherein the step of forming the protrusion portion and the groove portion by press working further includes a heat annealing step. 2 1. A method for manufacturing a partition member for a fuel cell, for manufacturing 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 a step of laminating a resin conductive layer; a step of coating a protective film on an outermost surface of the metal substrate of the resin conductive layer; and forming a protrusion and a groove forming a gas passage by press working on the substrate coated with the protective film Step; a step of peeling off the protective film from the substrate on which the protrusion and the groove are formed. 2. The method for producing a fuel cell partition member according to the second aspect of the invention, wherein the step of forming the protrusion and the groove portion constituting the gas passage by press working further includes a heating annealing step. The method for producing a fuel cell partition member according to the second aspect of the invention, wherein the step of peeling off the protective film from the substrate on which the protrusion portion and the groove portion are formed further includes a heat annealing step. The method for producing a separator for a fuel cell according to any one of claims 2 to 23, wherein the tensile elongation at break of the protective film is 150% or more in both the longitudinal and transverse directions. The method of manufacturing a separator for a fuel cell according to any one of claims 2 to 23, wherein the thickness of the protective film is 5 to 10 〇 // Page 35