JP5006028B2 - Fuel cell separator - Google Patents

Description

  The present invention relates to a separator for a fuel cell used for a solid polymer electrolyte fuel cell and a fuel cell using the same, and more particularly, a substance having strong corrosive properties such as fluoride ions or hydrofluoric acid (hydrofluoric acid). The present invention relates to a fuel cell separator that suppresses discharge and a fuel cell using the same.

Fuel cells are highly efficient because they can directly convert chemical changes into electrical energy, and do not burn fuels containing nitrogen, sulfur, etc., so emissions of air pollutants (NO _x , SO _x, etc.) There are few features that are friendly to the global environment. There are several types of fuel cells depending on the type of electrolyte.

  For example, a phosphoric acid fuel cell (PAFC) is a type that uses phosphoric acid soaked in a support, and is operated at a temperature of about 150 to 220 ° C. The molten carbonate fuel cell (MCFC) uses a mixture of lithium carbonate / potassium carbonate and is molded into an electrolyte holder, and operates at a temperature of about 600 to 700 ° C. Further, in a solid oxide fuel cell (SOFC), stabilized zirconia having oxygen ion conductivity is used as an electrolyte, and it operates at a temperature of about 700 to 1000 ° C. In any case, hydrogen, reformed gas, hydrocarbon or the like is used for fuel, and air is generally used for oxidant gas.

  On the other hand, the solid polymer electrolyte fuel cell (PEFC) and the direct methanol fuel cell (DMFC) use a solid polymer membrane as an electrolyte, and the temperature is much lower than that of the fuel cell. It has the feature of operating in an environment of about ℃. Due to this feature, PEFC and DMFC are expected to spread in the future as power sources for automobiles, general households, etc., as mobile device power sources and uninterruptible power sources. In the present specification, the solid polymer electrolyte fuel cell (PEFC) includes a direct methanol fuel cell (DMFC).

  FIG. 1 is a schematic exploded perspective view showing an example of a basic configuration in a fuel cell stack of a solid polymer electrolyte fuel cell. In the fuel cell stack, a plurality of basic units (single cells) composed of a combination of MEA 5, gas diffusion layer 7, and separator unit 1 ′ are sequentially stacked in series, and sandwiched between current collector plate 8, insulating plate 9, and end plate 10. It has a structure. If necessary, the cooling unit 6 may be inserted between single cells.

  The MEA (Membrane Electrode Assembly) 5 is a main member of PEFC power generation, and is configured by joining carbon electrodes carrying a catalyst such as platinum on both sides of a polymer-like solid electrolyte. The The gas diffusion layer 7 is usually made of a porous carbon sheet and plays a role of supplying the reaction gas to the electrodes efficiently and uniformly.

  FIG. 2 is a schematic exploded perspective view showing an example of the configuration of the separator unit 1 ′. The separator unit 1 ′ is composed of a separator 1 and a gasket 4. The separator 1 is a plate on which flow paths of fuel (gas containing hydrogen or methanol aqueous solution) and oxidant gas (oxygen or air) are formed. The separator 1 electrically connects adjacent single cells and oxidizes the fuel. It is a member for preventing the agent gas from being mixed. Moreover, the gasket 4 is a member for filling the gap between the separator 1 and the MEA 5 and maintaining the airtightness of the reaction gas.

  The fuel and the oxidant gas are collectively referred to as a reaction gas or a reaction fluid. For reference, the flow of the reaction gas is illustrated in the figure with a solid line. The reaction gas flows from the manifold 101 on the inlet side along the concavo-convex reaction gas flow path 106 (the portion where the flange portion 104 and the groove portion 105 are processed) provided in the separator 1. At that time, a reactive gas is supplied to the MEA 5 via the gas diffusion layer 7 shown in FIG. Thereafter, excess reaction gas reaches the outlet-side manifold 401 and is discharged.

  As shown in FIG. 1, in a fuel cell stack, a predetermined number of single cells are connected in series so as to obtain a desired output voltage. For this reason, depending on the desired output voltage, the number of separators may be several tens to one hundred or more.

  Conventionally, graphite-based materials have been mainly used as PEFC separator materials from the viewpoint of corrosion resistance and conductivity. However, the formation of the flow path by cutting the graphite separator has a high manufacturing cost, and there is a problem that the cost of the fuel cell system becomes very high as the number of used sheets increases as described above. In addition, a graphite separator using a resin molding method has a problem that it is difficult to reduce the thickness of the separator from the viewpoint of mechanical strength, and it is difficult to reduce the size of the fuel cell system.

  On the other hand, it has been proposed to use a metal having corrosion resistance such as stainless steel (SUS) as a separator material. This is because the conductivity of the metal is generally superior to that of the graphite material, and the high toughness and ductility make it possible to perform press molding, and the use of a thin plate makes it possible to reduce the size and weight of the separator. If the metal used as the separator material is a general-purpose metal, the material is easily available and inexpensive. Therefore, further cost reduction can be expected.

  On the other hand, when stainless steel is used as the separator material for the solid polymer electrolyte fuel cell, if it is used as it is without surface treatment, the constituent elements of stainless steel are eluted, the separator is damaged, and the fuel cell characteristics are deteriorated. It is known to let you.

  As a countermeasure, for example, a metal separator is known in which stainless steel is used as a base material, Au (gold) is formed on the surface thereof with a plating layer having a thickness of 0.01 to 0.06 μm, and contact resistance is reduced. (For example, refer to Patent Document 1).

  However, such a thin noble metal coating is porous and does not completely cover the surface of stainless steel. For this reason, although there is no dissatisfaction with conductivity, it is unsatisfactory from the viewpoint of corrosion resistance, and the constituent elements of stainless steel are eluted when used for a long time, and the fuel cell characteristics are deteriorated. On the other hand, if the noble metal film is thickened to such an extent that it does not become a problem in terms of corrosion resistance, the cost increases even if the problem of corrosion resistance is solved, and is not practical.

  As what solves this problem, there exists a thing shown by patent document 2, for example. This metal separator is made of stainless steel as a base material, and an acid-resistant film made of Ta (tantalum), Zr (zirconium), Nb (niobium), Ti (titanium), etc. is formed on the entire surface of the separator. Metal separators with improved corrosion resistance and conductivity are known in which a conductive film of Au, Pt (platinum), Pd (palladium), etc. is plated to a thickness of 0.1 μm or less and 0.03 μm as an example. Yes.

  Further, for example, Patent Document 3 discloses the following metal separator. This metal separator is made of Au, Ru (ruthenium), Rh (rhodium), Pd, Os (osmium), Ir (iridium), and Pt on the surface of a metal plate such as SUS, Al (aluminum), and Ti. More than at least one kind of noble metal selected from the above, or the oxide part of the noble metal is arranged in a thickness of 3 to 50 nm, and the part other than the noble metal or the oxide part of the noble metal is covered with a corrosion-resistant coating, Corrosion resistance is provided.

  Further, for example, Patent Document 4 discloses the following metal separator. In this metal separator, an alumite film having a thickness of 5 to 50 μm is formed on the entire surface of an Al metal plate having a purity of 99.5% or more, and after removing the alumite film on the electrode contact surface, Pt, Au, Pd, Ru A conductive film made of a metal selected from the group consisting of Rh, Ir, and Ag or an alloy thereof, carbon, or a conductive carbide is formed so as to have high conductivity and corrosion resistance.

For example, Patent Document 5 discloses the following metal separator. This metal separator is a separator made of three layers of metal, and at least one selected from iron, aluminum, copper, titanium, magnesium, zirconium, tantalum, niobium, tungsten, nickel, chromium and alloys thereof in the center layer. A metal selected from the group consisting of titanium, zirconium, tantalum, niobium and alloys thereof, and at least one conductive material selected from carbon, conductive ceramics and metal powder on the surface; It has a coating layer composed of a resin binder for fixing the conductive material, and is said to be able to obtain excellent conductivity and corrosion resistance.
JP-A-10-228914 JP 2001-93538 A JP 2001-297777 A JP 2001-338658 A JP 2003-272659 A

  On the other hand, as the development of fuel cells progresses, several new problems have become apparent in fuel cells using solid polymer electrolyte membranes. One of them is that the fluorine-based solid polymer electrolyte membranes (for example, perfluorosulfonic acid electrolyte membranes and perfluorocarboxylic acid electrolyte membranes), which are currently mainstream in PEFC and DMFC, have chemical effects during power generation. As a result, it was clarified that sulfate ions and fluoride ions constituting the electrolyte membrane were mixed in the wastewater accompanying power generation.

  In a conventional metal separator for a fuel cell, for example, corrosion resistance to sulfuric acid acidity of about pH 2 to 3 at about 80 ° C. is ensured to some extent. This is presumably because the acid-resistant layer or film described above was formed on the entire surface facing the electrolyte membrane.

  However, fluoride ions and hydrofluoric acid (hydrofluoric acid) are highly corrosive and corrode metal materials such as metal separators (including the acid-resistant layers and films described above) and piping materials. A new problem that has not been considered in the past has become a big problem. For example, if the acid-resistant layer or film described above corrodes, the conductivity inherent to the metal separator cannot be maintained, and the power generation efficiency of the fuel cell deteriorates. Furthermore, a separator, a piping material, etc. may be corroded. In addition, when the corrosion product is taken into the MEA, the decomposition of the electrolyte membrane may be accelerated, the ionic conductivity of the electrolyte membrane may be reduced, or the activity of the catalyst may be reduced.

  For such new problems (generation of highly corrosive substances such as fluoride ions or hydrofluoric acid), the metal separators of Patent Documents 2 to 5 also have long-term reliability (practical use). There is a concern that it may appear as a decrease in the durability.

  Accordingly, an object of the present invention is to reduce a substance having strong corrosive properties such as fluoride ions or hydrofluoric acid mixed in waste water accompanying power generation, and to ensure a practical durability and a metallic separator for a fuel cell. It is to provide a fuel cell using the same.

  In order to achieve the above object, the present invention provides a metal separator in a fuel cell using a solid polymer electrolyte, wherein a part of the surface facing the electrolyte has a thickness greater than or equal to a predetermined thickness. A separator for a fuel cell, wherein the aluminum or aluminum alloy is exposed, and has a film growth inhibiting layer that suppresses the growth of a passive film in the electrical contact region of the separator. .

  Further, in order to achieve the above object, the present invention provides a metal separator in a fuel cell using a solid polymer electrolyte, wherein titanium or a titanium alloy is formed on a surface of the substrate made of aluminum or an aluminum alloy facing the electrolyte. An area covered with a coating metal layer and an exposed portion of the substrate where the substrate is exposed, and a film growth inhibiting layer that suppresses the growth of a passive film in the electrical contact area of the separator. A fuel cell separator is provided.

  In order to achieve the above object, the present invention provides a fuel cell separator wherein the substrate exposed portion according to the present invention is formed by removing a part of the coated metal layer. provide.

  In order to achieve the above object, the present invention provides a fuel cell separator, wherein the film growth suppression layer according to the present invention comprises a conductive paint using a noble metal and / or carbon as a conductive material. provide.

  In order to achieve the above object, the present invention provides a fuel cell using the separator according to the present invention.

  According to the present invention, a substance having strong corrosive properties such as fluoride ions or hydrofluoric acid mixed in waste water accompanying power generation is reduced, and as a result, a separator for a fuel cell excellent in practical durability and the use thereof are used. The obtained fuel cell can be obtained.

(Effect of reducing fluoride ions)
First, the effect of reducing the concentration of fluoride ions mixed in the waste water accompanying power generation by the aluminum or aluminum alloy exposed on the surface facing the fluorine-based solid polymer electrolyte will be described with an example.

  As metal separator materials, industrial pure aluminum A1000 (typically JIS A1050), duralumin A2000 (typically JIS A2017), Al-Mn alloy A3000 (typically JIS A3003), Al-Mg alloy A separator unit 1 ′ as shown in FIG. 2 is used using A5000 (typically JIS A5052), A6000 of Al—Cr—Cu alloy (typically JIS A6063) and ultra-duralumin A7000 (typically JIS A7075). Produced. At this time, a conductive paint using Au powder as a conductive material and phenol resin as a binder is applied to the flange 104 (electrical contact region) of the reaction gas channel 106 by screen printing, and a film having a thickness of about 10 μm is grown. A suppression layer was formed. On the other hand, a conventional graphite separator was also prepared as a comparative sample.

A fuel cell stack similar to that shown in FIG. 1 was prepared using the above-described aluminum, aluminum alloy, and graphite separators. The MEA 5 uses a perfluorosulfonic acid electrolyte membrane having a thickness of about 50 μm, the electrode area is 9 cm ² , and the anode and cathode catalysts are both platinum 0.4 mg / cm ² . The fuel is hydrogen gas, the oxidant is air, the fuel utilization is 70%, the oxidant utilization is 40%, the anode humidifier temperature is 70 ° C., the cathode humidifier temperature is 70 ° C., the cell temperature is 70 ° C., and the current density is 0.25 A / Power generation was performed for 300 h under a power generation condition of cm ² , and the fluoride ion concentration in the wastewater collected during the power generation test was measured. The fluoride ion concentration was measured using an ion chromatograph (at Toray Research Center, Inc.).

  FIG. 3 shows the measurement results of the fluoride ion concentration mixed in the wastewater accompanying power generation in PEFC. The fluoride ion concentration contained in the waste water of the graphite separator is 0.29 and 0.15 ppm on the anode side and the cathode side, respectively, whereas in the case of the separator made of aluminum or aluminum alloy, the maximum is A3000. It was 0.05 ppm. As is clear from this result, it is possible to greatly reduce the concentration of fluoride ions mixed in the waste water accompanying power generation by being composed of aluminum or aluminum alloy in which at least a part of the surface facing the electrolyte is exposed. I understand.

  The mechanism that can significantly reduce the concentration of fluoride ions mixed in the wastewater generated by power generation as described above has not been fully elucidated at this time, but the aluminum ions and fluoride ions that are slightly eluted by the water in the electrolyte combine. This is probably because fluoride ions were captured (immobilized) as a non-corrosive aluminum fluoride-like compound.

  In other words, by using aluminum or aluminum alloy exposed on the surface facing the electrolyte as a kind of sacrificial metal to offset highly corrosive fluoride ions, the concentration of fluoride ions mixed in the wastewater from power generation It is considered that an effect that can greatly reduce the amount of sapphire appears. Moreover, it is considered that the practical durability of the metallic separator main body (particularly, the electrical contact region) is improved as a result of reducing the corrosive substance.

(Influence of aluminum ions on power generation characteristics)
Next, “catalyst poisoning”, “AC resistance”, and “decomposition of electrolyte membrane” will be described as effects of aluminum ions on the power generation characteristics of PEFC.

  Depending on the ionic species eluted from the metal separator, catalyst poisoning may occur that reduces the activity of the electrode catalyst. Therefore, when the platinum poisoning of the electrode catalyst was examined from the hydrogen desorption wave electric quantity of the cyclic voltammogram, the hydrogen desorption wave was found in any of the fuel cell stacks using the above-mentioned aluminum, aluminum alloy and graphite separators. There was no significant difference in the amount of electricity. From this, it is considered that the influence of aluminum ions on the electrocatalytic activity is negligibly small.

  In the electrolyte membrane, the mobility of metal ions is much smaller than that of protons. Therefore, when metal ions substitute for protons in the electrolyte membrane, the AC resistance is usually on the order of magnitude (on the order of 10 times or 100 times). May rise. Therefore, a fuel cell stack using A1000 as the anode separator and graphite as the cathode separator was prepared, and the AC resistance at each part was determined. The AC resistance of the MEA portion was slightly (100 h after the start of power generation) Only an increase was observed (about 2%). From this, it is considered that substitution of protons with aluminum ions is negligibly small.

  Further, it is known that when a metal ion such as iron is present in the electrolyte membrane, the electrolyte membrane is decomposed. Therefore, when a similar Fenton test using aluminum sulfate instead of ferrous sulfate was performed, there was no evidence that the electrolyte membrane was decomposed. From this, it is considered that the decomposition of the electrolyte membrane by aluminum ions is negligibly small. The Fenton test is an accelerated test method widely used for examining resistance to radicals of an electrolyte membrane, and a test object is added to a test solution to which a predetermined concentration of hydrogen peroxide and ferrous sulfate is added. This is a test used for evaluating the resistance to radicals of the electrolyte membrane by measuring the fluoride ion concentration, sulfate ion concentration, etc. contained in the test solution after the electrolyte membrane to be immersed for a certain time.

(Required thickness of aluminum or aluminum alloy)
The thickness of aluminum or aluminum alloy required to ensure practical durability is estimated as follows.

  In the power generation test using the above-mentioned aluminum or aluminum alloy (A1000-A7000) separator, it is considered that the aluminum contained in the moisture discharged from the anode and the cathode accompanying the power generation is eluted from the separator. In order to ensure durability, it is considered that an aluminum amount greater than this elution amount is necessary.

In the power generation test of the fuel cell using the separator made of A1000 to A7000, the concentration of aluminum contained in the waste water accompanying power generation was the highest in the case of the separator made of A1000, and was about 0.3 ppm. Moreover, the amount of drainage at this time was about 80 g on average per day. As described above, since the electrode area is 9 cm ² , the average aluminum discharge per unit area and unit time is estimated to be about 0.97 mg / cm ² / year. When this is divided by the aluminum density of 2.7 g / cm ³ , it can be seen that the thickness is reduced by about 3.6 μm per year. Therefore, the required thickness of aluminum is equal to or greater than the thickness obtained by multiplying the required service life by 3.6 μm / year.

  From the above, the metal separator with the aluminum or aluminum alloy having a thickness greater than or equal to a predetermined thickness exposed on the surface facing the fluorine-based solid polymer electrolyte membrane is fluoride ion mixed in the wastewater accompanying power generation. It is an excellent fuel cell separator that can greatly reduce the concentration and has almost no adverse effects that degrade the power generation characteristics of PEFC (for example, catalyst poisoning, increased AC resistance, and accelerated decomposition of the electrolyte membrane). Can do.

[First embodiment of the present invention]
The fuel cell separator according to the present embodiment is a metal separator in a fuel cell using a fluorine-based solid polymer electrolyte, in which a part of the surface facing the electrolyte has aluminum having a thickness equal to or greater than a predetermined thickness. It is made of an aluminum alloy, the aluminum or aluminum alloy is exposed, and has a film growth inhibiting layer that suppresses the growth of a passive film in the electrical contact region of the separator.

  Such a separator uses, for example, an aluminum or aluminum alloy plate (for example, A1000 to A7000 described above) having a thickness (for example, 0.1 to 2 mm) that is usually used as a metal separator for a fuel cell, and is pressed. After forming into a predetermined shape by a technique such as processing, a film growth suppression layer that suppresses the growth of the passive film is formed in the electrical contact region (for example, the flange 104 of the reaction gas channel 106 in FIG. 2). Can be manufactured. In forming the film growth suppression layer, conventional methods (for example, Japanese Patent Application Laid-Open No. 2003-272659, noble metals such as Au, Pt, and Pd and / or carbon such as graphite and carbon black are used as conductive materials, and silicon-based materials are used. A conductive paint having a binder of resin, phenol resin, epoxy resin, polyimide resin, polyamide resin, polyolefin resin, or the like is applied in a thickness of 10 to 100 μm.

  Also, the following configuration may be used. FIG. 4 is a schematic cross-sectional view of a metal separator in which the surface of a corrosion-resistant metal is coated with aluminum or an aluminum alloy (partial cross-sectional view taken along the line AA in FIG. 2). The separator 1 shown here is an example in which a metal thin plate is stretched and a flow path is formed by press working. In the separator 1, the entire surface of the central base metal 110 made of a corrosion-resistant metal facing the electrolyte membrane is coated with aluminum or an aluminum alloy having a thickness equal to or greater than a predetermined thickness, and the coated metal layer 111. Is forming. In addition, a film growth suppression layer 112 that suppresses the growth of the passive film is formed in the electrical contact region (for example, the flange 104). By setting it as such a structure, since aluminum is exposed to the surface, the fluoride ion density | concentration mixed in the waste_water | drain accompanying electric power generation can be reduced significantly.

  In addition, a corrosion-resistant metal means the metal (For example, stainless steel (SUS), Ti, Zr, W, Ta, Nb, and those alloys etc.) that an oxide forms a passive film in air | atmosphere. Of course, the metal separator materials described in Patent Documents 1 to 3 may be used as the corrosion-resistant metal. Further, the method of coating aluminum or aluminum alloy is not particularly limited as long as it can be formed to a thickness equal to or more than the predetermined thickness described above. For example, it can be produced by a conventional method such as a hot dip aluminum plating method, a clad method, or a dry plating method. Also, the conventional method can be applied to the formation of the film growth suppression layer as described above.

[Second Embodiment of the Present Invention]
The separator for a fuel cell in the present embodiment is a metal separator in a fuel cell using a fluorine-based solid polymer electrolyte. The separator is made of titanium or a titanium alloy on the surface of the base material made of aluminum or an aluminum alloy facing the electrolyte. An area covered with a coating metal layer and an exposed portion of the substrate where the substrate is exposed, and a film growth inhibiting layer that suppresses the growth of a passive film in the electrical contact area of the separator. It is characterized by having.

  FIG. 5 is a schematic cross-sectional view of a fuel cell separator according to the second embodiment. The separator 2 shown here is an example in which a metal thin plate is stretched and a flow path is formed by press working. In the separator 2, a coating metal layer 211 made of titanium or a titanium alloy is formed on the surface of the central base metal 210 made of aluminum or an aluminum alloy on the side facing the electrolyte membrane. In addition, a film growth suppression layer 112 that suppresses the growth of the passive film is formed in the electrical contact region (for example, the flange 104). A part of the covering metal layer 211 is provided with a base material exposed portion 213 that penetrates to the base metal 210. By setting it as such a structure, since aluminum is exposed to the surface, the fluoride ion density | concentration mixed in the waste_water | drain accompanying electric power generation can be reduced significantly.

  Moreover, a long-life separator can be obtained by using the coated metal layer 211 as titanium or a titanium alloy. This is because, among practical metals, a passive film of titanium or a titanium alloy is corrosion-resistant, and the film is difficult to thicken, so that an increase in electric resistance is small. However, since there is an increase in ohmic loss (iR loss) due to passive film growth, it is preferable to form the film growth suppression layer 112 also in the present embodiment in order to suppress this as much as possible. In forming the film growth suppression layer 112, a conventional method (for example, Japanese Patent Application Laid-Open No. 2003-272659) can be applied as described above.

  Examples of the titanium alloy include JIS 11, JIS 12, JIS 13, JIS 60, JIS 60E, JIS 61, ASTM Gr. 6 etc. can be used suitably. Also, JIS 60 types, JIS 60E types, JIS 61 types, ASTM Gr. The use of a titanium alloy containing aluminum such as 6 can also be expected to improve the mechanical strength of the separator.

  Such a separator 2 is formed by, for example, cutting or grinding reaching the substrate metal 210 through the coated metal layer 211 after cladding the titanium or titanium alloy of the coated metal layer 211 on the aluminum or aluminum alloy of the substrate metal 210. The base material exposed part 213 can be formed and manufactured by performing a process etc. and removing a part of the coating metal layer 211.

  Note that conventional methods (for example, Japanese Patent Application Laid-Open Nos. 2005-219478 and 2006-210320) are used for clad processing of the substrate metal 210 made of aluminum or an aluminum alloy and the coated metal layer 211 made of titanium or a titanium alloy. Can be applied.

  Further, when forming the substrate exposed portion 213, there is no particular limitation on the formation method as long as the substrate exposed portion 213 is formed as a result. In addition to the above method, for example, a method of punching the coating metal layer 211 made of titanium or a titanium alloy in advance to form a large number of holes and cladding the substrate metal 210 may be used. Further, a substrate metal 210 made of aluminum or an aluminum alloy and a coated metal layer 211 made of titanium or a titanium alloy are clad by a conventional method, and this is subjected to press working so that the reaction gas channel 106 (the flange 104 and the groove 105). ), When the processing exceeding the ductility limit of the coated metal layer 211 is performed, a crack is naturally generated in the coated metal layer 211, and as a result, a portion where the substrate metal 210 is exposed (base material exposed portion 213) is formed. A forming method may be used.

  In addition, since it is considered that fluoride ions generated by the decomposition of the electrolyte membrane reach the separator 2 via the gas diffusion layer 7, it is preferable that the position where the substrate exposed portion 213 is provided is closer to the gas diffusion layer 7. Further, the film growth suppression layer 112 may be formed before or after the base material exposed portion 213 is formed, but it is important not to block the base material exposed portion 213, and the process order is appropriately selected. It is desirable.

(Effect of embodiment)
According to this embodiment, the following effects can be obtained.
(1) Even in a conventional fuel cell using a fluorinated solid polymer electrolyte, it is possible to reduce substances having strong corrosive properties such as fluoride ions or hydrofluoric acid mixed in wastewater accompanying power generation. Corrosion of separators and piping materials due to ions or hydrofluoric acid can be suppressed.
(2) By suppressing the corrosion of the separator, the electrical contact condition with the gas diffusion layer of MEA can be improved, and the function as a current collector can be greatly enhanced.
(3) Practical durability as a whole fuel cell system can be secured.

  In addition, this invention is not limited to the said embodiment, A various deformation | transformation is possible within the range which does not change the summary.

[Production of Examples 1 to 3 and Comparative Examples 1 to 3]
Example 1 was prepared as follows. First, SUS304 having a thickness of 0.3 mm is pressed to form a reaction gas flow path as shown in FIG. 2, and then both sides of SUS304 are subjected to hot-dip aluminum plating with a thickness of about 10 μm using A1050 to form a coated metal layer. Formed. After that, conductive paint using graphite as the conductive material and phenol resin as the binder is applied to the buttocks (electrical contact area) of the reaction gas flow path by screen printing, and a film growth suppression layer is formed with a thickness of about 10 μm. did.

  Example 2 was prepared as follows. Using A5052, Ti (JIS 11 types) as a separator material, a 0.3 mm-thick plate material in which Ti (JIS 11 types) becomes a coated metal layer is produced by the method disclosed in Japanese Patent Laid-Open No. 2006-210320. Then, a conductive paint containing Pt as a conductive material and phenol resin as a binder was applied to a portion to be an electrical contact region by a screen printing method to form a film growth suppression layer with a thickness of about 10 μm. Thereafter, press working was performed to form a reaction gas channel as shown in FIG. At this time, a crack (substrate exposed portion) penetrating the coating metal layer was formed in the shoulder portion of the collar portion of the reaction gas channel.

  Example 3 was prepared as follows. Using A3003 and Ti (JIS 61 type) as the separator material, a 0.3 mm-thick plate material in which Ti (JIS 61 type) becomes a coated metal layer is produced by the method disclosed in Japanese Patent Laid-Open No. 2006-210320. Then, the reaction gas flow path as shown in FIG. 2 was formed by pressing. Next, a part of the groove portion of the reaction gas flow path was ground to expose the aluminum alloy base material. After that, a conductive paint containing carbon black as the conductive material and polyvinylidene fluoride (PVDF) as the binder is applied to the buttocks (electrical contact area) of the reaction gas flow path by screen printing, and the film growth suppression layer is applied approximately. It was formed with a thickness of 10 μm.

  Comparative Example 1 was prepared as follows. A SUS304 having a thickness of 0.3 mm was pressed to form a reaction gas flow path as shown in FIG. 2, and then Au plating with a thickness of about 0.06 μm was applied to both surfaces of the SUS304 to form a coated metal layer.

  Comparative Example 2 was prepared as follows. After pressing A1050 having a plate thickness of 0.3 mm to form a reaction gas flow path as shown in FIG. 2, an alumite film having a thickness of about 20 μm was formed on the entire surface of A1050. Then, after removing the alumite film on the collar part (electrical contact region) of the reaction gas flow channel, Au plating having a thickness of about 20 μm was applied to the electrical contact region to form a film growth suppression layer. As Comparative Example 3, a graphite separator was also prepared.

[Power generation test]
Using the separators of Examples 1 to 3 and Comparative Examples 1 to 3, fuel cell stacks as shown in FIG. 1 were produced, and a power generation test for 1000 hours was performed. Moreover, the fluoride ion concentration in the waste water accompanying the power generation collected during the power generation test was measured. The fluoride ion concentration was measured using an ion chromatograph (at Toray Research Center, Inc.).

In addition, MEA is an electrolyte membrane (manufactured by DuPont, Nafion 112) (fuel electrode and air electrode) catalyst (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., TEC10V50E) dispersed in a solution (Sigma Aldridge Japan, Nafion 5% solution). It was produced by a method of applying to and bonding by hot pressing. At this time, the coating thickness was adjusted so that the platinum amount of the electrode catalyst was 0.4 mg / cm ² on the anode side and the cathode side, respectively. Carbon paper (Toray Industries Inc., product number: TGP-H-060) was used for the gas diffusion layer. The conditions of the power generation test are as follows: the fuel (hydrogen gas) utilization rate is 70%, the oxidant (oxygen gas in the air) utilization rate is 40%, the anode humidifier temperature is 70 ° C, and the cathode humidifier temperature is 70 ° C. The cell temperature was set to 70 ° C., and constant current density was applied (current density = 0.25 A / cm ² ).

  When the separators of Examples 1 to 3 were used, the fluoride ion concentration in the wastewater accompanying power generation was 0.02 ppm or less. On the other hand, when the separators of Comparative Examples 1 to 3 were used, they were about 4.8, about 0.3, and about 0.4 ppm, respectively. From this result, it was confirmed that the concentration of fluoride ions mixed in the waste water accompanying power generation is significantly reduced by exposing the metal component of aluminum to at least a part of the surface facing the electrolyte membrane.

  When the electric resistance of each fuel cell stack was measured after the power generation test for 1000 h and compared with that before the power generation test, Examples 1 to 3 and Comparative Examples 2 to 3 showed almost no change. On the other hand, in the case of the comparative example 1, the electrical resistance increased about 3 times. In addition, when the inner surface of the reaction gas discharge side pipe (copper pipe) was observed, there was almost no change in Examples 1 to 3, whereas in Comparative Examples 1 to 3, the foot was mixed into the wastewater accompanying power generation. A brown-colored corrosion product that was attributed to fluoride ions was observed. These results strongly suggest that the metal separator of the present invention has the same durability as the graphite separator, and at the same time, the practical durability of the entire system in a fuel cell using the separator is improved. Yes.

  Further, after the power generation test of 1000 h, the fuel cell stacks of Examples 1 to 3 were disassembled and the separator surface was observed, and it was confirmed that the exposed aluminum or aluminum alloy remained sufficiently. This indicates that the power generation time has a sufficient thickness.

  As described above, the structure of the separator 1 is not necessarily limited to the above-described embodiment because a similar effect can be expected if a metal component of aluminum is exposed on a part of the surface facing the electrolyte membrane. Rather, a portion that substantially exposes the metal component of aluminum having a thickness equal to or greater than a predetermined thickness may be provided on a part of the surface of the separator 1 facing the electrolyte membrane. As a result, highly corrosive fluoride ions are reduced, and the effects of extending the life of the metal separator and the fuel cell can be obtained. In addition, as another means, the same effect can be expected by adding aluminum or an aluminum alloy to the MEA 5 or adding an aluminum compound having a strong affinity for fluoride ions.

It is a typical expansion perspective view showing one example of basic composition in a fuel cell stack of a solid polymer electrolyte fuel cell. It is a typical expansion perspective view showing an example of composition of separator unit 1 '. It is a measurement result of the fluoride ion concentration mixed in the waste water accompanying the power generation in PEFC. It is a cross-sectional schematic diagram of the metal separator which coat | covered the surface of the corrosion-resistant metal with aluminum or aluminum alloy (partial sectional drawing of the AA part of FIG. 2). It is a cross-sectional schematic diagram of the separator for fuel cells which concerns on 2nd Embodiment.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Separator, 1 '... Separator unit, 101 ... Manifold (separator), 104 ... Gutter part, 105 ... Groove part, 106 ... Reaction gas flow path, 110 ... Substrate metal, 111 ... Coated metal layer, 112 ... Film growth suppression layer DESCRIPTION OF SYMBOLS 2 ... Separator 210 ... Substrate metal, 211 ... Coated metal layer, 213 ... Base material exposed part, 4 ... Gasket, 401 ... Manifold (gasket), 5 ... MEA, 6 ... Cooling part, 7 ... Gas diffusion layer, 8 ... current collector plate, 9 ... insulating plate, 10 ... end plate.

Claims (4)

In a metal separator in a fuel cell using a solid polymer electrolyte, a surface of a base material made of aluminum or an aluminum alloy that is coated with a coating metal layer made of titanium or a titanium alloy on a surface facing the electrolyte and the base A base material exposed portion that is exposed and does not penetrate the separator is formed, and a film growth suppression layer that suppresses the growth of a passive film in the electrical contact region of the separator blocks the base material exposed portion. It is formed so that there may be no fuel cell separator. 2. The fuel cell separator according to claim 1 , wherein the base material exposed portion is formed by removing a part of the coated metal layer. 3. The fuel cell separator according to claim 1, wherein the film growth suppression layer is made of a conductive paint using a noble metal and / or carbon as a conductive material. 4. A fuel cell using the fuel cell separator according to any one of claims 1 to 3 .

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