WO2003079476A1 - Element metallique dote d'un revetement conducteur resistant a la corrosion et son procede de production - Google Patents

Element metallique dote d'un revetement conducteur resistant a la corrosion et son procede de production Download PDF

Info

Publication number
WO2003079476A1
WO2003079476A1 PCT/JP2003/003079 JP0303079W WO03079476A1 WO 2003079476 A1 WO2003079476 A1 WO 2003079476A1 JP 0303079 W JP0303079 W JP 0303079W WO 03079476 A1 WO03079476 A1 WO 03079476A1
Authority
WO
WIPO (PCT)
Prior art keywords
corrosion
resistant conductive
conductive film
metal
metal material
Prior art date
Application number
PCT/JP2003/003079
Other languages
English (en)
Japanese (ja)
Inventor
Hideki Shimada
Ken Ebihara
Hidehiko Ishii
Original Assignee
Nippon Light Metal Company, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2002299877A external-priority patent/JP2004134310A/ja
Application filed by Nippon Light Metal Company, Ltd. filed Critical Nippon Light Metal Company, Ltd.
Priority to AU2003213371A priority Critical patent/AU2003213371A1/en
Publication of WO2003079476A1 publication Critical patent/WO2003079476A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the base material is formed of a metal material such as an aluminum material made of aluminum or an aluminum alloy, a titanium material made of titanium or a titanium alloy, a stainless steel material, and a Ni—Fe alloy material.
  • a fuel cell separator having a conductive film for example, a fuel cell separator interposed between the unit cells when forming a fuel cell by stacking a plurality of unit cells; an electrode of the unit cell forming the fuel cell;
  • the present invention relates to a metal material having a corrosion-resistant conductive film useful for many uses such as an electrode material for a primary battery of a portable device, an electrode material used for electrolytic extraction of metal, and an electroplating method, and a method for producing the same.
  • a fuel cell is composed of a plurality of unit cells composed of a pair of electrodes consisting of an anode and a force source and an electrolyte membrane of a proton conductor interposed between the electrodes, and is made of an acid-resistant, conductive material.
  • the separator is made of a graphite material, etc., which has excellent gas permeability, and reacts with one of the electrodes between each unit cell electrode and the electrode contact surface of each separator in contact with this electrode.
  • a gas flow path is formed, and a fuel gas such as hydrogen is supplied to the anode side of each of the unit cells, and an oxidizing gas such as oxygen and air is supplied to the cathode side, respectively.
  • the anode gas causes an oxidation reaction of the fuel gas to generate protons and electrons.
  • the protons move through the electrolyte membrane and are supplied to the cathode, while the electrons are extracted to an external circuit.
  • Such a fuel cell is capable of converting reaction energy into electric energy with extremely high efficiency, and furthermore, the reaction product is basically water only, and harmful exhaust gas is generated. It is an extremely efficient and clean power generation means, especially for polymer electrolyte fuel cells that use a fluororesin-based ion-exchange membrane as the electrolyte. R & D for higher efficiency power generation performance (high power generation performance), durability for long-term stable output (long-term durability), light weight, low cost, etc. Is being promoted.
  • Separator base made of Ni / SUS clad material, aluminum material made of aluminum or aluminum alloy, titanium material made of titanium or titanium alloy, stainless steel material, Ni-Fe alloy, etc.
  • at least the noble metal such as gold (Au), silver (Ag), platinum (Pt), and palladium (Pd), silver, chromium nitride, platinum group composite oxide, or boron carbide and nickel Metal separator formed by plating a conductive film such as a material selected from the composite of 9
  • Ni / SUS clad material separators have a large contact resistance with the electrode of the unit battery.
  • the dissolved metal ions increase the membrane resistance of the electrolyte membrane and lower the battery output.
  • metal separators have low Balta electric resistance, high airtightness and mechanical strength.
  • the metal of the material is susceptible to corrosion, especially in the case of aluminum material, which has a problem of corrosion that the corrosion rate is high.
  • the thickness of the conductive film is increased in order to solve the problem of corrosion, High cost
  • the film thickness is reduced to reduce cost, pinholes or surface defects occur, making it difficult to solve the corrosion problem.
  • the electrode contact surface where the separator comes into contact with the electrode is partially plated with a thick gold plating by gold plating.
  • a graded Au-Ni composition film in which the Au-Ni composition changes continuously due to electrical plating on the electrode contact surface where the separator comes into contact with the electrode Japanese Patent Application Laid-Open No. 2001-345,109. (Japanese Patent Laid-Open No. 2001-357, 859) has been proposed.
  • the provision of a partially thick gold plating film in the former method has a problem that a masking step is required between the plating steps and the number of steps is increased, and the latter method is difficult.
  • Providing a Ni-graded composition film has the problem that even if 1 ppm of Ni ion is eluted, battery performance will be degraded. It cannot always be said that the high power generation performance, long-term durability, light weight, and low cost, which are particularly required in applications such as power generation equipment for automobiles, can be simultaneously satisfied.
  • Such problems are not limited to the above-described fuel cell separators, but include electrodes of unit cells constituting the fuel cell, electrodes of a primary battery of a portable device, electrode materials used in electrowinning and electroplating of metal, etc. The same is true in the field of use of a metal material having a corrosion-resistant conductive film formed on the surface of a metal substrate.
  • the present inventors have found that, for example, in the case of a noble metal element coating, the thickness of the noble metal element coating is 5 ⁇ m or less, which is much thinner than before, After conducting intensive studies on metal materials that can form a conductive film without surface defects and thereby solve both corrosion and cost problems, we will optimize the surface condition of the metal substrate Thus, the present invention has been completed.
  • the present inventors have developed a fuel cell that can simultaneously satisfy high power generation performance, long-term durability, light weight, and low cost, which are particularly useful for applications such as power generation devices for next-generation electric vehicles.
  • fuel cell separators that are useful in the field.
  • a precious metal stick treatment with a thickness of 0.01 to 1 m is performed, and at least the separator base material is used. thickness on the electrode contact surface 0 by. 0 1 ⁇ 1 ⁇ m and that allowed to electrochemical polarization characteristics evaluation method form forming a polarization current 1 0 ⁇ a / cm 2 or less of the precious metal main luck film measured in a purpose Of the present invention was completed.
  • an object of the present invention is to optimize the surface condition of a metal substrate, Inexpensive and durable, for example, a noble metal element film with a thickness of 5 ⁇ m or less on the surface of the metal substrate is extremely thin compared to the past, and has a conductive film free of pinholes and surface defects.
  • An object of the present invention is to provide a metal material having an excellent corrosion-resistant conductive film.
  • Another object of the present invention is to provide a method for producing a metal material having such a corrosion-resistant conductive film.
  • Another object of the present invention is to provide a fuel cell which can simultaneously achieve high power generation performance, long-term durability, light weight, and low cost, and which is suitable for use as a power generation device for a next-generation electric vehicle, for example. It is an object of the present invention to provide a metal separator for a fuel cell which is useful in production, and a metal material having a corrosion-resistant conductive film which can be used for an electrode of a unit cell constituting the fuel cell. Another object of the present invention is to provide a metal separator for a fuel cell, which is useful in manufacturing a fuel cell capable of simultaneously achieving high power generation performance, long-term durability, light weight, and low cost, and a fuel cell. An object of the present invention is to provide a method for producing a metal material having a corrosion-resistant conductive film that can be used for an electrode of a unit battery to be constituted. Disclosure of the invention
  • the present invention is a metal material having a corrosion-resistant conductive film formed by forming a corrosion-resistant conductive film on the surface of a metal substrate formed of a metal material, and is observed on the surface of the metal substrate.
  • the second phase compound of the metal substrate has a corrosion-resistant conductive film having a maximum length L of 5/6 times or less (L ⁇ 5X6T) the thickness T of the corrosion-resistant conductive film. It is a metal material.
  • a zinc immersion treatment of pickling and then immersing zinc in a metal substrate is repeated four times or more.
  • the present invention also provides a metal substrate formed of a metal material, and a metal substrate formed on the surface of the metal substrate having a film thickness of 0.01 to 5 / im, and a method for evaluating electrochemical polarization characteristics.
  • the present invention provides a metal substrate formed of a metal material, after the metal substrate is subjected to an etching process, a zinc substitution process of performing zinc immersion after pickling is repeated four times or more, and then the surface of the metal substrate is formed.
  • This is a method for producing a metal material having a corrosion-resistant conductive film that forms a corrosion-resistant conductive film having a thickness of 0.11 to 5 ⁇ m.
  • the metal material in the present invention can be used for, for example, a separator used when forming a fuel cell, an electrode of a unit cell constituting the fuel cell, and the like.
  • the separator substrate constituting the separator and the electrode substrate constituting the electrode are collectively referred to as “fuel cell forming material”.
  • fuel cell forming material a metal substrate containing the second phase compound satisfying the above conditions may be used, or a metal substrate not restricted by the second phase compound may be used.
  • a corrosion-resistant conductive film that satisfies the conditions for the above-mentioned film thickness and polarization current may be formed.
  • a corrosion-resistant conductive film that does not satisfy the current conditions may be formed.
  • the metal material in the present invention can be used for a metal separator for a fuel cell, an electrode of a unit cell constituting the fuel cell, and the like.
  • the separator will be described as a specific example, but the same applies to the electrode of the unit battery except where specifically described.
  • the metal material in the present invention includes a separator substrate formed of a metal material and at least a noble electrode contact surface of the separator substrate.
  • the method for producing a metal material according to the present invention includes forming a separator base material from a metal material, etching the separator base material, and immersing in zinc after pickling, followed by zinc substitution treatment four times or more.
  • This is a method for producing a metal separator for a fuel cell, in which at least the electrode contact surface of the separator substrate is subjected to a noble metal plating treatment with a thickness of 0.01 to 1 ⁇ ra.
  • the metal base material constituting the metal material is, for example, a metal material such as an aluminum material made of aluminum or an aluminum alloy, a titanium material made of titanium or a titanium alloy, a stainless steel material, a Ni-Fe alloy material, or the like. It is preferably made of aluminum because of its low electric resistance and light weight.
  • the aluminum material used for this purpose is not particularly limited.
  • various kinds of aluminum such as high-purity aluminum (JISH4170; 1N99), A1100, A5052, and A6063 can be used.
  • Aluminum alloys can be mentioned.
  • the metal material for forming a separator base material constituting such a separator is also, for example, aluminum or aluminum alloy made of aluminum alloy.
  • the aluminum material is not particularly limited. For example, high-purity aluminum (JIS H4170; 1N99) or various aluminum alloys such as A1100, A5052, and A6063 are used.
  • the second phase compound of the metal base means a substance (compound) that forms a phase with a substance other than the base metal in the metal base. Can be used to examine the size and distribution of reflected electrons using a scanning electron microscope (SEM), and to identify compounds by X-ray diffraction.
  • SEM scanning electron microscope
  • the metal base is formed of aluminum material
  • a substance other than aluminum (A1) of the base metal Fe, Si, Cu, Mg, Zn and other impurities
  • compounds such as Al 3 Fe, a AlFeSi, Al 3 Mg 2 , Mg 2 Si, and Al-Mg-Zn compounds.
  • the metal substrate is made of titanium, it contains substances other than titanium (Ti) (A1, Mn, Mo, Ta, Fe, Sn, Zr, and other impurities).
  • Ti titanium
  • Ti titanium
  • the metal base is formed of stainless steel
  • a substance other than iron (Fe) of the material metal Cr, Ni, Mo, Nb, Ti, including C other impurities
  • FeCr, Cr 2 3 C 6, Fe 3 C, MoC, Ru can and Ageruko compounds such as NbC
  • the maximum value L of the major axis L of the second phase compound of the metal substrate observed on the surface is 5/6 times or less the thickness T of the corrosion-resistant conductive film. (L 5/6 T), preferably 2/3 times or less (L ⁇ 2/3 T), and the second phase compound on the surface of the metal substrate is a corrosion-resistant conductive film.
  • the maximum value L of the major axis of the second phase compound, which is observed up to a depth of 5 ⁇ below the surface of the metal substrate, is the starting point for defects such as pinholes in the film.
  • the observed second phase compound of the metal substrate is substantially absent, and likewise, The second phase compound, which is observed up to a depth of 5 IX m below the surface of the metal substrate, should be substantially absent.
  • the above-mentioned maximum value L of the major axis of the second phase compound which is less than or equal to 5 Z 6 times (L ⁇ 5/6 T) of the thickness T of the corrosion-resistant conductive film is, for example, a metal.
  • the maximum value L of the major axis of the second phase compound observed on the surface of the metal base material is 1. 1. ⁇ or less, and in the present invention, when the corrosion-resistant conductive film is a noble metal element film, the target of the film thickness is ⁇ or less, and as a result, it is observed on the surface of the metal substrate.
  • the maximum value L of the major axis of the second phase compound must also be 4.2 ⁇ m or less. If the maximum value L of the major axis of the second phase compound observed on the surface of the metal substrate exceeds 5/6 times the thickness of the corrosion-resistant conductive film, the second phase compound becomes It becomes a starting point for defects such as pinholes, and as a result, surface defects such as pinholes occur.
  • a second phase compound of the metal substrate to be above observations substantially absent the second phase when the microscope observation range of 1 mm 2 in 1 0 0 0 times magnification
  • the major diameter of the second phase compound is substantially equal to 0.05 ⁇ , and the second phase compound below this can be ignored. I do.
  • the number of the second phase compound when the second phase compound is observed on the surface of the metal substrate, is preferably 20 / mm 2 or less, and more preferably. Or 10 or less per mm 2 . If the number of the second phase compounds observed on the surface of the metal substrate exceeds 20 / mm 2 , the adhesion of the corrosion-resistant conductive film is insufficient, and the film in the relevant portion is easily lifted.
  • the metal substrate when the metal substrate is an aluminum material, its chemical composition is preferably magnesium (Mg) of less than 7% by mass, Less than 3% by mass of zinc (Zn), less than 0.01% by mass of silicon (Si), less than 0.01% by mass of iron (Fe), and 0.01% by mass of copper (Cu). /. And the balance is preferably aluminum (A1) and unavoidable impurity elements. This is because, when rolling slabs are manufactured by the normal DC (direct chilling) method, the solidification rate during fabrication is high and solidification occurs in a non-equilibrium state, so unavoidable impurities are forcibly dissolved. However, if the content of the above Mg, Zn, Si, Fe, and Cu exceeds the above regulation value, it may crystallize as a coarse second phase compound.
  • the separator substrate made of a metal material may have a reaction gas flow path formed on an electrode contact surface thereof.
  • the reaction gas flow path may not be formed, the separator base material is formed of a metal material, so that precise machining is easy and the processing cost is low.
  • the separator substrate be a reaction gas flow path formed on the electrode contact surface thereof.
  • a reaction gas flow path is formed on the electrolyte side of the unit battery for the electrode substrate formed of the metal material. It is good to have
  • the corrosion-resistant conductive film formed on the surface of the metal substrate is preferably gold (Au), silver (Ag), platinum (Pt), palladium (Pd), rhodium ( Examples include a metal element film, a nickel film, and a copper film formed using Rh), ruthenium (Ru), or an alloy of these noble metals.
  • the method for forming such a corrosion-resistant conductive film is not particularly limited, and includes various methods such as sputtering and plating. From the viewpoint of the presence or absence of a gas step, it is preferably a plating method.
  • the corrosion-resistant conductive film formed on the surface of the metal substrate is a noble metal plating film formed by a noble metal plating process, particularly, a separator substrate for forming a metal separator for a fuel cell is used.
  • the noble metal plating film formed on the surface of such a metal is made of gold (Au), silver (Ag), or platinum (Pt). , Palladium (Pd), rhodium (Rh), luteuium (Ru), or precious metal plating films formed using alloys of these precious metals. From the viewpoint of being extremely stable, it is preferably a gold-mesh coating.
  • the noble metal plating film may be formed on at least the electrode contact surface of the separator substrate, but is preferably used from the viewpoint of maintaining long-term durability and simplifying the manufacturing process. It is good to be formed on the whole surface. In the case of an electrode substrate for forming an electrode constituting a unit battery, it is preferable that the above-mentioned noble metal plating film is formed on the surface of the electrolyte constituting the unit battery.
  • the corrosion-resistant conductive film is a noble metal element film, it differs depending on the use of the metal material, the type of metal forming the film, and the like, but is usually 0.01 ⁇ l ⁇ or more. It is preferably 5 ⁇ m or less, more preferably 0.05 ⁇ m or more and 5 m or less. If the thickness is less than 0.1 ⁇ , pinholes are likely to occur even on the surface where no second-phase compound is present. Conversely, if the thickness is greater than 5 Xm, the corrosion resistance will increase. Does not change, but it is difficult to achieve cost reduction. This corrosion-resistant conductive film must be completely defect-free with no pinholes or surface defects. If any pinholes or surface defects exist, corrosion starts from these pinholes and surface defects.
  • the corrosion-resistant conductive film preferably has a thickness of 0.01 to 5 ⁇ m and a polarization current measured by an electrochemical polarization characteristic evaluation method of 10 ⁇ Ara / cm 2 or less.
  • the corrosion-resistant conductive film is a noble metal plating film formed by a noble metal plating process, in particular, the noble metal formed on the surface of a separator substrate for forming a metal separator for a fuel cell.
  • the thickness of the noble metal plating film formed on the surface of the separator substrate is from 0.01 / im to 1 / zm, preferably from 0.05 ⁇ to 0.
  • the polarization current is preferably 5 ⁇ or less, and the polarization current measured by the electrochemical polarization property evaluation method is 10 ⁇ A / cm 2 or less, preferably 7 ⁇ A / cm 2 or less. Good. Regarding the film thickness, if it is thinner than 0.01 ⁇ m, there is a problem that pinholes are likely to occur.On the other hand, if it is thicker than 1 ⁇ m, it is possible to achieve low cost. It becomes difficult. If the polarization current is higher than 10 ⁇ A / cm 2 , the obtained noble metal plating film may not be completely defect-free without pinholes. The noble metal plating film must be completely defect-free with no pinholes or surface defects. If any pinholes or surface defects exist, corrosion starts from these pinholes or surface defects, and the battery output A problem of performance degradation occurs.
  • the method of measuring the polarization current is the force performed by the electrochemical polarization characteristic evaluation method, and the specific method is as follows. That is, for example, a sample is placed in an electrolyte solution such as an aqueous acetic acid solution so as to face a platinum counter electrode, and a silver-silver chloride electrode is used as a reference electrode. Immerse in an aqueous solution, connect a saturated potassium chloride aqueous solution and the sample with a salt bridge, connect the sample, platinum counter electrode, and silver-silver chloride electrode to a potentiostat, and apply the sample potential to the silver-silver chloride electrode.
  • an electrolyte solution such as an aqueous acetic acid solution so as to face a platinum counter electrode
  • a silver-silver chloride electrode is used as a reference electrode.
  • Immerse in an aqueous solution connect a saturated potassium chloride aqueous solution and the sample with a salt bridge, connect the sample, platinum counter electrode
  • the peak current flowing through the sample electrode is measured as the polarization current.
  • the maximum value B of the major axis of the second phase compound observed on the surface is as small as possible, or It is preferred to prepare a metal substrate that is substantially free of the observed second phase compound.
  • Methods for producing such a metal substrate include, for example, dissolving a high-purity aluminum base metal, adding an alloy element as necessary, adjusting the components, and then forming an aluminum alloy having a desired component composition. After the alloy is melted and further DC-formed to produce an ingot, it is rolled to a predetermined thickness by hot rolling and cold rolling, and further annealed under controlled conditions, if necessary.
  • a method of performing a grinding process for example, see Japanese Patent Application Laid-Open No. 9-235,640; see Japanese Patent Application Laid-Open No. 4-341,536).
  • the maximum value of the major axis L of the second phase compound of the metal substrate, which is observed on the surface of the metal substrate is set to 1 It is preferable to form a corrosion-resistant conductive film having a film thickness T of 2 times or more, preferably 1. 5 times or more, preferably, a surface polishing treatment prior to forming a corrosion-resistant conductive film. It is preferable to perform a zinc immersion treatment in which zinc is immersed after etching, pickling and the like.
  • the surface roughness ⁇ JIS B 0601 (2001) ⁇ is preferably 0.02 to 0.3; um, more preferably 0.03 to 0.2. it is better to adjust to the range of m. If the surface roughness of the metal substrate at this time is greater than 0.3 zm, pinholes and surface defects are likely to occur in the formed corrosion-resistant conductive film due to recesses on the surface of the metal substrate. As a result, the corrosion resistance is reduced, and if the corrosion resistance is smaller than 0.02 ⁇ m, the adhesion between the formed corrosion-resistant conductive film and the surface of the metal substrate is reduced, and In some cases, the peeling of the film occurs locally when the used metal material is used.
  • the surface roughness of the metal substrate is expressed in the range of 0.02 to 0.
  • the method for the surface polishing treatment is not particularly limited, but usually, a method such as electrolytic polishing, mechanical polishing, puff polishing, blast polishing, barrel polishing, or the like is employed, preferably electrolytic polishing. Processing.
  • the surface polishing treatment of the metal base material may be performed using only one of the above-described processing methods in consideration of the material of the metal base material or the like, or may be performed in combination of two or more processing methods.
  • the above-mentioned etching treatment is usually performed by immersing the degreased metal base material in an etching treatment liquid.
  • the etching solution used for this purpose is usually an aqueous solution of sodium hydroxide such as sodium hydroxide, potassium hydroxide, sodium carbonate, or sulfuric acid-phosphoric acid.
  • An aqueous acid solution such as a mixed aqueous solution is used.
  • concentration is 20 g / L or more and 200 g / L or less, preferably 50 g / L or more and 150 g / L or less.
  • the immersion temperature is from 30 ° C to 70 ° C, preferably from 40 ° C to 60 ° C, and the immersion time is from 0.5 minutes to 5 minutes. Preferably, it is 1 minute or more and 3 minutes or less.
  • the concentration of the sulfuric acid is 10 g / L or more and 500 g / L or less, preferably 30 g / L or more. Phosphoric acid concentration of 10 g / L or more at 0 g / L or less
  • the immersion temperature is usually 30 ° C or more and 110 ° C as the processing conditions. C or less, preferably 55 ° C or more and 75 ° C or less, and immersion time of 0.5 minutes or more
  • the pickling bath is an acid such as nitric acid, sulfuric acid, hydrochloric acid, etc., and the concentration is 5 wt ° /. More than 5
  • An aqueous acid solution of the following preferably an acid aqueous solution having an acid concentration of 10 wt% / 0 to 40 wt%, more preferably nitric acid having a concentration of 25 to 30 wt%.
  • the immersion temperature is 15 ° C or more and 30 ° C or less
  • the immersion time is preferably from 20 ° C to 25 ° C, and the immersion time is preferably from 5 seconds to 120 seconds, preferably from 15 seconds to 60 seconds.
  • the zinc immersion bath has a zinc oxide concentration of 1.5 g / L or more and 60 g / L or less, preferably 3.5 g / L or more and 50 g or more. / L or less, and the alkaline concentration of alkaline such as sodium hydroxide and hydroxylating bead 40 g / L or more and 400 g / L or less, preferably 80 g / L
  • the immersion time is preferably 5 seconds or more and 120 seconds or less, more preferably 15 seconds or more and 50 seconds or less.
  • the zinc oxide concentration in the zinc immersion bath is lower than 1.5 g / L, there is a problem that the substituted zinc layer becomes non-uniform.
  • the zinc oxide concentration is higher than 60 g / L, the gold plating film will There is a problem of non-uniformity, and if the alkali concentration is lower than 40 g / L, there is a problem that the adhesion of the substituted zinc layer is reduced, and conversely, it is higher than 400 g / L. This causes a problem that the surface roughness of the metal substrate increases.
  • the zinc substitution treatment of immersing in zinc after the above pickling is preferably repeated at least four times or more. If this zinc substitution treatment is performed up to three times, pinholes and surface defects may occur in the corrosion-resistant conductive film, and a completely defect-free noble metal plating film without pinholes and surface defects may be formed. And it becomes difficult.
  • the surface of the metal substrate is polished, then subjected to an etching process, and further subjected to zinc substitution treatment four times or more.
  • a corrosion-resistant conductive film having a thickness of 0.01 to 5 m.
  • a plating treatment die Although a method such as a putting treatment can be used, preferably, a plating treatment is used.
  • a plating treatment is used.
  • an electroless plating (Me-ELP), a substitution plating (Me-SP), an electrolytic plating ( A plating treatment method such as Me-EP) or electrolytic strike plating (Me-EPS) can be used, and a plating bath having the same bath composition as the conventional plating bath can be used.
  • the same processing conditions as in the past can be used for this plating process, and the processing conditions vary depending on the type of plating metal used.
  • the temperature is about 50 to 75 ° C, and the current density is about 0.1 to 0.5 A / dm 2 .
  • a completely defect-free corrosion-resistant conductive film having no pinholes and no surface defects is formed on the surface of a metal substrate, although the film is as thin as possible. Therefore, even when an expensive precious metal corrosion-resistant conductive film is formed, its thickness can be reduced as much as possible, and it is inexpensive and has excellent durability.
  • Metal materials with a corrosion-resistant conductive film useful in many applications such as electrodes for unit cells constituting fuel cells, electrodes for primary batteries of mobile devices, and electrode materials used in electrowinning and electroplating of metals Can be easily manufactured.
  • a metal material having a corrosion-resistant conductive film having a thickness of 0.01 to 5 ⁇ m as described above and a polarization current of 10 ⁇ A / cm 2 or less measured by an electrochemical polarization property evaluation method is manufactured.
  • a metal separator with a film thickness of 0.01 to 1 ⁇ m and a polarization current of 10 ⁇ A / cm 2 or less measured by the electrochemical polarization characteristic evaluation method First, a separator substrate is formed from a metal material, and after the separator substrate is subjected to an etching treatment, a zinc substitution treatment of pickling and immersing in zinc is repeated four times or more. Perform precious metal plating treatment of ⁇ 1 ⁇ .
  • the etching of the separator substrate is usually performed by a degreasing treatment. This is performed by immersing the separated separator substrate in an etching solution.
  • the etching solution used for this purpose is usually an aqueous solution of sodium hydroxide, such as sodium hydroxide, sodium hydroxide or sodium carbonate, or a mixture of sulfuric acid and phosphoric acid.
  • An aqueous acid solution such as an aqueous solution is used.
  • concentration is from 20 g / L to 200 g / L, preferably from 5 Og / L to 15 Og / L.
  • the immersion temperature is 30 ° C to 70 ° C, preferably 40 ° C to 60 ° C, and the immersion time is 0.5 minutes to 5 minutes. It is preferably 1 minute or more and 3 minutes or less.
  • the concentration of the sulfuric acid is 10 g / L or more and 500 g / L or less, preferably 30 g / L or more.
  • the concentration of phosphoric acid is 10 g / L or more and 1200 g / L or less, preferably 30 g / L or more and 500 g / L or less.
  • the immersion temperature is 30 ° C or more and 110 ° C or less, preferably 55 ° C or more and 75 ° C or less, and the immersion time is 0.5 minute or more and 15 minutes or less. It is preferably 1 minute or more and 6 minutes or less.
  • the acid is a nitric acid, a sulfuric acid, a hydrochloric acid, or the like, and the concentration is 5 wt% or more.
  • An aqueous acid solution of 50 or less preferably an acid aqueous solution having an acid concentration of 10 wt% or more and 40 wt% or less, more preferably a nitric acid solution of 25 wt% or more and 30 wt% or less.
  • the immersion temperature is 15 ° C or more and 30 ° C or less, preferably 20 ° C or more and 25 ° C or less, and the immersion time is 5 seconds or more and 120 seconds or less, preferably It is better to do it for 15 seconds or more and 60 seconds or less.
  • the zinc immersion bath is provided with a zinc oxide concentration of 1.5 g / L or more and 60 g / L or less, preferably 3.5 g / L or less. 50 g / L or less, and alkaline concentration of alkaline such as sodium hydroxide and potassium hydroxide 40 g / L or more and 400 g / L or less, preferably Use an aqueous zinc oxide solution of 80 g / L or more and 200 g / L or less, and immersion temperature of 15 ° (30 ° ⁇ or more, preferably 20 ° C or more and 25 ° C or less) The immersion time should be 5 seconds or more and 120 seconds or less, preferably 15 seconds or more and 50 seconds or less.
  • the zinc oxide concentration in the zinc immersion bath should be 1.5 g / L.
  • the substituted zinc layer will be non-uniform. Conversely, if it is higher than 60 g / L, if the gold plating film becomes non-uniform, there will be problems with the re-emission and the alkali concentration If it is lower than 400 g / L, the adhesion of the substituted zinc layer will be reduced.On the other hand, if it is higher than 400 g / L, the roughness of the aluminum surface will increase. Occurs.
  • the present invention for producing a metal material having a corrosion-resistant conductive film having a film thickness of 0.01 to 5 m and a polarization current of 10 ⁇ A / cm 2 or less measured by the electrochemical polarization characteristic evaluation method, thickness 0.0 1 when manufacturing the polarization current 1 0 ⁇ ⁇ / cm 2 or less of metallic separator made measured in l / zm and electrical chemical polarization characteristic evaluation method, zinc after said pickling It is preferable to repeat the zinc substitution treatment for immersion at least four times or more. When the zinc substitution treatment is performed up to three times, when the number of pinholes generated in the noble metal plating film is measured, it depends on the thickness of the noble metal plating film. It is difficult to form a completely defect-free noble metal plating film without pinholes or surface defects.
  • the separator substrate is etched in this way, and then zinc-substituted four or more times, followed by a noble metal plating process with a thickness of 0.01 to 1 ⁇ m.
  • This noble metal plating treatment includes, for example, electroless plating (Me-ELP), substitution plating (Me-SP), electrolytic plating (Me-EP), electrolytic strip plating (Me-EPS), etc.
  • the method of masking can be mentioned.
  • the plating bath having the same bath composition as the conventional bath can be used.
  • the processing conditions for the precious metal plating process can be the same as those used in the past, and vary depending on the type of noble metal used.
  • the current density is about 0.1 to 0.5 A / dm 2 at about 0 to 75 ° C.
  • a metal material having a corrosion-resistant conductive film having a thickness of 0.01 to 5 ⁇ m and a polarization current of 10 ⁇ A / cm 2 or less measured by an electrochemical polarization characteristic evaluation method is manufactured.
  • the method of the present invention is particularly necessary when manufacturing a metal separator having a film thickness of 0.1 to 1 ⁇ m and a polarization current of 10 nA / cm 2 or less measured by an electrochemical polarization characteristic evaluation method.
  • the surface of the separator base material before the etching treatment is subjected to a polishing treatment to obtain a surface roughness of ⁇ JIS B 0601 (2001) ⁇ , preferably from 0.02 to 0.3 ⁇ , more preferably.
  • the surface roughness is set to the range of 0.02 to 0.3.
  • the method is not particularly limited as long as the method can be adjusted to a range of ⁇ m, but usually, methods such as electrolytic polishing, mechanical polishing, buff polishing, plastic polishing, barrel polishing, etc. are employed, and preferably, electrolytic polishing is performed. It is.
  • the surface polishing treatment of the separator base material In consideration of the material of the substrate, etc., the treatment may be performed using only one of the above-described treatment methods, or may be performed using a combination of two or more treatment methods.
  • electrochemical polarization property evaluation is performed on a surface of a separator substrate formed of a metal material and a surface defect of an electrode substrate that cannot be detected by a normal pinhole detection method. It is possible to form a thin and defect-free noble metal plating film as much as possible by detecting the polarization current by the polarization method. Combined with excellent performance, it is possible to manufacture a metal separator / unit cell electrode that can simultaneously satisfy the high power generation performance, long-term durability, light weight, and low cost of a fuel cell.
  • DC was manufactured to produce aluminum slabs (slab lumps).
  • the aluminum ingot was soaked at 300 to 550 ° C., hot-rolled, and then cold-rolled to prepare a 5.5 mm-thick aluminum plate.
  • This aluminum plate is cut into a size of 100 mm X 100 mm, and is subjected to grinding with a grinding wheel to obtain a size of 5 mm X 100 mm X 100 ram.
  • An aluminum substrate was prepared.
  • Reactor gas channels having a depth of 0.8 mm and a width of 0.8 mm were formed on both sides of each of the 5 mm-thick aluminum base materials obtained above by press caulking, and In a degreasing bath having a composition of 25 g / L sodium, 25 g / L sodium carbonate, 25 g / L sodium phosphate, and 1.5 g / L surfactant. After degreased at 60 ° C and a immersion time of 5 minutes, rinsed with water, and then immersed in 50 g / sodium hydroxide solution as an etching solution at 50 ° C. Etching was performed under the conditions of 3 minutes and immersion time.
  • the etched aluminum base material obtained in this manner is 30wt /.
  • -Use nitric acid aqueous solution as pickling bath add sodium hydroxide 100 g / L, zinc oxide 50 g / L, ferric chloride 1 g / L, and mouth shell salt 10 g / L
  • a zinc immersion bath having the following composition, the zinc substitution treatment of immersing for 30 seconds at room temperature and then immersing in zinc for 30 seconds at room temperature is performed four times, followed by electrolytic gold plating bath ( Te "click, using a 'service Co.
  • the temperature was raised to 70 ° C using an electrolytic silver plating bath (Te, Kalsa Alta, Alna CF).
  • Current density 5 0 A / dm performed in electrolytic Ginme luck process 2 conditions, electrolytic Ginme Tsu ratio of the maximum value L of the major axis of the thickness T and the second phase compounds of key film (T / L) pixels
  • T / L second phase compounds of key film
  • the zinc-substituted separator substrate was heated to a temperature of 40 ° C and a current density of 40 ° C by using an electrolytic platinum plating bath (Te, K-Sulfur® K).
  • Te, K-Sulfur® K an electrolytic platinum plating bath
  • Each prototype separator thus produced was immersed in a 20 g / L aqueous solution of copper sulfate at room temperature for 5 minutes, the copper deposition was counted, and the number of pinholes (pcs / cm) was measured. 2 ) was measured.
  • an aqueous acetic acid solution of pH 3 was used as the test solution
  • a silver-silver chloride electrode was used as the reference electrode
  • the scanning potential was 0 to: L 0 OmV vs Ag / AgClCl.
  • the polarization current (/ A / cm 2 ) was measured by the electrochemical polarization characteristic evaluation method.
  • an aluminum substrate was prepared in which the maximum length L of the second phase compound on the surface and the maximum length L of the second phase compound up to 5 ⁇ ra below the surface had the values shown in Table 4. Then, apply the noble metal plating treatment shown in Table 4 to determine the thickness T of the noble metal plating film and the maximum major axis length L of the second phase compound on the surface or the maximum major axis length of the second phase compound up to 5 ⁇ m below the surface.
  • a prototype of an aluminum separator was produced in the same manner as in Experimental Example 1 except that a noble metal plating film having a ratio to L (T / L) was formed. Polarization current ( ⁇ A / cm 2 ) and separator life (hrs.) Were measured for each of the obtained separator prototypes in the same manner as in Experimental Example 1, and the results are shown in Table 4.
  • a 5 mm thick aluminum substrate (1N99) is used to cut out a separator base material of size 5111 [11 s 100 111 1 111 s 100 mm], and both sides of this separator base are pressed by pressing.
  • Reactant gas channels having a depth of 0.8 mm and a width of 0.8 mm were formed respectively, and then sodium hydroxide 25 g / L, sodium carbonate 25 g / L, and sodium phosphate
  • Etching was performed using a 50 g / L aqueous solution of sodium hydroxide as an etching solution at an immersion temperature of 50 ° C and an immersion time of 3 minutes.
  • a 30 wt% aqueous solution of nitric acid was used as an pickling bath, sodium hydroxide 100 g / L, zinc oxide 50 g / L.
  • a zinc immersion bath having a composition of 1 g / L of ferric chloride and 1 Og / L of Rochelle salt, immerse for 30 seconds at room temperature. 1 to 6 times (zinc replacement times: 1 to 6 times), followed by 10 g / L of potassium cyanide and 30 g / L of potassium cyanide.
  • a gold plating bath having a composition of 30 g / L of carbon dioxide roll and 30 g / L of potassium phosphate, the bath temperature was 55 ° C and the current density was 0.5 A / dm.
  • the electroless gold plating was performed by controlling the processing time under the conditions of 2 , and the thickness of the separator base material at each number of zinc substitution treatments was 0.01 m, 0.1 ⁇ and 0.1 1.
  • a prototype of an aluminum separator with a ⁇ gold film was fabricated.
  • a unit battery was assembled using the membrane electrode assembly described above, and hydrogen gas and air were supplied to the reaction gas flow path of the separator prototype, and a battery power generation test was continuously performed.
  • the time during which the battery electromotive force at the time of the power generation test decreased by 10% compared to the electromotive force at the start of power generation was measured and defined as the separator life.
  • Electroless noble metal plating (Me-ELP), substituted noble metal plating (Me-SP),
  • the degreasing-treated separator substrate obtained in the same manner as in Experimental Example 2 was subjected to a surface polishing treatment by the following method before the etching treatment, and then As in Experimental Example 2, an aluminum separator having a 0.1-meter-thick gold plating film on the surface was subjected to etching treatment, four zinc substitution treatments, and gold plating treatment shown in Table 10. Prototype was made.
  • Electropolishing treatment was performed for 5 minutes under the condition of 1 OA / dm 2 , followed by washing with water and drying.
  • a cotton buff was used as a puff, and alumina fine powder (particle size: P2500) was used as an abrasive.
  • a mixture of fine glass beads (particle size FOO) was sprayed at an air pressure of 2 kg / cra 2 , washed with water after polishing, and dried.
  • the surface state of the metal substrate is optimized, and the thickness of the precious metal element film on the surface of the metal substrate is, for example, 5 ⁇ m or less, which is much thinner than the conventional one, It is possible to provide a metal material having an inexpensive and highly durable corrosion-resistant conductive film formed with a conductive film free of defects and surface defects.
  • the metal separator for a fuel cell obtained by the present invention can simultaneously achieve high power generation performance, long-term durability, light weight, and low cost. It is extremely useful in producing suitable fuel cells.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne un élément métallique comprenant une base métallique et, superposé dessus, un revêtement conducteur résistant à la corrosion, le maximum (L) des majeures diamètres de composés de deuxième phase observés à la surface de la base métallique représente au maximum 5/6ème de l'épaisseur du revêtement conducteur (T) résistant à la corrosion (L ≤ 5/6 T). L'invention concerne également un procédé de production d'un élément métallique qui consiste à soumettre une base métallique à un traitement d'immersion dans du zinc, l'immersion dans le zinc intervient après le nettoyage à l'acide pendant minimum quatre heures puis à former un revêtement conducteur résistant à la corrosion sur une surface de la base métallique. L'invention concerne notamment un élément métallique doté d'un revêtement conducteur résistant à la corrosion qui peut être utilisé dans un séparateur métallique d'une pile à combustible ou d'une électrode de pile à combustible qui sont utiles dans la production de piles de combustible. L'invention concerne enfin leur procédé de production.
PCT/JP2003/003079 2002-03-15 2003-03-14 Element metallique dote d'un revetement conducteur resistant a la corrosion et son procede de production WO2003079476A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003213371A AU2003213371A1 (en) 2002-03-15 2003-03-14 Metal member having corrosion-resistant conductive coating and process for producing the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2002-71780 2002-03-15
JP2002071780 2002-03-15
JP2002299877A JP2004134310A (ja) 2002-10-15 2002-10-15 耐食導電性皮膜を有する金属材及びその製造方法
JP2002-299877 2002-10-15

Publications (1)

Publication Number Publication Date
WO2003079476A1 true WO2003079476A1 (fr) 2003-09-25

Family

ID=28043723

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/003079 WO2003079476A1 (fr) 2002-03-15 2003-03-14 Element metallique dote d'un revetement conducteur resistant a la corrosion et son procede de production

Country Status (2)

Country Link
AU (1) AU2003213371A1 (fr)
WO (1) WO2003079476A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103046051A (zh) * 2012-12-13 2013-04-17 苏州新区化工节能设备厂 水电解极板镀覆前的表面腐蚀处理方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000036309A (ja) * 1998-07-17 2000-02-02 C Uyemura & Co Ltd 燃料電池用金属セパレーター
GB2342223A (en) * 1998-09-30 2000-04-05 Aisin Takaoka Ltd Fuel cell and separator for fuel cell
JP2001351642A (ja) * 2000-06-08 2001-12-21 Riken Corp 燃料電池用セパレータ
JP2001357859A (ja) * 2000-06-13 2001-12-26 Riken Corp 燃料電池用セパレータ
US20020009630A1 (en) * 2000-05-26 2002-01-24 Kabushiki Kaisha Riken Embossed current collector separator for electrochemical fuel cell

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000036309A (ja) * 1998-07-17 2000-02-02 C Uyemura & Co Ltd 燃料電池用金属セパレーター
GB2342223A (en) * 1998-09-30 2000-04-05 Aisin Takaoka Ltd Fuel cell and separator for fuel cell
US20020009630A1 (en) * 2000-05-26 2002-01-24 Kabushiki Kaisha Riken Embossed current collector separator for electrochemical fuel cell
JP2001351642A (ja) * 2000-06-08 2001-12-21 Riken Corp 燃料電池用セパレータ
JP2001357859A (ja) * 2000-06-13 2001-12-26 Riken Corp 燃料電池用セパレータ

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103046051A (zh) * 2012-12-13 2013-04-17 苏州新区化工节能设备厂 水电解极板镀覆前的表面腐蚀处理方法

Also Published As

Publication number Publication date
AU2003213371A1 (en) 2003-09-29

Similar Documents

Publication Publication Date Title
JP4327489B2 (ja) 燃料電池用金属製セパレータおよびその製造方法
TWI353394B (en) Hydrogen evolving cathode
JP4926730B2 (ja) 固体高分子型燃料電池セパレーター用チタン材およびその製造方法、このチタン材を用いてなるセパレーター、ならびにこのセパレーターを用いてなる固体高分子型燃料電池
CA2373344A1 (fr) Element metallique resistant a la corrosion, separateur metallique de pile a combustible comportant un tel element metallique et methode de production connexe
JPWO2003079477A1 (ja) 固体高分子電解質型燃料電池のセルユニット
WO2015133296A1 (fr) Corps métallique poreux et procédé de fabrication d'un corps métallique poreux
CN107408713B (zh) 固体高分子型燃料电池的隔板用金属板
CN109983606B (zh) 燃料电池及制造金属多孔体的方法
JP4901864B2 (ja) 純チタンまたはチタン合金製固体高分子型燃料電池用セパレータおよびその製造方法
US11380907B2 (en) Substrate stainless steel sheet for fuel cell separators and production method therefor
US20200280073A1 (en) Metal porous body, fuel cell and method for producing metal porous body
JP2007134107A (ja) 燃料電池用セパレータ、その製造方法、及び燃料電池
JPWO2020049851A1 (ja) 金属多孔体、燃料電池および金属多孔体の製造方法
WO2006022027A1 (fr) Matériau à base de titane pour séparateur de pile à combustible et processus de production
WO2003079476A1 (fr) Element metallique dote d'un revetement conducteur resistant a la corrosion et son procede de production
JP2009087909A (ja) 燃料電池用セパレータの製造方法
JP2004134310A (ja) 耐食導電性皮膜を有する金属材及びその製造方法
JP4040008B2 (ja) 燃料電池用金属製セパレータおよびその製造方法
JP2003123782A (ja) 燃料電池用セパレータおよびその製造方法、ならびに燃料電池
JP3991701B2 (ja) 燃料電池用金属セパレータ及びその製造方法
JP4274737B2 (ja) 燃料電池用金属製セパレータおよびその製造方法
WO2009034845A1 (fr) Procédé de production d'un séparateur pour pile à combustible
EP3181728B1 (fr) Matériau métallique et composant de transport de courant utilisant ledit matériau métallique
JP4523234B2 (ja) 燃料電池用セパレータ
WO2020179693A1 (fr) Corps poreux, cellule électrochimique et procédé de production de corps poreux

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase