WO2006126613A1 - 燃料電池用セパレータ及びその製造方法 - Google Patents
燃料電池用セパレータ及びその製造方法 Download PDFInfo
- Publication number
- WO2006126613A1 WO2006126613A1 PCT/JP2006/310399 JP2006310399W WO2006126613A1 WO 2006126613 A1 WO2006126613 A1 WO 2006126613A1 JP 2006310399 W JP2006310399 W JP 2006310399W WO 2006126613 A1 WO2006126613 A1 WO 2006126613A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- layer
- fuel cell
- separator
- polymer electrolyte
- Prior art date
Links
Classifications
-
- 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
- H01M8/0208—Alloys
- H01M8/021—Alloys based on iron
-
- 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
- H01M8/0206—Metals or alloys
- H01M8/0208—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
- H01M8/0226—Composites in the form of mixtures
-
- 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
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- 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
Definitions
- the present invention relates to a fuel cell separator used in a solid polymer electrolyte fuel cell and a method for producing the same, and in particular, the amount of noble metal used while maintaining conductivity with a membrane / electrode assembly (MEA).
- MEA membrane / electrode assembly
- the present invention relates to a separator for a fuel cell and a method for producing the same, which are excellent in corrosion resistance and durability against substances having strong corrosive properties such as fluorine ions or hydrofluoric acid (hydrofluoric acid).
- Fuel cells are highly efficient because they can directly convert chemical changes into electrical energy, and they do not burn fuels containing nitrogen, sulfur, etc., so that air pollutants (NO, SO, etc.) It has the feature of low emissions and environmental friendliness.
- These fuel cells include solid polymer electrolyte type (PEFC), phosphoric acid type (PAFC), molten carbonate type (MCFC), and solid oxide type (SOFC).
- solid polymer electrolyte fuel cells are expected to spread in the future as power sources for automobiles, general households, etc., as power sources for mopile equipment, and as uninterruptible power sources.
- FIG. 8 is a schematic cross-sectional view of a unit cell configuration of a solid polymer electrolyte fuel cell provided with a separator made of graphite (hereinafter referred to as a graphite separator) as a prior art.
- This solid polymer electrolyte fuel cell (hereinafter referred to as fuel cell) 100 is a MEA (Membrane Electrode Assembly, membrane electrode) composed of a solid polymer electrolyte membrane 101, a fuel electrode 102, and an oxidizer electrode 103.
- MEA Membrane Electrode Assembly, membrane electrode
- the fuel electrode 102 is formed on one surface of the solid polymer electrolyte membrane 101 so as to include an anode catalyst layer and a gas diffusion (dispersion) layer disposed outside the anode catalyst layer.
- Oxidant electrode 1 03 is formed on the other surface of the solid polymer electrolyte membrane 101 with a structure including a force sword catalyst layer and a gas diffusion (dispersion) layer disposed outside the force sword catalyst layer.
- the graphite separators 106 and 108 are members for electrically connecting the fuel electrode 102 and the oxidant electrode 103 and preventing the fuel and the oxidant from being mixed.
- Such a fuel cell 100 generates electricity by an electrochemical reaction in an environment of about 80 ° C using hydrogen in fuel gas and oxygen in oxidant gas.
- Hydrogen ions H + move in the solid polymer electrolyte membrane 101 to the counter electrode side, reach the catalyst layer of the oxidant electrode 103, react with oxygen in the oxidant gas in the oxidant gas channel 107, and react with water. It becomes.
- a predetermined number of fuel cells 100 as shown in FIG. 8 are connected in series so as to obtain a desired output voltage.
- the number of separators may be several tens to one hundred or more.
- black lead-based materials have been mainly used as separator materials for fuel cells from the viewpoint of corrosion resistance and conductivity.
- the graphite separator produced by cutting has a problem that the cost of the fuel cell system becomes very high as the number of sheets used increases as described above due to the high manufacturing cost.
- the graphite separator by the resin molding method also has a problem in that it is difficult to reduce the thickness of the graphite separator, and it is difficult to reduce the size of the fuel cell system.
- a corrosion-resistant metal such as stainless steel (SUS) as the separator material.
- SUS stainless steel
- the constituent elements of the stainless steel are eluted, the separator is damaged, and the fuel cell characteristics are deteriorated. It is known that it will let you.
- a separator is known in which stainless steel is used as a base material and Au (gold) is formed on its surface with a plating layer having a thickness of 0.01 to 0.06 m to reduce contact resistance. (For example, see Patent Document 1).
- an acid-resistant film made of Ta (tantalum), Zr (zirconium), Nb (niobium), Ti (titanium), etc. is formed on the surface of stainless steel, and Au, Pt is formed on the acid-resistant film.
- Metal separators with improved corrosion resistance and conductivity are known by applying a coating thickness of 0.1 ⁇ m or less for conductive films such as (platinum) and Pd (palladium), and 0.03 ⁇ m as an example. (For example, see Patent Document 2).
- the thin noble metal coating as described above is porous and does not completely cover the surface of stainless steel. For this reason, there is no dissatisfaction with conductivity, but it is unsatisfactory in terms of corrosion resistance (corrosion resistance), and the component elements of stainless steel may elute over a long period of use, which degrades fuel cell characteristics. Become. On the other hand, if the noble metal film is made thick enough that it does not become a problem in terms of corrosion resistance, the cost will increase even if the problem of corrosion resistance is solved, and it is not practical.
- Patent Document 3 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, A1 (aluminum), and Ti. At least one or more kinds of noble metals selected from the group or an acid oxide portion of the noble metal is disposed at 3 to 50 nm so as to have high conductivity and corrosion resistance.
- Patent Document 4 discloses the following metal separator.
- This metal separator is in contact with a gas diffusion layer using a precious metal such as Au, Pt, Ru, and Pd as a conductive contact layer on a Ti clad material with a Ti-based corrosion-resistant metal clad on the surface of a corrosion-resistant metal material such as stainless steel.
- the portion is coated with a film thickness of less than 0.0005-0.01 m, and excellent conductivity and corrosion resistance can be obtained.
- Patent Document 1 Japanese Patent Application Laid-Open No. 10-228914 ([0006], [0010], FIG. 4)
- Patent Document 2 Japanese Patent Laid-Open No. 2001-93538 ([0015] to [0018])
- Patent Document 3 Japanese Patent Laid-Open No. 2001-297777 ([0012] to [0017])
- Patent Document 4 Japanese Unexamined Patent Application Publication No. 2004-158437 ([0037 G [0041], [0047], FIGS. 1 to 4
- a conventional metal separator for a fuel cell also has a certain degree of corrosion resistance against sulfuric acid acidity of about pH 2 to 3 at about 80 ° C, for example.
- a strong and corrosive substance such as fluorine or hydrofluoric acid is generated due to deterioration or decomposition of the electrolyte membrane, which is used for the metal separator.
- a new problem that has not been considered in the past, which corrodes metal materials such as piping materials, has become a major problem.
- the metal separators of Patent Document 3 to Patent Document 4 also show a decrease in long-term reliability. There is concern.
- the object of the present invention is to reduce the amount of precious metal used at a high material cost while maintaining conductivity with MEA and to have a strong corrosive property such as fluorine ion or hydrofluoric acid.
- An object of the present invention is to provide a metal separator for a fuel cell capable of obtaining corrosion resistance and durability against quality and a method for producing the same.
- the present invention provides a separator for a fuel cell used in a solid polymer fuel cell constituted by using a fluorinated solid polymer electrolyte membrane, and at least the fluorinated solid polymer.
- the surface layer on the electrolyte membrane side is made of a metal plate made of a first metal made of T or Ti alloy, and a second metal formed on the surface of the first metal on the fluorine-based solid polymer electrolyte membrane side.
- the present invention provides a metal plate having a predetermined thickness at least on the surface of the fluorine-based solid polymer electrolyte membrane side of the first metal made of T or Ti alloy.
- the method for producing a fuel cell separator is provided. The invention's effect
- the amount of noble metal used can be reduced while maintaining electrical conductivity with MEA, and the substance has strong corrosive properties such as fluorine ions or hydrofluoric acid. It is possible to obtain a fuel cell separator that is excellent in corrosion resistance and durability.
- FIG. 1 is a schematic cross-sectional view showing an example of a unit cell of a polymer electrolyte fuel cell according to an embodiment of the present invention.
- FIG. 2 is a schematic cross-sectional view showing details of the metal separator of FIG.
- FIG. 3 is a diagram showing an example of a result of surface analysis of a Ti clad material in which a pure Ti layer is coated with a Pd layer according to the present invention by a scanning electron microscope-energy dispersive X-ray analyzer (SEM-EDX). is there.
- SEM-EDX scanning electron microscope-energy dispersive X-ray analyzer
- FIG. 4 is a photograph showing the results of a fluorine resistance environmental test for a metal separator material in an embodiment of the present invention.
- FIG. 5 is a diagram showing evaluation results of contact resistance characteristics based on the difference in the configuration of the metal separator material.
- FIG. 6 is a diagram showing the evaluation results of contact resistance characteristics based on the difference in heat treatment conditions in the manufacturing process of the metal separator material.
- FIG. 7 is an external view photograph of the produced metal separator.
- FIG. 8 is a schematic cross-sectional view showing a unit cell configuration of a solid polymer electrolyte fuel cell using a graphite separator.
- FIG. 1 is a schematic cross-sectional view of an example of a unit cell of a polymer electrolyte fuel cell according to an embodiment of the present invention.
- the MEA 13 is composed of a fluorine-based solid polymer electrolyte membrane 10 that is an electrolyte, a fuel electrode 11 provided on one surface of the fluorine-based solid polymer electrolyte membrane 10, and the other of the fluorine-based solid polymer electrolyte membrane 10. It is formed from an oxidant electrode 12 provided on the surface.
- the fuel electrode 11 and the oxidant electrode 12 are each formed with a catalyst layer and a gas diffusion (dispersion) layer outside thereof.
- the fuel cell 1 includes a MEA 13 and a metal separator 15 as a fuel cell separator having a plurality of fuel gas passages 14 having a cross-sectional shape of a concave groove with respect to one surface (fuel electrode 11) of the MEA 13.
- a metal separator 17 as a separator for a fuel cell having a plurality of oxidant gas passages 16 having a cross-sectional shape of a concave groove, and a member interposed between the metal separators 15 and 17 and sealing the periphery of the MEA 13 Gaskets 18 and 19 are provided as (seal members).
- the fuel cell 1 is assembled by pressurizing and fixing a pair of metal separators 15 and 17 with an appropriate pressure while being sealed with gaskets 18 and 19.
- the fluorine-based solid polymer electrolyte membrane 10 may be made of a perfluorosulfonic acid ion exchange material, a perfluorocarboxylic acid ion exchange material, or the like. Registered trademark) and Flemion (registered trademark) of Asahi Glass Co., Ltd. can be used!
- the contact resistance between the MEA and the metal separator should be at least about 150 m ⁇ 'cm 2 or less as desired. More desirably, it is ⁇ ⁇ 'cm 2 or less, and more desirably 70 ⁇ ⁇ ' cm 2 or less.
- FIG. 2 shows a schematic diagram of a detailed configuration of the metal separator 15.
- the metal separator 15 includes a base material 20 made of a corrosion-resistant metal such as stainless steel, a pure Ti layer 21 as a first metal layer formed on both surfaces of the base material 20, and at least one side of the base material 20.
- This composite metal layer 22 is formed by forming a Ti—Pd alloy at the junction between the pure Ti layer 21 and the Pd layer 23.
- “Corrosion-resistant metal” means a metal (for example, stainless steel, aluminum alloy, magnesium alloy, Ti, etc.) in which an acid oxide forms a passive film in the atmosphere. ⁇ O shall mean 1 to 3 types of IS.
- the thickness of the Pd layer 23 is preferably formed so that the average thickness is 2 to: LOnm before alloying with the pure Ti layer 21. More preferably, it is formed to 3 to 9 nm. More preferably, it is formed to 4 to 8 nm.
- the reason why the upper limit is set to lOnm is that the noble money with high material cost This is to reduce the amount of genus used.
- the reason why the lower limit is set to 2 nm is that if the thickness of the Pd layer 23 is less than 2 nm, the probability that the Pd layer 23 will be covered with Ti oxide by the heat treatment described later increases, and it becomes difficult to ensure conductivity ( This is because the contact resistance against MEA increases. It is generally said that the thickness of the Ti oxide film is about 2nm.
- the average yarn composition ratio of the surface layer portion (for example, thickness of about 1 ⁇ m) in which the Pd layer 23 is formed by the composite metal layer 22 is Pd of 0.005 or more in terms of atomic ratio with respect to Ti.
- 0 (oxygen) is 0.1 to 1 in terms of atomic ratio to Ti
- Pd is 0.02 to 0.08 in terms of atomic ratio to O.
- the atomic ratios are 0.01 ⁇ Pd / Ti ⁇ 0.03, 0.2 ⁇ O / Ti ⁇ 0.9, and 0.02 ⁇ Pd / O ⁇ 0.06, respectively.
- the atomic ratio should be 0.0015 ⁇ Pd / Ti ⁇ 0.03, 0.2 ⁇ O / Ti ⁇ 0.85, 0.02 ⁇ Pd / O ⁇ 0.05.
- the average composition ratio of the above-mentioned surface layer portion is obtained by, for example, surface analysis using an energy dispersive X-ray analyzer (for example, acceleration voltage: 15 kV, area: about 60 X about 80 Quantitative analysis can be performed by m 2 ).
- a pure Ti layer 21 as a first metal layer is clad-bonded to a thickness of 20 m on both sides of a plate-like stainless steel material (for example, SUS316L) having a thickness of 0.16 mm.
- a plate-like stainless steel material for example, SUS316L
- a Pd layer 23 as a second metal layer is formed on the pure Ti layer 21 on the MEA 13 side surface, for example, to an average thickness of 5 nm by sputtering or EB vapor deposition (electron beam vapor deposition).
- sputtering or EB vapor deposition electron beam vapor deposition
- a Ti-Pd alloy is formed between the pure Ti layer 21 and the Pd layer 23 by performing a heat treatment under a predetermined condition and generating a diffusion phenomenon at the interface between the pure Ti layer 21 and the Pd layer 23.
- Produce and composite gold Form a genus layer 22.
- a pure Ti layer part not covered by the Pd layer and oxygen in the atmosphere combine to form a Ti oxide film.
- a Ti layer is formed on the substrate 20 side, a Pd layer 23 is formed on the fluorine-based solid polymer electrolyte membrane 10 side (MEA 13 side), and a Ti—Pd alloy is formed in the middle. .
- the Pd layer 23 may be formed on both surfaces of the pure Ti layer 21, it is desirable to form the Pd layer 23 only on the surface of the fluorine-based solid polymer electrolyte membrane 10 side (MEA 13 side) in terms of cost and the like.
- the average thickness of the Pd layer 23 is obtained by measuring the average film formation rate of Pd in advance (for example, measuring the film thickness formed in a film shape (not in an island shape) and dividing the film formation time by the film formation time.
- the heat treatment is performed in the air or in an aerobic atmosphere at a temperature in the range of higher than 250 ° C and lower than or equal to 400 ° C.
- the heat treatment temperature is preferably in the range of 280 ° C or more and 390 ° C or less, more preferably around 350 ° C (about 300 ° C to 370 ° C).
- the reason why heat treatment at a temperature higher than 250 ° C is appropriate is the reason for Ti platinum group alloying (effective diffusion).
- the reason why heat treatment at 400 ° C or lower is appropriate is to suppress the excessive formation of Ti oxide film that leads to increased contact resistance to MEA. Conceivable.
- the heat treatment time is preferably adjusted so that the average composition specific force of the surface layer portion (for example, about a thickness) in which the Pd layer 23 is formed by the composite metal layer 22 falls within the above-mentioned range.
- the alloying method is preferably performed by heat treatment using a normal electric furnace or the like from the viewpoint of simplicity and cost, but other methods can also be applied.
- a metal separator material is formed.
- the metal separator is manufactured by applying a forming process (cutting or pressing) to the metal separator material.
- the second step and the third step may be performed before or after the metal separator is molded.
- a nano-level film formation technology such as sputtering is used to form a platinum group element such as Ti and Pd with high precision, and further subjected to diffusion heat treatment, so that There is no chemical bond with oxygen on the surface, and there are atoms of platinum group elements in the vicinity of Ti atoms, so it is thought that electrons are supplied and become electrochemically noble.
- the Ti-Pd alloy is not limited to the structure formed at the junction between the pure Ti layer 21 and the Pd layer 23, and the entire composite metal layer 22 may depend on diffusion conditions. Ti—Pd alloy may also be used.
- the alloy state is not particularly limited, and there may be a difference in Pd concentration depending on the location, but the part in contact with the gas diffusion (dispersion) layer of the fuel electrode 11 and the oxidant electrode 12 may be used. It is desirable to ensure that the Pd concentration does not decrease.
- the first metal layer may be a pure Ti alloy of Ti (for example, JIS 11 types). A Ti alloy with a corrosion resistance equivalent to or higher than that of pure Ti is used.
- the second metal layer can use Pt (platinum), Ru (ruthenium), Rh (rhodium), Ir (iridium), or two or more kinds in place of Pd. These may be combined with oxygen. Among these, it is preferable to use one or more of Pd, Pt, and Ru, or those obtained by combining oxygen with these. In these cases as well, Pt, Ru, Rh, etc. have an average yarn composition ratio of the surface layer portion (for example, about 1 ⁇ m thick) in which the second metal layer is formed of a composite metal layer with Ti.
- the atomic ratio to Ti is 0.005 to 0.03, the atomic ratio to Ti is 0 (oxygen) 0.1 to 1, and the second metal is 0 to O. .02 or more and 0.08 or less are preferable. More preferably, the atomic ratios of 0.01 ⁇ second metal / Ti ⁇ 0.03, 0.2 ⁇ O / Ti ⁇ 0.9, 0.02 ⁇ second metal /0 ⁇ 0.06 To be. More preferably, the atomic ratios are 0.015 ⁇ second gold J3 ⁇ 4 / Ti ⁇ 0.03, 0.2 ⁇ O / Ti ⁇ 0.85, 0.002 ⁇ second metal /O ⁇ 0.05. Try to be.
- a plate-shaped stainless steel (SUS316L) with a thickness of 1 mm is prepared as the base material, and the first metal (Ti: JIS type 1) layer is placed on both sides of the base material so that the thickness ratio is 10% each.
- the clad was rolled and joined to form a plate with a total thickness of 0.2 mm (metal plate 1).
- a plate-shaped aluminum alloy material (A1—Mg alloy: JIS 508 3) having a thickness of 1 mm is prepared as the base material, and the thickness ratio of the constituent materials is 20% of the first metal layer, and the bonding metal layer
- the joining metal (A1: JIS 1050) layer and the first metal (Ti: JIS type 1) layer were clad-rolled and joined so as to be 5% and the base material 7 5%.
- the bonding metal layer was formed so as to be interposed between the base material and the first metal layer.
- bonding heat treatment for example, 500 ° C. ⁇ 10 min
- finish rolling were performed to form a plate having a total thickness of 0.3 mm (metal plate 2).
- Ti plate material Ti: JIS Class 1 having an overall thickness of 0.2 mm was prepared (Metal plate 3).
- the second metal layer was formed using an RF sputtering apparatus (ULVAC, Inc., model: SH-350).
- the atmosphere during formation was Ar, the pressure was IPa, and the RF output was appropriately adjusted according to the type of metal.
- the thickness of the second metal layer was controlled by measuring the average film formation speed in advance for each metal species and adjusting the film formation time.
- Figure 3 shows the surface of the composite metal layer 22 according to the present invention. : 15 kV, area: approx. 60 X approx. 80 ⁇ m 2 )
- An example of surface analysis results is shown.
- SEM is Hitachi, Ltd. S-4300
- EDX is Horiba, Ltd. EMAX-300.
- the sample shown in the figure is a sample immediately after forming a Pd layer of 5 nm (average film thickness) on the metal plate 1. From this analysis result, the nano thin film by Pd layer 23 is very thin, or clustered (dispersed in islands) in clusters on the surface. Therefore, it can be seen that the signal strength of the underlying pure Ti layer 21 is clearly observed.
- FIG. 4 shows the results of the hydrofluoric acid resistance test A for the metal separator in this embodiment.
- This hydrofluoric acid environment test A was maintained at a temperature of 80 ° C. in a 0.5 mass% hydrofluoric acid aqueous solution vapor atmosphere for 24 hours. Thereafter, the surface condition after the test was observed.
- Samples used in the test were prepared as follows.
- a Pd layer 23 is formed to 5 nm (average film thickness) on the metal plate 1, and is 250 ° C X lh (250 ° C is the set temperature of the apparatus, and the actual temperature near the sample is about 260 ° C in the atmosphere. ° C) heat treatment.
- the heat treatment was performed using a commercially available oven (Yamato Scientific Co., Ltd., model: DV600).
- the metal plate 1 was formed without forming the Pd layer 23.
- the left side is the case where the outermost layer is pure Ti layer 21 only (comparative example), and the right side is the case where Pd layer 23 is applied and a predetermined heat treatment is performed to form composite metal layer 22 (implementation) Example).
- the metal separator without the Pd layer has a clearly altered surface, whereas the metal separator with the Pd layer 23 and subjected to the prescribed heat treatment to form the composite metal layer 22 shows almost no alteration and is good. It shows that it shows excellent corrosion resistance and durability.
- the contact resistance with the gas diffusion (dispersion) layer of MEA before and after the implementation of hydrofluoric acid environment test A was measured by various changes in the composition (material) of the metal separator material, and the characteristics were evaluated. It was.
- the contact resistance measurement was performed as follows. Carbon PENO (Toray Industries, Inc., product number: TGP-H-060) was used as the gas diffusion (dispersion) layer of MEA.
- the prepared metal separator material (2 X 2cm 2 ) is sandwiched between the Cu (copper) blocks plated with Au via the carbon paper, and the load (20kg / cm 2 ) is applied with a hydraulic press.
- the contact resistance between the metal separator material and the carbon paper was measured by a 4-terminal measurement method (Adex Co., Ltd., model number: AX-125A).
- Samples used for this evaluation test were prepared as follows. Pd with an average thickness of 5 nm as the second metal layer on the surface of the Ti clad material (the metal plate 1) having the pure 1 layer 21 on both surfaces of the base material 20 (SUS316L) (Example 1) , Pt (Example 2), Ru (Example 3), Au (Comparative Example 1) thin films were formed by sputtering, respectively, and 250 ° C X lh (250 ° C is the set temperature of the device) in the atmosphere. The actual temperature near the sample was about 260 ° C).
- Example 1 ′ a sample (Example 1 ′) in which a Pd thin film having an average thickness of 5 nm was formed as a second metal layer on the surface of the metal plate 2 by the sputtering method and subjected to the same heat treatment as in Example 1, and A Pd thin film having an average thickness of 5 nm was similarly formed on the surface of the metal plate 3 by sputtering, and a sample (Example 1 ") that was subjected to the same heat treatment as Example 1 was prepared.
- the layers were formed using an RF sputtering apparatus (Al Knock Co., Ltd., model: SH-350, atmosphere: Ar, pressure: lPa), and heat treatment was performed using a commercially available oven (Yamato Scientific Co., Ltd., model: DV600). ).
- Comparative Example 2 Ti-SUS-Ti only, metal plate 1 and Comparative Example 3 (on the Ti of metal plate 1, for example, a method disclosed in Japanese Patent Application Laid-Open No. 2000-138067) Then, a conductive carbon coating (approx. 20 ⁇ m thick) was also prepared.
- FIG. 5 shows the evaluation results of the contact resistance characteristics based on the difference in the configuration of the metal separator material.
- the left side shows the characteristics before conducting the hydrofluoric acid resistance test A
- the right side shows the characteristics after the hydrofluoric acid resistance test A.
- the contact resistance before and after the hydrofluoric acid environment test B was measured by variously changing the heat treatment conditions in the metal separator manufacturing process, and the relationship between the heat treatment conditions and the contact resistance characteristics was investigated.
- Samples for this evaluation test were prepared as follows. Both sides of base material 20 (SUS316L) A Pd thin film with an average thickness of lOnm is formed by sputtering on the surface of a Ti clad material (the metal plate 1) formed by applying a pure Ti layer 21 to the surface, and the atmosphere is kept in the atmosphere or argon (Ar) for 1 hour. Heat treatment was performed at the temperature shown in FIG. As a comparison, a sample was also prepared that was heat-treated at the temperature shown in Table 2 for 1 hour in the air using the metal plate 1 on which no Pd thin film was formed.
- normal electric furnace (Denken Co., Ltd., model: KDF S80) is used for heat treatment in the atmosphere
- heat treatment in Ar is normal electric furnace (ULVAC RIKO, Inc., model: VF-616 Y).
- UVAC RIKO, Inc. model: VF-616 Y
- the contact resistance with the carbon paper was measured by the same method as described above.
- Table 1 shows the measurement results of contact resistance and the hydrofluoric acid environment test B ratio before and after B (contact resistance after B test, contact resistance before ⁇ test) of the sample with Pd thin film formed on the surface of pure Ti layer.
- Table 2 shows the measurement results of the hydrofluoric acid resistance test before and after the hydrofluoric acid resistance test B on a sample with no Pd thin film formed on the surface of a pure layer. .
- FIG. 6 is a graph showing the contact resistance measurement results shown in Table 1 and Table 2, and shows the evaluation results of the contact resistance characteristics based on the difference in heat treatment conditions in the manufacturing process of the metal separator material. .
- the mouth, ⁇ , and ⁇ indicate the characteristics before the HF acid resistance test B
- the country and ⁇ indicate the characteristics after the Fluorine resistance test B.
- the samples (Examples 4 to 6) heat-treated near 350 ° C (280 to 390 ° C) in the atmosphere hardly increased.
- the sample heat-treated at 500 ° C in the atmosphere (Comparative Example 5) has a large contact resistance at the time of heat treatment, although the ratio before and after the hydrofluoric acid resistance test B (contact resistance increase rate) was small. I helped. In other words, those treated at 500 ° C in the atmosphere are considered unsuitable for practical use due to their high practical contact resistance.
- the sample (Comparative Example 7) that was heat-treated at 200 to 400 ° C in the air without forming a Pd thin film on the surface of the pure Ti layer had a contact resistance at the time when the heat treatment was performed. It was observed that the surface was dissolved by the hydrofluoric acid environment test B, which was higher than ⁇ 6. This indicates that the corrosion resistance to hydrofluoric acid environment is insufficient. In other words, it strongly suggests the significance of forming the composite metal layer 22 according to the present invention.
- the surface of the composite metal layer 22 according to the present invention is subjected to a scanning electron microscope energy dispersive X-ray analyzer (SEM—EDX: Scanning Electron Microscopy—Energy Dispersive X-ray spectrometer). ⁇ accelerating electrostatic J earth: L5kV, the area was carried out a surface analysis by about 60 X to about 80 m 2). The results are shown in Table 3. SEM is Hitachi, Ltd. S-4300, and EDX is Horiba, Ltd. EMAX-300. [0067] [Table 3] Table 3 Average composition ratio of the surface part of the composite metal layer 22 in the sample heat-treated in air
- Ti-Pd alloy Ti-Platinum group alloy
- Ti-Platinum group alloy has the effect of ensuring the conduction path (contributing to the reduction of contact resistance) and regenerating the Ti oxyhydride film corroded (dissolved) by hydrofluoric acid.
- a metal separator member was prepared by the same procedure as in Example 5 (metal plate 1 + Pd coat (10 nm) + heat treatment in air (350 ° C. Xlh)), and then press working to produce a metal separator.
- Figure 7 shows a photograph of the appearance of the fabricated metal separator.
- the length of the fuel gas (or oxidant gas) flow path (left and right grooves and recesses in Fig. 7) is 48 mm, and the flow path pitch is 3 mm (in the vertical direction in Fig. 7, the recesses and protrusions are (Alternately formed) and the depth of the channel (depth direction in Fig. 7, difference in height between the concave and convex portions) was 0.5 mm.
- Nafion 112 (registered trademark) manufactured by DuPont Co., Ltd. was used as the fluorine-based solid polymer electrolyte membrane, and the size of the power generation electrode part was 50 ⁇ 50 mm 2 .
- a fuel cell having a structure as shown in Fig. 1 (Fig. 2) was fabricated by sandwiching a gasket having a fuel gas (or oxidizing agent gas) flow path and a sealing member.
- the power generation conditions were such that the load current density was 0.5 A / cm 2 , and the gas was used so that the utilization rates of fuel gas and oxygen in the air (oxidant gas) were 70% and 40%, respectively. Supplied.
- a continuous energization test (1500h) was performed, two types of fuel cells (metal separator according to the present invention) It was confirmed that the reduction in electromotive force per operating time was suppressed to 5 mV / kh or less, and the same power generation characteristics were obtained for both fuel cells using a battery and a conventional fuel cell using a graphite separator.
- the Pd-coated one is heat-treated under a predetermined condition, so that the tolerable fluorine ion concentration is improved and the hydrofluoric acid resistance is further improved.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007517876A JP4702365B2 (ja) | 2005-05-25 | 2006-05-24 | 燃料電池用セパレータ及びその製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005152730 | 2005-05-25 | ||
JP2005-152730 | 2005-05-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006126613A1 true WO2006126613A1 (ja) | 2006-11-30 |
Family
ID=37452037
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2006/310399 WO2006126613A1 (ja) | 2005-05-25 | 2006-05-24 | 燃料電池用セパレータ及びその製造方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20080057371A1 (ja) |
JP (1) | JP4702365B2 (ja) |
CN (1) | CN100472864C (ja) |
WO (1) | WO2006126613A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009123528A (ja) * | 2007-11-15 | 2009-06-04 | Kobe Steel Ltd | 燃料電池セパレータ用チタン基材およびこれを用いた燃料電池セパレータの製造方法 |
JP2009533830A (ja) * | 2006-04-14 | 2009-09-17 | アプライド マテリアルズ インコーポレイテッド | 信頼性のある燃料電池電極の設計 |
JP2009238438A (ja) * | 2008-03-26 | 2009-10-15 | Kobe Steel Ltd | 燃料電池用セパレータ及びその製造方法 |
JP2009289511A (ja) * | 2008-05-28 | 2009-12-10 | Kobe Steel Ltd | 燃料電池セパレータ用チタン基材、および、燃料電池セパレータ、ならびに燃料電池セパレータの製造方法 |
JP2009289707A (ja) * | 2008-06-02 | 2009-12-10 | Nissan Motor Co Ltd | 燃料電池用セパレータ |
JP2012226889A (ja) * | 2011-04-18 | 2012-11-15 | Hitachi Ltd | 燃料電池用セパレータ及びこれを用いた燃料電池 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060257555A1 (en) * | 2005-05-12 | 2006-11-16 | Brady Brian K | Sub-layer for adhesion promotion of fuel cell bipolar plate coatings |
US8133591B2 (en) * | 2006-06-27 | 2012-03-13 | GM Global Technology Operations LLC | Adhesion of polymeric coatings to bipolar plate surfaces using silane coupling agents |
JP2009295346A (ja) * | 2008-06-03 | 2009-12-17 | Hitachi Cable Ltd | 電気接点層付金属材及びその製造方法 |
RU2472257C1 (ru) * | 2008-11-25 | 2013-01-10 | Ниссан Мотор Ко., Лтд. | Электропроводный узел и топливный элемент с полимерным электролитом с его использованием |
CN107429330A (zh) * | 2015-03-18 | 2017-12-01 | 新日铁住金株式会社 | 钛合金、分隔件、及固体高分子型燃料电池 |
DE102016202372A1 (de) | 2016-02-17 | 2017-08-17 | Friedrich-Alexander-Universität Erlangen-Nürnberg | Schicht und Schichtsystem, sowie Bipolarplatte, Brennstoffzelle und Elektrolyseur |
CN108336371A (zh) * | 2018-02-05 | 2018-07-27 | 大连融科储能技术发展有限公司 | 一种全钒液流电池用双极板 |
JP7172056B2 (ja) * | 2018-02-28 | 2022-11-16 | トヨタ自動車株式会社 | ステンレス鋼基材、燃料電池用セパレータ及び燃料電池 |
JP7375721B2 (ja) * | 2020-10-09 | 2023-11-08 | トヨタ自動車株式会社 | セパレータ及びセパレータの製造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002254180A (ja) * | 2001-02-28 | 2002-09-10 | Daido Steel Co Ltd | 高耐食性材料及びその製造方法 |
JP2002260681A (ja) * | 2001-02-28 | 2002-09-13 | Daido Steel Co Ltd | 固体高分子型燃料電池用金属セパレータ及びその製造方法 |
JP2003187817A (ja) * | 2001-12-17 | 2003-07-04 | Riken Corp | 燃料電池用セパレータ |
JP2004134276A (ja) * | 2002-10-11 | 2004-04-30 | Daido Steel Co Ltd | 固体高分子形燃料電池用素材及びその製造方法 |
JP2004158437A (ja) * | 2002-10-18 | 2004-06-03 | Hitachi Cable Ltd | 燃料電池用セパレータ |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4707786B2 (ja) * | 1998-05-07 | 2011-06-22 | トヨタ自動車株式会社 | 燃料電池用ガスセパレータの製造方法 |
CA2373344C (en) * | 2001-02-28 | 2012-03-20 | Daido Tokushuko Kabushiki Kaisha | Corrosion-resistant metallic member, metallic separator for fuel cell comprising the same, and process for production thereof |
US20040081879A1 (en) * | 2002-10-18 | 2004-04-29 | Mineo Washima | Fuel cell bipolarplate |
-
2006
- 2006-05-24 JP JP2007517876A patent/JP4702365B2/ja not_active Expired - Fee Related
- 2006-05-24 CN CNB2006800012835A patent/CN100472864C/zh not_active Expired - Fee Related
- 2006-05-24 WO PCT/JP2006/310399 patent/WO2006126613A1/ja active Application Filing
- 2006-05-24 US US11/791,317 patent/US20080057371A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002254180A (ja) * | 2001-02-28 | 2002-09-10 | Daido Steel Co Ltd | 高耐食性材料及びその製造方法 |
JP2002260681A (ja) * | 2001-02-28 | 2002-09-13 | Daido Steel Co Ltd | 固体高分子型燃料電池用金属セパレータ及びその製造方法 |
JP2003187817A (ja) * | 2001-12-17 | 2003-07-04 | Riken Corp | 燃料電池用セパレータ |
JP2004134276A (ja) * | 2002-10-11 | 2004-04-30 | Daido Steel Co Ltd | 固体高分子形燃料電池用素材及びその製造方法 |
JP2004158437A (ja) * | 2002-10-18 | 2004-06-03 | Hitachi Cable Ltd | 燃料電池用セパレータ |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009533830A (ja) * | 2006-04-14 | 2009-09-17 | アプライド マテリアルズ インコーポレイテッド | 信頼性のある燃料電池電極の設計 |
JP2009123528A (ja) * | 2007-11-15 | 2009-06-04 | Kobe Steel Ltd | 燃料電池セパレータ用チタン基材およびこれを用いた燃料電池セパレータの製造方法 |
JP2009238438A (ja) * | 2008-03-26 | 2009-10-15 | Kobe Steel Ltd | 燃料電池用セパレータ及びその製造方法 |
JP2009289511A (ja) * | 2008-05-28 | 2009-12-10 | Kobe Steel Ltd | 燃料電池セパレータ用チタン基材、および、燃料電池セパレータ、ならびに燃料電池セパレータの製造方法 |
JP2009289707A (ja) * | 2008-06-02 | 2009-12-10 | Nissan Motor Co Ltd | 燃料電池用セパレータ |
JP2012226889A (ja) * | 2011-04-18 | 2012-11-15 | Hitachi Ltd | 燃料電池用セパレータ及びこれを用いた燃料電池 |
Also Published As
Publication number | Publication date |
---|---|
JP4702365B2 (ja) | 2011-06-15 |
JPWO2006126613A1 (ja) | 2008-12-25 |
CN100472864C (zh) | 2009-03-25 |
US20080057371A1 (en) | 2008-03-06 |
CN101069315A (zh) | 2007-11-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4702365B2 (ja) | 燃料電池用セパレータ及びその製造方法 | |
CN105895927B (zh) | 用于pemfc的包括自由基捕获剂的耐腐蚀金属双极板 | |
US6875537B2 (en) | Membrane electrode assembly for polymer electrolyte fuel cell | |
US7674546B2 (en) | Metallic separator for fuel cell and method for anti-corrosion treatment of the same | |
CA2747858C (en) | Fuel cell separator material, fuel cell separator using same, fuel cell stack, and method for producing fuel cell separator material | |
US9793554B2 (en) | Fuel cell separator and fuel cell | |
JP5192908B2 (ja) | 燃料電池セパレータ用チタン基材、および、燃料電池セパレータ、ならびに燃料電池セパレータの製造方法 | |
JP4367062B2 (ja) | 燃料電池用セパレータ | |
US20040081879A1 (en) | Fuel cell bipolarplate | |
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 | |
US8101319B2 (en) | Approach to make a high performance membrane electrode assembly (MEA) for a PEM fuel cell | |
US20110159173A1 (en) | Conductive coating for solid oxide fuel cells | |
US20090176139A1 (en) | Passivated metallic bipolar plates and a method for producing the same | |
JP4639434B2 (ja) | バイポーラプレートおよび固体高分子型燃料電池 | |
Liu et al. | Degradation effects at the porous transport layer/catalyst layer interface in polymer electrolyte membrane water electrolyzer | |
JP2009295343A (ja) | 金属セパレータ用板材及びその製造方法、並びに燃料電池用金属セパレータ | |
WO2009118991A1 (en) | Fuel cell separator | |
JP6947009B2 (ja) | 燃料電池用セパレータ及び燃料電池 | |
WO2005101555A1 (en) | Fuel cell separator, fuel cell stack, fuel cell vehicle, and method of manufacturing the fuel cell separator | |
JP2007128908A (ja) | 固体高分子電解質型燃料電池のセルユニット | |
EP3181728B1 (en) | Metal material and current-carrying component using said metal material | |
JP2009224151A (ja) | 燃料電池セパレータ | |
JP5006028B2 (ja) | 燃料電池用セパレータ | |
EP2712012A2 (en) | A method of manufacturing a fuel cell stack having an electrically conductive interconnect. | |
JP2005302610A (ja) | 燃料電池及び燃料電池用金属製拡散層の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2007517876 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200680001283.5 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11791317 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
NENP | Non-entry into the national phase |
Ref country code: RU |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 06746828 Country of ref document: EP Kind code of ref document: A1 |