WO2017170066A1 - Cellule pour pile à combustible à polymère solide, et empilement de piles à combustible à polymère solide - Google Patents

Cellule pour pile à combustible à polymère solide, et empilement de piles à combustible à polymère solide Download PDF

Info

Publication number
WO2017170066A1
WO2017170066A1 PCT/JP2017/011554 JP2017011554W WO2017170066A1 WO 2017170066 A1 WO2017170066 A1 WO 2017170066A1 JP 2017011554 W JP2017011554 W JP 2017011554W WO 2017170066 A1 WO2017170066 A1 WO 2017170066A1
Authority
WO
WIPO (PCT)
Prior art keywords
stainless steel
content
less
steel material
fuel cell
Prior art date
Application number
PCT/JP2017/011554
Other languages
English (en)
Japanese (ja)
Inventor
樽谷　芳男
Original Assignee
新日鐵住金株式会社
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
Application filed by 新日鐵住金株式会社 filed Critical 新日鐵住金株式会社
Priority to JP2017535113A priority Critical patent/JP6278157B1/ja
Publication of WO2017170066A1 publication Critical patent/WO2017170066A1/fr

Links

Images

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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • 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 polymer electrolyte fuel cell and a polymer electrolyte fuel cell stack.
  • Fuel cells are cells that generate direct current using hydrogen and oxygen, and are roughly classified into solid electrolyte type, molten carbonate type, phosphoric acid type, and solid polymer type. Each type is derived from the constituent material of the electrolyte part constituting the basic part of the fuel cell.
  • fuel cells that have reached the commercial stage include a phosphoric acid type operating near 200 ° C. and a molten carbonate type operating near 650 ° C.
  • solid polymer type that operates near room temperature
  • solid electrolyte type that operates at 700 ° C. or more are attracting attention as compact power supplies for automobiles or home use.
  • FIG. 1 is an explanatory view showing the structure of a solid polymer fuel cell
  • FIG. 1 (a) is an exploded view of a fuel cell (single cell)
  • FIG. 1 (b) is a perspective view of a fuel cell stack. is there.
  • the fuel cell stack 1 is an assembly of single cells.
  • a fuel electrode film (anode) 3 is laminated on one surface of a solid polymer film 2
  • an oxidant electrode film (cathode) 4 is laminated on the other surface.
  • the separators 5a and 5b are stacked.
  • the fuel electrode film 3 and the oxidant electrode film 4 each include a diffusion layer and a catalyst layer provided on the surface of the diffusion layer on the solid polymer film 2 side.
  • the diffusion layer is made of carbon paper or carbon cloth composed of carbon fibers
  • the catalyst layer is made of a particulate platinum catalyst, graphite powder, and a fluororesin having hydrogen ion (proton) exchange groups.
  • the catalyst layers of the fuel electrode film 3 and the oxidant electrode film 4 are in contact with the fuel gas or the oxidizing gas that has permeated the diffusion layer.
  • a fuel gas (hydrogen or hydrogen-containing gas) A is flowed from a flow path 6 a provided in the separator 5 a and hydrogen is supplied to the fuel electrode film 3. Further, an oxidizing gas B such as air is flowed from the flow path 6b provided in the separator 5b, and oxygen is supplied. The supply of these gases causes an electrochemical reaction to generate DC power.
  • the functions required of the polymer electrolyte fuel cell separator are (1) a function as a “flow path” for uniformly supplying fuel gas in the surface on the fuel electrode side, and (2) water generated on the cathode side as fuel. Functions as a "flow path” that efficiently discharges the battery together with carrier gas such as air and oxygen after reaction from the battery, and (3) a single cell that maintains low electrical contact resistance and good electrical conductivity as an electrode over a long period of time A function as an electrical “connector” between them, and (4) a function as a “partition wall” between an anode chamber of one cell and a cathode chamber of an adjacent cell in adjacent cells.
  • the application of carbon plate materials to separators has been intensively studied at the laboratory level.
  • the carbon plate material has a problem that it is easily broken, and further has a problem that the machining cost for flattening the surface and the machining cost for forming the gas flow path are very high. Each of these is a major problem, and it has been difficult to commercialize fuel cells.
  • the thermally expansive graphite processed product is remarkably inexpensive, and is thus attracting the most attention as a material for polymer electrolyte fuel cell separators.
  • it is necessary to deal with stricter dimensional accuracy, deterioration of organic resin with age, which occurs during the application of fuel cells, carbon corrosion that progresses under the influence of battery operating conditions, and when fuel cells are assembled and in use. Problems such as unexpected cracking accidents that occur in Japan are still issues to be solved.
  • Patent Document 1 discloses a fuel cell separator made of a metal member and directly plated with gold on a contact surface with an electrode of a unit cell.
  • the metal member include stainless steel, aluminum, and nickel-iron alloy, and SUS304 is used as the stainless steel.
  • Patent Document 2 discloses a polymer electrolyte fuel cell in which a separator made of a metal material in which a passive film formed on the surface is easily generated by the atmosphere is used. Stainless steel and titanium alloy are mentioned as metal materials.
  • Patent Document 3 discloses stainless steel suitable as a separator for a solid oxide fuel cell.
  • Patent Documents 4 and 5 disclose a polymer electrolyte fuel cell including a separator made of ferritic stainless steel.
  • Patent Document 6 discloses a ferritic stainless steel for a separator of a polymer electrolyte fuel cell containing 0.01 to 0.15% by mass of C in the steel and depositing Cr-based carbides, and a solid high A molecular fuel cell is disclosed.
  • Patent Document 7 discloses an austenitic stainless steel for a separator of a polymer electrolyte fuel cell containing 0.015 to 0.2% C and 7 to 50% Ni and depositing Cr carbide in steel. Steel is shown.
  • Patent Document 8 discloses that among M 23 C 6 type, M 4 C type, M 2 C type, MC type carbide metal inclusions and M 2 B type boride inclusions having conductivity on a stainless steel surface.
  • Stainless steel for separators of polymer electrolyte fuel cells in which one or more of the above are dispersed and exposed is disclosed, and by mass%, C: 0.15% or less, Si: 0.01 to 1.5% , Mn: 0.01 to 1.5%, P: 0.04% or less, S: 0.01% or less, Cr: 15 to 36%, Al: 0.001 to 6%, N: 0.035%
  • a ferritic stainless steel is described that contains the following, the Cr, Mo, and B contents satisfying 17% ⁇ Cr + 3 ⁇ Mo ⁇ 2.5 ⁇ B, and the balance being Fe and inevitable impurities.
  • Patent Document 9 the surface of the stainless steel by corrosion by the acidic aqueous solution, M 23 C 6 type having conductivity in its surface, M 4 C type, M 2 C type, MC type carbide-based metal inclusions and M 2 shows a method for producing a stainless steel material for a separator of a polymer electrolyte fuel cell in which one or more of B-type boride-based metal inclusions are exposed, and in mass%, C: 0.15% or less, Si: 0.01 to 1.5%, Mn: 0.01 to 1.5%, P: 0.04% or less, S: 0.01% or less, Cr: 15 to 36%, Al: 0.001 ⁇ 1%, B: 0 ⁇ 3.5%, N: 0.035% or less, Ni: 0 ⁇ 5%, Mo: 0 ⁇ 7%, Cu: 0 ⁇ 1%, Ti: 0 ⁇ 25 ⁇ (C % + N%), Nb: 0 to 25 ⁇ (C% + N%), and the content of Cr, Mo and B is 1
  • Patent Document 10 discloses that an M 2 B type boride-based metal compound is exposed on the surface, and when the anode area and the cathode area are each 1, the area where the anode is in direct contact with the separator, and A solid polymer fuel cell is shown in which the area where the cathode is in direct contact with the separator is from 0.3 to 0.7, and M 23 C 6 type having conductivity on the stainless steel surface.
  • M 4 C type, M 2 C type, MC type carbide based metal inclusions and M 2 B type boride type inclusions are disclosed.
  • stainless steel constituting the separator is, by mass%, C: 0.15% or less, Si: 0.01 to 1.5%, Mn: 0.01 to 1.5%, P: 0.04% or less, S: 0.01% or less, Cr: 15 to 36%, Al: 0.2% or less, B: 3.5% or less (excluding 0%), N: 0.035%
  • Nb 25 ⁇ It is shown that it is a ferritic stainless steel material that is (C% + N%) or less and the content of Cr, Mo, and B satisfies 17% ⁇ Cr + 3 ⁇ Mo ⁇ 2.5 ⁇ B.
  • Patent Documents 11 to 15 disclose an austenitic stainless clad steel material in which M 2 B type boride conductive metal deposits are exposed on the surface and a method for manufacturing the same.
  • Patent Document 16 C: 0.08% or less, Si: 0.01 to 1.5%, Mn: 0.01 to 1.5%, P: 0.035% or less, S: 0.01%
  • Cr 17 to 36%
  • Al 0.001 to 0.2%
  • B 0.0005 to 3.5%
  • N 0.035% or less
  • the chemical composition is composed of the balance Fe and impurities
  • B in the steel precipitates as M 2 B type boride-based metal inclusions.
  • a fuel cell comprising a separator made of ferritic stainless steel is disclosed.
  • Patent Document 17 for example, C: 0.2% or less, Si: 2% or less, Mn: 3% or less, Al: 0.001% or more and 6% or less, P: 0.06% or less, S: 0 0.03% or less, N: 0.4% or less, Cr: 15% to 30%, Ni: 6% to 50%, B: 0.1% to 3.5%, balance Fe and impurities
  • C 0.2% or less, Si: 2% or less, Mn: 3% or less, Al: 0.001% or more and 6% or less, P: 0.06% or less, S: 0 0.03% or less, N: 0.4% or less, Cr: 15% to 30%, Ni: 6% to 50%, B: 0.1% to 3.5%, balance Fe and impurities
  • An austenitic stainless steel material for a separator of a polymer electrolyte fuel cell having a chemical composition and having a conductive material made of M 2 B type boride metal inclusions is disclosed.
  • Patent Document 18 C: 0.02% or less, Si: 0.15% or less, Mn: 0.3 to 1%, P: 0.04% or less, S: 0.003% or less, Cr: 20 -25%, Mo: 0.5-2%, Al: 0.1% or less, N: 0.02% or less, Nb: 0.001-0.5%, and 2.5 ⁇ Mn / (Si + Al) ⁇ 8.0 is contained, and as optional elements, Ti: 0.5% or less, V: 0.5% or less, Ni: 2% or less, Cu: 1% or less, Sn: 1% or less, B: 0.0.
  • a ferritic stainless steel sheet having a chemical composition comprising impurities and having an oxide film having good electrical conductivity at high temperatures is disclosed.
  • Patent Document 19 C: 0.001 to 0.03%, Si: 0.01 to 2%, Mn: 0.01 to 1.5%, P: 0.005 to 0.05%, S: 0.0001 to 0.01%, Cr: 16 to 30%, N: 0.001 to 0.03%, Al: more than 0.8% to 3%, Sn: 0.01 to 1%, the balance being Fe And a ferritic stainless steel sheet having a chemical composition comprising impurities and having a small amount of Sn added to improve oxidation resistance and high-temperature strength.
  • Patent Document 20 C: 0.01% or less, Si: 0.01 to 0.20%, Mn: 0.01 to 0.30%, P: 0.04% or less, S: 0.01% Hereinafter, Cr: 13 to 22%, N: 0.001 to 0.020%, Ti: 0.05 to 0.35%, Al: 0.005 to 0.050%, Sn: 0.001 to 1% Also disclosed is a ferritic stainless steel having a chemical composition consisting of Fe and impurities in the balance and containing Sn to improve the corrosion resistance by modifying the passive film.
  • the anode volume side volume is reduced to shorten the gas replacement time, or the fuel gas (hydrogen) flow rate at startup is increased so that the gas replacement proceeds in a short time. Devising the channel design has been done. Further, introduction of fuel gas (hydrogen) into the anode electrode side in a pressurized state is also performed.
  • the consumption of the cathode-supported catalyst-supporting carbon at the time of starting the polymer electrolyte fuel cell is a big issue in order to ensure the long-term durability of the polymer electrolyte fuel cell and reduce the performance degradation. .
  • Patent Document 21 discloses an invention in which a gas sensing layer is interposed inside a cell of a polymer electrolyte fuel cell, between an anode flow field plate and an anode catalyst layer.
  • the gas sensing layer includes, for example, semiconductor oxide nanostructures less than about 30 nanometers.
  • the semiconductor oxide nanostructure is composed of titanium oxide, tin oxide, zinc oxide, zirconium oxide, and combinations thereof.
  • the gas sensing layer reduces electrical resistance when contacted with hydrogen gas and increases electrical resistance when contacted with oxygen-containing gas to protect the cell from corrosion when O 2 remains in the anode channel. .
  • the gas sensing layer comes into contact with hydrogen and the electric resistance decreases, and the original cell reaction proceeds.
  • the gas sensing layer has an electrical property that causes a decrease in battery performance caused by an induced voltage between the anode and the cathode through an MEA (Membrane Electrode Assembly) composed of a gas diffusion layer, a polymer film, and a catalyst layer. Suppress chemical reactions.
  • Patent Document 21 further discloses SnO 2 as tin oxide and TiO 2 nanotubes as titanium oxide.
  • the gas sensing layer can be formed by coating on a gas diffusion layer or bipolar plate and heat treatment at 200-400 ° C. to improve adhesion, physical vapor deposition on the bipolar plate, chemical Deposition methods such as vapor deposition and electrodeposition are disclosed. It is also disclosed to convert the nanostructured semiconductor oxide into a gas sensing layer using known techniques such as electrochemical etching or acid corrosion of these metal films.
  • JP 2000-239806 JP 2000-294255 A JP 2000-294256 A JP 2000-303151 A JP 2000-309854 A JP 2003-193206 A JP 2001-214286 A JP 2002-151111 A JP 2004-71319 A JP 2004-156132 A JP 2004-306128 A JP 2007-1118025 A JP 2009-215655 A JP 2000-328205 A JP 2010-140886 A JP 2014-031572 A JP 2012-172160 A JP 2009-174036 A JP2015-128064A
  • the present invention solves the above-mentioned problem, and at the time of starting the solid molecular fuel cell, the fuel gas is introduced into the anode electrode side while the oxidizing gas remains inside the anode electrode side of the fuel cell. It is an object of the present invention to provide a polymer electrolyte fuel cell, which can reduce corrosion of carbon and separator on the cathode electrode side, and a polymer electrolyte fuel cell stack including the same.
  • the present invention has been made in order to solve the above-mentioned problems, and has the following gist and a polymer electrolyte fuel cell stack and a polymer electrolyte fuel cell stack.
  • a cell for a polymer electrolyte fuel cell comprising an anode electrode side cell constituent member and a cathode electrode side cell constituent member
  • the anode electrode side cell constituent member includes a ferritic stainless steel material
  • the cathode electrode side cell constituent member includes a stainless steel material
  • the ferritic stainless steel material contained in the anode electrode side cell constituent member has a chemical composition of mass% and Sn content of 0.02 to 2.50%, and In the ferritic stainless steel material, there are precipitates containing M 2 B type boride finely dispersed and precipitated, A part of the precipitate protrudes from the surface of the ferritic stainless steel material
  • the stainless steel material contained in the cathode electrode side cell constituent member has a chemical composition in which the Sn content is less than 0.02% by mass%. Solid polymer fuel cell.
  • the stainless steel material included in the cathode electrode side cell constituent member is: In the stainless steel material, having a precipitate containing M 2 B type boride finely dispersed and precipitated, A part of the precipitate protrudes from the surface of the stainless steel material.
  • the stainless steel material included in the cathode electrode side cell constituent member is: It has a corrosion-resistant plating layer with conductivity on the surface, The polymer electrolyte fuel cell according to the above (1) or (2).
  • the cathode electrode is caused by the fuel gas being introduced into the anode electrode side while the oxidizing gas remains inside the anode electrode side of the fuel cell. It is possible to obtain a polymer electrolyte fuel cell, and a polymer electrolyte fuel cell stack including the same, which can reduce corrosion of carbon and separator on the side.
  • FIG. 1A and 1B are explanatory views showing the structure of a solid polymer fuel cell.
  • FIG. 1A is an exploded view of a fuel cell (single cell), and
  • FIG. 1B is a perspective view of a fuel cell stack. is there.
  • FIG. 2 is a schematic cross-sectional view of a polymer electrolyte fuel cell.
  • FIG. 3 is a photograph showing the shape of the separator used in the example.
  • the present inventor has found that the metal of MEA composed of a diffusion layer, a polymer membrane, and a catalyst layer has little metal elution from the separator surface even when used for a long time as a separator of a polymer electrolyte fuel cell for many years.
  • FIG. 2 is a schematic cross-sectional view of the polymer electrolyte fuel cell 10.
  • the polymer electrolyte fuel cell 10 includes an MEA 20 in which catalyst layers 17 and 18 and diffusion layers 15 and 16 are provided on both sides of a polymer membrane 19, respectively, and an anode electrode side cell configuration provided on both sides of the MEA 20 respectively.
  • an anode electrode side fuel gas channel 13 and a cathode electrode side gas channel 14 are provided, respectively.
  • FIG. 2 schematically illustrates a chemical reaction that proceeds inside the solid polymer fuel cell 10 at the time of startup.
  • a transient phenomenon that occurs inside the polymer electrolyte fuel cell 10 at the time of startup will be described in more detail.
  • Reaction (i) is a reaction in which the remaining air generates H + deficiency, and is a transient reaction at the time of start-up that proceeds in the catalyst layer 17 on the anode electrode side.
  • Reaction (ii) is a C exhaustion reaction that proceeds on the catalyst layer 18 side on the cathode side.
  • the reaction (iii) is a water splitting reaction (oxidation reaction) for compensating for the H + deficiency that proceeds on the catalyst layer 18 side on the cathode side.
  • the catalyst-carrying carbon is consumed (corroded) in the cathode-side catalyst layer 18 and the cathode-electrode-side cell component 12 is further corroded.
  • the corrosion of the catalyst-carrying carbon directly leads to a decrease in fuel cell performance.
  • the corrosion of the catalyst-supporting carbon is an irreversible reaction, it causes a cumulative decrease in fuel cell performance.
  • the present inventor has intensively studied without being bound by such premise. That is, it was examined to apply a material that exhibits the performance required in each environment for the anode electrode side cell constituent member and the cathode electrode side cell constituent member.
  • the anode-side cell component member has excellent surface corrosion resistance in addition to low surface contact resistance during normal operation and excellent electrical conductivity (contact electrical resistance). It is desirable to be high and to suppress the formation of local batteries. Then, this inventor examined the steel material which has such performance, As a result, it came to obtain the following knowledge.
  • M 2 B type boride finely dispersed in the steel material and projecting on the surface (hereinafter sometimes simply referred to as “M 2 B”) is formed on the surface of the stainless steel covered with a passive film.
  • Passage conductive path
  • the electrical conductivity of metal tin or tin oxide varies depending on the oxygen potential of the gas atmosphere to be exposed (hereinafter referred to as “oxygen concentration”). Specifically, the lower the oxygen concentration, the more the electrical conductivity. Become good. Therefore, the contact electrical resistance of the steel material surface increases when the oxygen concentration of the atmosphere to which the steel material surface is exposed is high as in air, and decreases when the oxygen concentration is extremely low as in a hydrogen atmosphere.
  • the cathode electrode side cell constituent member is used in an oxidizing atmosphere even during normal operation. Therefore, when a stainless steel material containing Sn is applied to the cathode electrode side cell constituent member, the surface of the mother phase is inferior in conductivity due to the dissolution of the mother phase (corrosion) that proceeds extremely slowly during operation. To become. As a result, the contact electrical resistance increases and the battery output decreases.
  • the polymer electrolyte fuel cell 10 includes an anode electrode-side cell component 11 and a cathode electrode-side cell component 12. Each will be described in detail.
  • the “cell constituent member” is a separator or a current plate.
  • the separator is sometimes called a bipolar plate.
  • the rectifying plate is a member for rectifying or distributing fuel gas or oxidizing gas, and is sometimes referred to as a porous plate, fin, or mesh.
  • Anode electrode side cell constituent member 11 includes a ferritic stainless steel material described below.
  • the member used for the surface part of a gas flow path at least among the anode electrode side cell structural members 11 is comprised by the ferritic stainless steel material mentioned later.
  • the ferritic stainless steel material contained in the anode electrode side cell constituent member 11 has an Sn content of 0.02 to 2.50%. The reason why the Sn content is limited to the above range will be described later.
  • the chemical composition of the ferritic stainless steel material is as follows: C: 0.001 to 0.15%, Si: 0.01 to 1.5%, Mn: 0.01 to 1.5%, P: 0.00. 035% or less, S: 0.01% or less, Cr: 22.5-35.0%, Mo: 0.01-6.0%, Ni: 0.01-6.0%, Cu: 0.01 -1.0%, N: 0.035% or less, V: 0.01-0.35%, B: 0.5-1.0%, Al: 0.001-6.0%, Sn: 0 0.02 to 2.50%, REM: 0 to 0.1%, Nb: 0 to 0.35%, Ti: 0 to 0.35%, and the balance: Fe and impurities, represented by the following formula (iv) Is preferably satisfied. 20.0 ⁇ Cr + 3 ⁇ Mo ⁇ 2.5 ⁇ B-17 ⁇ C ⁇ 45.0 (iv) However, each element symbol in a formula means content (mass%) of each element contained in steel materials.
  • impurities are components mixed by various factors such as melting raw materials, additive elements, scraps, and manufacturing processes used when industrially producing steel materials, and are allowed within a range that does not adversely affect the present invention. Means what will be done.
  • ferritic stainless steel materials include the following two types of ferritic stainless steel materials.
  • C 0.001 to 0.15% C depends on the structure and composition of the parent phase, particularly the Cr content in the steel, but steel as Cr-based M 23 C 6 type Cr-based carbide (hereinafter sometimes simply referred to as “M 23 C 6 ”). May precipitate out.
  • M 23 C 6 Cr-based M 23 C 6 type Cr-based carbide
  • the C content is set to 0.001 to 0.15%.
  • the C content when a Cr-based carbide such as M 23 C 6 is actively used, the C content may be 0.020 to 0.15%. In this case, the C content is preferably 0.030% or more, and preferably 0.14% or less.
  • Si 0.01 to 1.5%
  • Si is a deoxidizing element as effective as Al in mass-produced steel.
  • the Si content is less than 0.01%, not only deoxidation becomes unstable, but also the amount of Al added increases and the production cost increases. Also, steel surface flaws are likely to occur.
  • the Si content is set to 0.01 to 1.5%.
  • the Si content is preferably 0.05% or more, and more preferably 0.1% or more.
  • it is preferable that Si content is 1.2% or less, and it is more preferable that it is 1.0% or less.
  • Mn 0.01 to 1.5%
  • Mn has an effect of fixing S in steel as a Mn-based sulfide, and has an effect of improving hot workability.
  • the Mn content exceeds 1.5%, the adhesion of the high-temperature oxide scale formed on the surface during heating during production is reduced, and scale peeling that causes surface roughness is likely to occur. Therefore, the Mn content is set to 0.01 to 1.5%.
  • the Mn content is preferably 0.05% or more, and more preferably 0.1% or more. Further, the Mn content is preferably 1.2% or less, and more preferably 1.0% or less.
  • P 0.035% or less P is a harmful impurity element along with S. If the P content exceeds 0.035%, the productivity decreases. Therefore, the P content is 0.035% or less.
  • S 0.01% or less S is an impurity element extremely harmful to corrosion resistance. For this reason, S content shall be 0.01% or less. Depending on the coexisting elements in steel and the amount of S in steel, S is mostly precipitated as Mn-based sulfides, Fe-based sulfides, or composite non-metallic precipitates with these composite sulfides and oxides. is doing.
  • any non-sulfide sulfide precipitate of any composition will act as a starting point for corrosion to some extent, but it will maintain the passive film and elute metal ions. Harmful to suppression.
  • the S content of ordinary mass-produced steel is more than 0.005% to around 0.008%, but in order to suppress the harmful effects described above, the S content should be 0.003% or less. Preferably, it is 0.002% or less, more preferably less than 0.001%. The lower the S content, the better. It is possible to make the S content less than 0.001% at an industrial mass production level with a slight increase in production cost if the current refining technology is used.
  • Cr 22.5-35.0% Cr is an element having an action of ensuring the corrosion resistance of the base material. The higher the Cr content, the higher the corrosion resistance. Also, in order to precipitate M 2 B in the steel material, it is necessary to include Cr. On the other hand, if the Cr content exceeds 35.0%, production on a mass production scale becomes difficult. Therefore, the Cr content is 22.5 to 35.0%.
  • the Cr concentration that contributes to the improvement of the corrosion resistance in the matrix phase may be lower than the Cr concentration in the molten steel stage, and the corrosion resistance may be lowered.
  • Cr is a necessary element when M 23 C 6 is deposited.
  • the Cr concentration that contributes to improving the corrosion resistance in the matrix may be lower than the Cr concentration at the molten steel stage, and the corrosion resistance may be lowered.
  • the C content is 0.020 to 0.15%, and in order to ensure the corrosion resistance inside the polymer electrolyte fuel cell, it is preferable to satisfy the following formula (iv). 20.0 ⁇ Cr + 3 ⁇ Mo ⁇ 2.5 ⁇ B-17 ⁇ C ⁇ 45.0 (iv)
  • Mo 0.01 to 6.0% Mo has an effect of improving the corrosion resistance in a small amount as compared with Cr. Further, even if Mo is eluted, the influence on the performance of the catalyst supported on the anode and cathode is relatively small. This is thought to be because the eluted Mo exists as molybdate ions, which are anions, so that the influence of inhibiting the proton conductivity of the fluorine-based ion exchange resin membrane having a hydrogen ion (proton) exchange group is small. .
  • Mo is contained in an amount exceeding 6.0%, it is difficult to avoid precipitation of intermetallic compounds such as sigma phase during the production, and production is difficult due to the problem of steel embrittlement.
  • Mo is an expensive additive element. Therefore, the Mo content is set to 0.01 to 6.0%.
  • the Mo content is preferably 0.05% or more, and preferably less than 5.0%.
  • Ni 0.01 to 6.0%
  • Ni is an element that improves corrosion resistance and toughness. However, if the Ni content exceeds 6.0%, it becomes difficult to obtain a ferrite single phase structure even if heat treatment is applied industrially. Therefore, the Ni content is set to 0.01 to 6.0%.
  • the Ni content is preferably 0.03% or more.
  • Cu 0.01 to 1.0% Cu is inevitably mixed in by 0.01% or more from the melting raw material. Although it is possible to dissolve at less than 0.01%, the production cost increases. If the Cu content exceeds 1.0%, hot workability will be reduced, and it will be difficult to ensure mass productivity. Therefore, the Cu content is set to 0.01 to 1.0%. Cu needs to be dissolved in the matrix. When dispersed as a metal-based precipitate, it becomes a starting point for corrosion in the fuel cell, resulting in a decrease in cell performance.
  • the Cu content is preferably 0.02% or more, and preferably 0.8% or less.
  • N 0.035% or less
  • N is an element that is contained in steel as an impurity and deteriorates room temperature toughness. Therefore, the N content is 0.035% or less.
  • the N content is desirably 0.007% or less.
  • N content is 0.001% or more, and it is more preferable that it is 0.002% or more.
  • V 0.01 to 0.35%
  • V is not an intentionally added element, but is unavoidably contained in a Cr source used as a melting raw material during mass production.
  • V improves the room temperature toughness of ferritic stainless steel, albeit slightly. For this reason, the V content is set to 0.01 to 0.35%.
  • the V content is preferably 0.03% or more, and preferably 0.30% or less.
  • B 0.5 to 1.0%
  • M 2 B precipitated and dispersed in the steel material and exposed to the surface improves the surface conductivity and also serves as a precipitation nucleus for controlling the precipitation of M 23 C 6 .
  • the B content is less than 0.5%, the amount of M 2 B deposited is small and it is difficult to ensure the surface conductivity.
  • the content exceeds 1.0%, the ductility is remarkably lowered and it becomes difficult to produce a steel material. Therefore, the B content is 0.5 to 1.0%.
  • the B content is preferably 0.5% or more, and preferably 0.85% or less.
  • Al 0.001 to 6.0%
  • Al is an effective deoxidizing element. Since B, which is essential, is an element having a strong binding force with oxygen in the molten steel, it is necessary to sufficiently reduce the oxygen concentration in the molten steel by Al deoxidation. Therefore, it is necessary to contain 0.001% or more of Al. On the other hand, when an amount of Al exceeding 6.0% is contained, an aluminum oxide film having poor conductivity is easily generated on the steel material surface, and the manufacturing cost increases. Therefore, the Al content is made 0.001 to 6.0%. The Al content is preferably 0.01% or more, and preferably 5.5% or less.
  • Sn 0.02 to 2.50% Sn is dissolved in the matrix phase by adding it as an alloy element in the molten steel stage.
  • Sn dissolved in the mother phase is not only the surface of the mother phase but also M 2 due to the acid solution treatment performed in advance or the gentle mother phase dissolution that occurs during the operation of the fuel cell.
  • the surface of B is also concentrated as metallic tin or tin oxide.
  • Metal tin and tin oxide have semiconducting properties, and the surface contact resistance value in an oxidizing atmosphere is about 2 to 3 times the surface contact resistance value in a non-oxidizing atmosphere. Get higher. This action exerts an action of suppressing a local cell reaction that occurs transiently at the time of starting the polymer electrolyte fuel cell.
  • the Sn content is less than 0.02%, such an effect may not be stably obtained. On the other hand, if the Sn content exceeds 2.50%, the productivity may decrease. Therefore, the Sn content is 0.02 to 2.50%.
  • the Sn content is preferably 0.05% or more, and preferably 1.0% or less.
  • REM 0 to 0.1% Since REM (rare earth element) has an effect of improving hot manufacturability, it may be contained as necessary. However, excessive inclusion leads to an increase in manufacturing cost. Therefore, the REM content is 0.1% or less.
  • the REM content is preferably 0.05% or less. In order to obtain the above effect, the REM content is preferably 0.001% or more, and more preferably 0.005% or more.
  • REM refers to a total of 17 elements of Sc, Y and lanthanoid, and the content of REM means the total content of these elements.
  • the lanthanoid is industrially added in the form of misch metal.
  • Nb 0 to 0.35%
  • Ti are C and N stabilizing elements in steel. That is, Nb and Ti form carbides and nitrides in the steel. Therefore, in particular, when the C content is 0.001% or more and less than 0.020%, one or two of these may be contained as necessary.
  • the contents of Ti and Nb are both 0.35% or less.
  • the Nb and Ti contents are preferably 0.30% or less. In order to acquire said effect, it is preferable to contain 0.001% or more of 1 type or 2 types of Nb and Ti.
  • Nb is preferably contained so that the (Nb / C) value is 3.0 to 25.0
  • Ti is contained so that the ⁇ Ti / (C + N) ⁇ value is 3.0 to 25.0. .
  • Ferritic stainless steel material included in anode electrode side cell constituting member 11 has a precipitate containing M 2 B finely dispersed and precipitated in the steel material.
  • This precipitate may further include a composite precipitate in which M 23 C 6 is precipitated on the surface using M 2 B as a precipitation nucleus.
  • M in M 23 C 6 is Cr, Cr, Fe, or the like, and a part of C may be substituted with B.
  • M in M 2 B is Cr, Cr, Fe, or the like, and a part of B may be substituted with C.
  • M 2 B or M 23 C 6 protruding from the surface of the steel material functions as a conductive path and has an effect of reducing contact resistance.
  • M 2 B protruding from the surface of the steel material may fall off.
  • M 2 B is a metal precipitate, it is metal-bonded to the parent phase and does not fall off.
  • M 2 B is a large and very hard precipitate. Therefore, it is mechanically crushed in each process of hot forging, hot rolling, and cold rolling, and is uniformly dispersed.
  • M 2 B has electrical conductivity and is a very large metal precipitate even when crushed. Therefore, a sufficient function as a conductive path can be obtained even with M 2 B alone.
  • M 23 C 6 is more excellent in conductivity than M 2 B. Therefore, by depositing M 23 C 6 excellent in conductivity on the surface of M 2 B which is large and dispersed in a large amount, a composite precipitate having large and excellent conductivity is dispersed and exists. A more desirable surface state can be obtained as a steel material used for the pole-side cell constituent member.
  • M 2 B is precipitated by a eutectic reaction that proceeds at the end of solidification. Therefore, it has the characteristics that the composition is uniform and is extremely stable thermally. There is no re-dissolution, re-precipitation, or component change due to the thermal history in the manufacturing process of the steel material.
  • M 23 C 6 depends on the C content in the steel, a part or all of it is dissolved in the heating process and re-precipitated on the surface of M 2 B in the subsequent cooling process. That is, by performing a heat treatment in which appropriate heating and cooling conditions are set, it is possible to obtain a composite precipitate in which M 23 C 6 is precipitated on the surface using M 2 B as a precipitation nucleus.
  • the cathode pole side cell constituent member 12 includes a stainless steel material described below. In addition, it is preferable that the member used for at least the surface part of a gas flow path among the cathode electrode side cell structural members 12 is comprised by the stainless steel material mentioned later.
  • the chemical composition of the above stainless steel material is as follows: C: 0.001 to 0.2%, Si: 0.01 to 1.5%, Mn: 0.01 to 2.5%, P: 0.035%
  • S 0.01% or less
  • Cr 16.0-35.0%
  • Mo 0-7.0%
  • Ni 0.01-50.0%
  • Cu 0.01-3.0 %
  • N 0.001 to 0.4%
  • V 0 to 0.35%
  • B 0.5 to 1.0%
  • W 0 to 4. 0%
  • Sn less than 0.02%
  • REM 0 to 0.1%
  • Nb 0 to 0.35%
  • Ti 0 to 0.35%
  • balance Fe and impurities.
  • the above stainless steel material may be a ferritic stainless steel material or an austenitic stainless steel material.
  • the ferritic stainless steel material include the following two types of ferritic stainless steel materials, and examples of the austenitic stainless steel material include the following one type of austenitic stainless steel material.
  • Each chemical composition will be described in detail.
  • a duplex stainless steel material is a cell for a polymer electrolyte fuel cell. It is not suitable as a component.
  • (C) C: 0.001% or more and less than 0.020%, Si: 0.01 to 1.5%, Mn: 0.01 to 1.5%, P: 0.035% or less, S: 0.0. 01% or less, Cr: 22.5 to 35.0%, Mo: 0.01 to 6.0%, Ni: 0.01 to 6.0%, Cu: 0.01 to 1.0%, N: 0.035% or less, V: 0.01 to 0.35%, B: 0.5 to 1.0%, Al: 0.001 to 6.0%, Sn: less than 0.02%, REM: 0 A ferritic stainless steel material that is 0.1%, Nb: 0-0.35%, Ti: 0-0.35%, and the balance: Fe and impurities, satisfying the following formula (v). 20.0 ⁇ Cr + 3 ⁇ Mo ⁇ 2.5 ⁇ B ⁇ 45.0 (v)
  • Chemical composition of ferritic stainless steel C 0.001 to 0.15% C may precipitate in steel as M 23 C 6 mainly composed of Cr, although it depends on the structure and composition of the parent phase, particularly the Cr content in the steel.
  • M 23 C 6 mainly composed of Cr
  • the C content is set to 0.001 to 0.15%.
  • C content is good also as 0.001% or more and less than 0.020%.
  • the C content is preferably 0.0015% or more, and preferably less than 0.010%.
  • the C content when a Cr-based carbide such as M 23 C 6 is actively used, the C content may be 0.020 to 0.15%. In this case, the C content is preferably 0.030% or more, and preferably 0.14% or less.
  • Si 0.01 to 1.5%
  • Si is a deoxidizing element as effective as Al in mass-produced steel.
  • the Si content is less than 0.01%, not only deoxidation becomes unstable, but also the amount of Al added increases and the production cost increases. Also, steel surface flaws are likely to occur.
  • the Si content is set to 0.01 to 1.5%.
  • the Si content is preferably 0.05% or more, and more preferably 0.1% or more.
  • it is preferable that Si content is 1.2% or less, and it is more preferable that it is 1.0% or less.
  • Mn 0.01 to 1.5%
  • Mn has an effect of fixing S in steel as a Mn-based sulfide, and has an effect of improving hot workability.
  • the Mn content exceeds 1.5%, the adhesion of the high-temperature oxide scale formed on the surface during heating during production is reduced, and scale peeling that causes surface roughness is likely to occur. Therefore, the Mn content is set to 0.01 to 1.5%.
  • the Mn content is preferably 0.05% or more, and more preferably 0.1% or more. Further, the Mn content is preferably 1.2% or less, and more preferably 1.0% or less.
  • P 0.035% or less P is a harmful impurity element along with S. If the P content exceeds 0.035%, the productivity decreases. Therefore, the P content is 0.035% or less.
  • S 0.01% or less S is an impurity element extremely harmful to corrosion resistance. For this reason, S content shall be 0.01% or less. Depending on the coexisting elements in steel and the amount of S in steel, S is mostly precipitated as Mn-based sulfides, Fe-based sulfides, or composite non-metallic precipitates with these composite sulfides and oxides. is doing.
  • any non-sulfide sulfide precipitate of any composition will act as a starting point for corrosion to some extent, but it will maintain the passive film and elute metal ions. Harmful to suppression.
  • the S content of ordinary mass-produced steel is more than 0.005% to around 0.008%, but in order to suppress the harmful effects described above, the S content should be 0.003% or less. Preferably, it is 0.002% or less, more preferably less than 0.001%. The lower the S content, the better. It is possible to make the S content less than 0.001% at an industrial mass production level with a slight increase in production cost if the current refining technology is used.
  • Cr 22.5-35.0% Cr is an element having an action of ensuring the corrosion resistance of the base material. The higher the Cr content, the higher the corrosion resistance. Also, in order to precipitate M 2 B in the steel material, it is necessary to include Cr. On the other hand, if the Cr content exceeds 35.0%, production on a mass production scale becomes difficult. Therefore, the Cr content is 22.5 to 35.0%.
  • the Cr concentration that contributes to the improvement of the corrosion resistance in the matrix phase may be lower than the Cr concentration in the molten steel stage, and the corrosion resistance may be lowered.
  • Cr is a necessary element when M 23 C 6 is deposited.
  • the Cr concentration that contributes to improving the corrosion resistance in the matrix may be lower than the Cr concentration at the molten steel stage, and the corrosion resistance may be lowered.
  • the C content is 0.020 to 0.15%, and in order to ensure the corrosion resistance inside the polymer electrolyte fuel cell, it is preferable to satisfy the following formula (iv). 20.0 ⁇ Cr + 3 ⁇ Mo ⁇ 2.5 ⁇ B-17 ⁇ C ⁇ 45.0 (iv)
  • Mo 0.01 to 6.0% Mo has an effect of improving the corrosion resistance in a small amount as compared with Cr. Further, even if Mo is eluted, the influence on the performance of the catalyst supported on the anode and cathode is relatively small. This is thought to be because the eluted Mo exists as molybdate ions, which are anions, so that the influence of inhibiting the proton conductivity of the fluorine-based ion exchange resin membrane having a hydrogen ion (proton) exchange group is small. .
  • Mo is contained in an amount exceeding 6.0%, it is difficult to avoid precipitation of intermetallic compounds such as sigma phase during the production, and production is difficult due to the problem of steel embrittlement.
  • Mo is an expensive additive element. Therefore, the Mo content is set to 0.01 to 6.0%.
  • the Mo content is preferably 0.05% or more, and preferably less than 5.0%.
  • Ni 0.01 to 6.0%
  • Ni is an element that improves corrosion resistance and toughness. However, if the Ni content exceeds 6.0%, it becomes difficult to obtain a ferrite single phase structure even if heat treatment is applied industrially. Therefore, the Ni content is set to 0.01 to 6.0%.
  • the Ni content is preferably 0.03% or more.
  • Cu 0.01 to 1.0% Cu is inevitably mixed in by 0.01% or more from the melting raw material. Although it is possible to dissolve at less than 0.01%, the production cost increases. If the Cu content exceeds 1.0%, hot workability will be reduced, and it will be difficult to ensure mass productivity. Therefore, the Cu content is set to 0.01 to 1.0%. Cu needs to be dissolved in the matrix. When dispersed as a metal-based precipitate, it becomes a starting point for corrosion in the fuel cell, resulting in a decrease in cell performance.
  • the Cu content is preferably 0.02% or more, and preferably 0.8% or less.
  • N 0.035% or less
  • N is an element that is contained in steel as an impurity and deteriorates room temperature toughness. Therefore, the N content is 0.035% or less.
  • the N content is desirably 0.007% or less.
  • N content is 0.001% or more, and it is more preferable that it is 0.002% or more.
  • V 0.01 to 0.35%
  • V is not an element intentionally added, but is unavoidably contained in a Cr source used as a melting raw material during mass production.
  • V improves the room temperature toughness of ferritic stainless steel, albeit slightly. For this reason, the V content is set to 0.01 to 0.35%.
  • the V content is preferably 0.03% or more, and preferably 0.30% or less.
  • B 0.5 to 1.0%
  • M 2 B precipitated and dispersed in the steel material and exposed to the surface improves the surface conductivity and also serves as a precipitation nucleus for controlling the precipitation of M 23 C 6 .
  • the B content is less than 0.5%, the amount of M 2 B deposited is small and it is difficult to ensure the surface conductivity.
  • the content exceeds 1.0%, the ductility is remarkably lowered and it becomes difficult to produce a steel material. Therefore, the B content is 0.5 to 1.0%.
  • the B content is preferably 0.5% or more, and preferably 0.85% or less.
  • Al 0.001 to 6.0%
  • Al is an effective deoxidizing element. Since B, which is essential, is an element having a strong binding force with oxygen in the molten steel, it is necessary to sufficiently reduce the oxygen concentration in the molten steel by Al deoxidation. Therefore, it is necessary to contain 0.001% or more of Al. On the other hand, when an amount of Al exceeding 6.0% is contained, an aluminum oxide film having poor conductivity is easily generated on the steel material surface, and the manufacturing cost increases. Therefore, the Al content is made 0.001 to 6.0%. The Al content is preferably 0.01% or more, and preferably 5.5% or less.
  • Sn Less than 0.02%
  • the cathode electrode side cell constituent member is used in an oxidizing atmosphere even during normal operation. Therefore, when a stainless steel material containing Sn is applied to the cathode electrode side cell constituent member, tin oxide having poor conductivity becomes thicker on the surface of the parent phase and the like.
  • Sn content shall be less than 0.02%.
  • the Sn content is preferably 0.015% or less. The Sn content may be at the impurity level.
  • REM 0 to 0.1% Since REM (rare earth element) has an effect of improving hot manufacturability, it may be contained as necessary. However, excessive inclusion leads to an increase in manufacturing cost. Therefore, the REM content is 0.1% or less.
  • the REM content is preferably 0.05% or less. In order to obtain the above effect, the REM content is preferably 0.001% or more, and more preferably 0.005% or more.
  • REM refers to a total of 17 elements of Sc, Y and lanthanoid, and the content of REM means the total content of these elements.
  • the lanthanoid is industrially added in the form of misch metal.
  • Nb 0 to 0.35%
  • Ti are C and N stabilizing elements in steel. That is, Nb and Ti form carbides and nitrides in the steel. Therefore, in particular, when the C content is 0.001% or more and less than 0.020%, one or two of these may be contained as necessary.
  • the contents of Ti and Nb are both 0.35% or less.
  • the Nb and Ti contents are preferably 0.30% or less. In order to acquire said effect, it is preferable to contain 0.001% or more of 1 type or 2 types of Nb and Ti.
  • Nb is preferably contained so that the (Nb / C) value is 3.0 to 25.0
  • Ti is contained so that the ⁇ Ti / (C + N) ⁇ value is 3.0 to 25.0. .
  • C is an austenite phase stabilizing element. If the C content is less than 0.005%, the austenite phase becomes unstable and sensitization is likely to occur, and the corrosion resistance due to sensitization is liable to be lowered, and the normal temperature toughness is lowered and productivity is lowered. On the other hand, if C is contained excessively, the productivity is remarkably deteriorated. Therefore, the C content is set to 0.005 to 0.20%.
  • the C content is preferably 0.015% or more.
  • the C content is preferably 0.15% or less, and more preferably 0.025% or less.
  • Si 0.01 to 1.5%
  • Si is a deoxidizing element as effective as Al in mass-produced steel.
  • the Si content is less than 0.01%, not only deoxidation becomes unstable, but also the amount of Al added increases and the production cost increases. Steel surface flaws are also likely to occur.
  • the Si content is set to 0.01 to 1.5%.
  • the Si content is preferably 0.05% or more, and more preferably 0.1% or more.
  • it is preferable that Si content is 1.2% or less, and it is more preferable that it is 1.0% or less.
  • Mn 0.01 to 2.5%
  • Mn has an effect of fixing S in steel as a Mn-based sulfide, and has an effect of improving hot workability. If the Mn content is less than 0.01%, the above effect cannot be obtained. On the other hand, when the Mn content exceeds 2.5%, the adhesion of the high-temperature oxide scale formed on the surface during heating during production is reduced, and scale peeling that causes surface roughness is likely to occur. Therefore, the Mn content is set to 0.01 to 2.5%.
  • the Mn content is preferably 0.05% or more, and more preferably 0.1% or more. Moreover, it is preferable that Mn content is 1.0% or less, and it is more preferable that it is 0.6% or less.
  • P 0.035% or less
  • P is a harmful impurity element along with S. If the P content exceeds 0.035%, the productivity decreases. Therefore, the P content is 0.035% or less. From the viewpoint of manufacturability, the P content is preferably 0.030% or less.
  • S 0.01% or less S is an impurity element extremely harmful to corrosion resistance. For this reason, S content shall be 0.01% or less. Depending on the coexisting elements in steel and the amount of S in steel, S is mostly precipitated as Mn-based sulfides, Fe-based sulfides, or composite non-metallic precipitates with these composite sulfides and oxides. is doing.
  • any non-sulfide sulfide precipitate of any composition will act as a starting point for corrosion to some extent, but it will maintain the passive film and elute metal ions. Harmful to suppression.
  • the S content of ordinary mass-produced steel is more than 0.005% to around 0.008%, but in order to suppress the harmful effects described above, the S content should be 0.003% or less. Preferably, it is 0.002% or less, more preferably less than 0.001%. The lower the S content, the better. It is possible to make the S content less than 0.001% at an industrial mass production level with a slight increase in production cost if the current refining technology is used.
  • Cr 16.0-30.0%
  • Cr is an element having an action of ensuring the corrosion resistance of the base material. The higher the Cr content, the higher the corrosion resistance. Also, in order to precipitate M 2 B in the steel material, it is necessary to include Cr. On the other hand, since Cr is a ferrite-forming element, if the Cr content exceeds 30.0%, it is necessary to contain a large amount of Ni, which is an austenite-forming element, in order to stabilize the austenite phase. The decrease becomes noticeable. Therefore, the Cr content is 16.0 to 30.0%.
  • Cr is a necessary element also when M 23 C 6 is deposited.
  • the Cr concentration that contributes to improving the corrosion resistance in the matrix may be lower than the Cr concentration at the molten steel stage, and the corrosion resistance may be lowered.
  • Mo 0 to 7.0% Mo has an effect of improving the corrosion resistance in a small amount as compared with Cr. Since the inside of the polymer electrolyte fuel cell is a severe environment as a corrosive environment, Mo may be contained if necessary. Further, even if Mo is eluted, the influence on the performance of the catalyst supported on the anode and cathode is relatively small. This is thought to be because the eluted Mo exists as molybdate ions, which are anions, so that the influence of inhibiting the proton conductivity of the fluorine-based ion exchange resin membrane having a hydrogen ion (proton) exchange group is small. .
  • Mo is contained in an amount exceeding 7.0%, it is difficult to avoid precipitation of intermetallic compounds such as sigma phase during the production, and production is difficult due to the problem of steel embrittlement.
  • Mo is an expensive additive element. Therefore, the Mo content is 7.0% or less.
  • the Mo content is preferably 6.5% or less. In order to acquire the said effect, it is preferable that Mo content is 0.5% or more.
  • Ni 7.0 to 50.0% Since Ni is an austenite forming element, it is contained by 7.0% or more. However, since Ni is an expensive element, if it is contained in excess of 50.0%, the moldability deteriorates and it becomes unsuitable for processing as a structural member, and the production cost increases, so that the polymer electrolyte fuel cell It becomes difficult to apply as a cell structure member. Therefore, the Ni content is 7.0 to 50.0%.
  • Cu 0.01 to 3.0% Since Cu is an austenite forming element, it is contained in an amount of 0.01% or more. However, if the Cu content exceeds 3.0%, the corrosion resistance may decrease. Therefore, the Cu content is set to 0.01 to 3.0%. Cu needs to be dissolved in the matrix. When dispersed as a metal-based precipitate, it becomes a starting point for corrosion in the fuel cell, resulting in a decrease in cell performance.
  • the Cu content is preferably 0.02% or more, and preferably less than 0.8%.
  • N 0.001 to 0.4% Since N is the cheapest austenite forming element, 0.001% or more is contained. However, when the N content exceeds 0.4%, the manufacturability is remarkably lowered and the thin plate workability is also remarkably lowered. Therefore, the N content is set to 0.001 to 0.4%.
  • the N content is preferably 0.002% or more, and preferably 0.1% or less.
  • V 0.3% or less V is inevitably contained in a Cr source added as a melting raw material used in mass production. V does not need to be added intentionally, but excessive reduction of the content causes an increase in cost. Therefore, the V content is 0.3% or less.
  • B 0.5 to 1.0%
  • M 2 B precipitated and dispersed in the steel material and exposed to the surface improves the surface conductivity and also serves as a precipitation nucleus for controlling the precipitation of M 23 C 6 .
  • the B content is less than 0.5%, the amount of M 2 B deposited is small and it is difficult to ensure the surface conductivity.
  • the content exceeds 1.0%, the ductility is remarkably lowered and it becomes difficult to produce a steel material. Therefore, the B content is 0.5 to 1.0%.
  • the B content is preferably 0.5% or more, and preferably 0.85% or less.
  • Al 0.001 to 0.2%
  • B which is essential, is an element having a strong binding force with oxygen in the molten steel, it is necessary to sufficiently reduce the oxygen concentration in the molten steel by Al deoxidation. Therefore, the Al content is set to 0.001 to 0.2%.
  • Sn Less than 0.02%
  • the cathode electrode side cell constituent member is used in an oxidizing atmosphere even during normal operation. Therefore, when a stainless steel material containing Sn is applied to the cathode electrode side cell constituent member, tin oxide having poor conductivity becomes thicker on the surface of the parent phase and the like.
  • Sn content shall be less than 0.02%.
  • the Sn content is preferably 0.015% or less. The Sn content may be at the impurity level.
  • the stainless steel material contained in the cathode electrode side cell constituting member 12 may have a precipitate containing M 2 B finely dispersed and precipitated in the steel material, if necessary. Further, this precipitate may further include a composite precipitate in which M 23 C 6 is precipitated on its surface with M 2 B as a precipitation nucleus. And when it has said precipitate, the one part protrudes from the surface of steel materials. M 2 B or M 23 C 6 protruding from the surface of the steel material functions as a conductive path and has an effect of reducing contact resistance.
  • Corrosion-resistant plating layer on the surface of the stainless steel material may have a corrosion-resistant plating layer having conductivity on the surface of the steel material, if necessary. By having a corrosion-resistant plating layer on the steel material surface, the contact resistance is greatly reduced. Examples of the corrosion resistant plating layer include a gold plating layer.
  • Manufacturing Method There are no particular restrictions on the manufacturing conditions of the ferritic stainless steel material included in the anode electrode side cell constituent member 11 and the stainless steel material included in the cathode electrode side cell constituent member 12. For example, it can manufacture by performing a hot rolling process, an annealing process, a cold rolling process, and a final annealing process in order with respect to steel which has said chemical composition.
  • the crystal grain size and control the precipitation of M 23 C 6 by utilizing the phase transformation of ⁇ phase and ⁇ phase at high temperature.
  • the crystal grain size and the intragranular precipitates can be controlled by controlling so as to have an ⁇ - ⁇ two-phase structure during rolling.
  • pickling (etching) treatment is most excellent in mass productivity.
  • an etching process in which an aqueous ferric chloride solution is sprayed is preferable.
  • the spray etching process using a high-concentration ferric chloride aqueous solution is widely used as an etching process for stainless steel, and the processing liquid after use can be reused.
  • the spray etching process using a high concentration ferric chloride aqueous solution is often performed as a local thinning process or a through-drilling process after the masking process. Used in the cutting process for
  • the spray etching process will be described in more detail.
  • the ferric chloride solution used is a very concentrated acid solution.
  • the ferric chloride solution concentration is quantified by the Baume degree, which is an indication measured with a Baume hydrometer.
  • the etching treatment for surface roughening may be performed by dipping in a stationary state or flowing ferric chloride solution, but it is desirable to roughen the surface by spray etching. This is because it is possible to control the etching depth, the etching rate, and the degree of surface roughening efficiently and accurately in production on an industrial scale.
  • the spray etching process can be controlled by the pressure discharged from the nozzle, the amount of liquid, the liquid flow velocity (linear flow velocity) on the surface of the etching material, the spray hit angle, and the liquid temperature.
  • the ferric chloride solution to be applied has a low copper ion concentration and Ni concentration in the liquid, but there is no problem in purchasing and using industrial products that are generally distributed in Japan.
  • the concentration of the ferric chloride solution used is 40 to 51 ° in terms of Baume degree. If the concentration is less than 40 °, the tendency to perforate corrosion becomes strong and is not suitable for surface roughening. On the other hand, if it exceeds 51 °, the etching rate is remarkably slow, and the deterioration rate of the liquid is also fast. It is not suitable as a roughening solution for the surface of the core material of a polymer electrolyte fuel cell separator that needs to be mass-produced.
  • the ferric chloride solution concentration is more preferably 42 to 46 ° in terms of Baume degree.
  • the temperature of the ferric chloride solution is preferably 20 to 60 ° C. When the temperature decreases, the etching rate decreases, and when the temperature increases, the etching rate increases. When the temperature is high, the liquid deterioration proceeds in a short time.
  • the degree of liquid deterioration can be continuously quantitatively evaluated by measuring the natural potential of a platinum plate immersed in a ferric chloride solution.
  • a simple method of recovering the liquid capacity when the liquid deteriorates there is a method of adding a new liquid or exchanging the whole liquid with a new liquid. Further, chlorine gas may be blown.
  • Sn dissolved in the matrix phase is preliminarily metal tin or oxidized on the surface of the matrix phase and the surface of the precipitate. It is desirable to concentrate it as tin.
  • spray washing using a sulfuric acid aqueous solution or immersion treatment may be further performed. Since the ferric chloride solution used in the previous step has a very low pH and a high flow rate, metallic tin and tin oxide are in a state where surface concentration is difficult. However, for example, spray cleaning or immersion treatment using a sulfuric acid aqueous solution of less than 20% is slower than the liquid flow rate (linear flow rate) on the etching material surface in spray cleaning with ferric chloride solution, or close to standing. When carried out in the state, surface enrichment of tin oxide is promoted.
  • the concentration of sulfuric acid solution to be applied varies depending on the corrosion resistance of the material to be treated. When soaked, the concentration is adjusted so as to be corrosive enough to start to generate bubbles on the surface. Concentration conditions that generate violent bubbles with corrosion are undesirable. This is because the above-mentioned metal or its oxide may interfere with concentration on the surface, and there is a possibility that the function of lowering the contact resistance immediately after application of the polymer electrolyte fuel cell may be reduced.
  • the material (steel material) used for the anode electrode side separator and the cathode electrode side separator is any one of steel materials 1 to 6 shown in Table 1.
  • Steel materials 1 to 6 are all bright annealing specification (BA specification) cold rolled stainless steel coil materials, with a plate thickness of 0.126 mm and a coil width of 240 mm.
  • the molding process was performed using a dedicated progressive die and a general-purpose 250-ton press.
  • FIG. 3 is a photograph showing the shape of the separator used in the example.
  • the separator channel is a serpentine type with three parallel channels, the channel width is 1 mm, and the depth is 0.7 mm.
  • a separator having the same shape was inverted and arranged on the cathode side and the anode side to constitute a polymer electrolyte fuel cell.
  • the effective reaction area as a cell is 100 cm 2 .
  • MEA a commercially available integrated MEA in which a catalyst layer was provided on both sides of a polymer membrane and carbon paper was applied as a diffusion layer was used. Platinum catalyst supported amount of anode side 0.05 mg / cm 2, a cathode-side 0.4 mg / cm 2.
  • M 2 B was dispersed in the steel.
  • M 23 C 6 was further deposited on the surface of the dispersed M 2 B.
  • ferrous chloride aqueous solution spray etching treatment for adjusting the surface roughness was performed on the steel materials 1 to 6 described above.
  • the amount of welding is 8 ⁇ m on each side, and the plate thickness after spray etching is 0.11 mm.
  • the steel material 6 was provided with conductive corrosion-resistant plating having an average weight per unit area of 20 nm by gold plating in a cyan bath.
  • M 2 B precipitated in the steel in steel materials 1, 3 and 5 was precipitated on the surface in steel materials 2 and 4 with M 2 B as a precipitation nucleus. A part of each of the composite precipitates, M 23 C 6 , protruded from the steel surface.
  • the surface roughness was adjusted by the concentration of the ferric chloride solution, the liquid temperature, the spray speed (linear flow velocity on the plate surface), and the spray treatment time. Specifically, spray treatment was performed using a ferric chloride aqueous solution having a Baume degree of 43 degrees and a temperature of 35 ° C. The spray discharge pressure was 2 kg / cm 2 and the spray time was about 40 seconds.
  • an EPDM gasket and a PEN film having tackiness were used. After integration as a cell, it was confirmed after assembly as a fuel cell that there was no leakage of hydrogen gas and cooling water.
  • the fuel cell evaluation operation equipment used in the examples was manufactured by combining commercially available equipment.
  • a gas retention tank having an internal volume of 50 ml was provided which was directly connected to the anode electrode side gas inlet and the anode electrode side gas outlet of the fuel cell stack to keep the gas temperature from decreasing. This corresponds to a capacity 10 times the set hydrogen gas flow rate at startup.
  • a three-way solenoid valve is provided in the piping in front of the entry side tank so that the gas can be instantaneously switched from air to hydrogen and from hydrogen to air in the anode side supply gas to the fuel cell. This makes it possible to reproduce the H + deficiency state that occurs on the anode electrode side when the fuel cell is activated.
  • the air in the gas retention tank installed at the anode electrode side gas inlet is replaced with hydrogen gas over a period of 10 to 20 seconds.
  • the anode electrode flows into the anode electrode side in the cell.
  • the hydrogen concentration in the side gas also decreases because it flows in diluted with the air in the residence tank installed at the anode electrode side gas inlet, and gradually increases with the progress of the hydrogen gas replacement in the residence tank. It becomes.
  • the anode electrode side gas after the reaction in the battery is further diluted by the air in the gas retention tank installed on the outlet side.
  • the gas retention tank is connected to the anode gas electrode side gas inlet and the anode gas electrode side gas outlet for about 20 seconds. It is possible to reproduce the transient in-cell conditions at the time of starting the battery.
  • the fuel cell is assembled in a single-cell configuration.
  • nitrogen gas replacement is performed on both the anode and cathode sides, including the inside of the piping, and then air is introduced into the anode and hydrogen is introduced into the cathode. Introduced and started the battery reaction.
  • the gas flow rate was kept constant such that hydrogen was 300 cc / min and air was constant at 600 cc / min and the current density was constant at 0.1 A / cm 2 .
  • Performance evaluation was performed by measuring the degree of cell voltage decrease and cell resistance increase, and the amount of MEA film metal contamination after the end of operation.
  • the amount of MEA film metal contamination indicates the degree of corrosion of the separator. Specifically, the amounts of Fe, Cr, Ni, Sn and Pt were quantified. However, since the amounts of Cr, Ni, Sn, and Pt were small, the amount of Fe was used as an indicator of the degree of corrosion of the separator.
  • the electric cell resistance value during operation as a battery was measured with a resistance meter (MODEL 3565) manufactured by Tsuruga Electric Co., Ltd.
  • the displayed cell resistance value is an AC impedance value at a frequency of 1 kHz according to the four-terminal method.
  • the increase in the cell resistance value indicates an increase in the polymer film resistance value, and is an index for confirming the dry and wet state of the MEA during battery operation and the decrease in MEA film performance.
  • the cell resistance value starts to increase greatly exceeding 2 m ⁇ , it indicates that the deterioration of MEA is progressing.
  • Table 2 summarizes the types of steel materials used for the anode-side and cathode-side separators of each cell and the measurement results described above.
  • the cell resistance value after the operation is less than 1 m ⁇ , and it can be judged that the deterioration of the polymer film itself is hardly a problem.
  • the present embodiment does not introduce air to the anode electrode side while hydrogen is filled on the anode electrode side, and the set current value during operation is constant, and the battery is not paused or started.
  • the example environment it can be seen that there is no difference in performance degradation due to the separator material. That is, the effect of the polymer electrolyte fuel cell according to the present invention could not be confirmed under the constant current operation environment in which air does not enter the anode side.
  • an increase in the amount of Fe ions accompanying the operation could not be confirmed.
  • Example 2 mode operation (repeated operation under a certain condition) was performed. At the first start-up, both the anode electrode side and the cathode electrode side were replaced with nitrogen gas, including the inside of the pipe, and then hydrogen was introduced into the anode electrode side and air was introduced into the cathode electrode side to start battery operation. During the entire evaluation time, air is not introduced to the anode side during operation.
  • the cell voltage (constant) is 1.0 V from the outside while the anode side remains in the hydrogen atmosphere.
  • Specific operation modes are: (s1) cell voltage 1.0 V (constant) holding operation for 20 seconds, (s2) holding operation for 5 minutes at a current density of 0.1 A / cm 2 , (s3) current density of 0.2 A / cm 3 min holding operation at cm 2 , (s4) 3 min holding operation at a current density of 0.3 A / cm 2 , (s5) 5 min holding operation at a current density of 0.4 A / cm 2 , and (s6) open circuit It is a repetition of 6 steps of holding for 20 seconds in a state (a state where no load is applied to the battery by an external power source).
  • the gas flow rate was 300 cc / min of hydrogen and 600 cc / min of air per current density of 0.1 A / cm 2 .
  • the set current density is 0.4 A / cm 2
  • the set flow rates are 1200 cc / min for hydrogen and 2400 cc / min for air.
  • the optimum flow rate is determined to compensate for the most stable operation.
  • the cell voltage of 1.0 V is a cell voltage increase value confirmed as the main stack when hydrogen gas is introduced in a state where the anode electrode is filled with air.
  • the overpassive region it is an electric potential range called a overpassive region, and is a potential environment in which the passive film formed on the stainless steel surface changes into a stable overpassive film in the overpassive region. It can be regarded as an environment in which metal elution is likely to proceed due to surface coating changes.
  • the evaluation operation time is 1000 hours, and the number of mode repetitions is 3600 cycles.
  • Table 3 summarizes the types of steel materials used for the anode and cathode electrode separators of each cell and the measurement results.
  • the MEA performance drop is caused under this mode operation condition. Can be confirmed.
  • the cell voltage after 1000 hours is almost the same as after 100 hours, and no significant cell voltage drop has occurred. It can be determined that the cell performance is stable.
  • the Fe ion concentration in the MEA after the operation was also less than 100 ppb, and it was judged that the Fe ion concentration was not reached so as to promote performance degradation.
  • Example 3 mode operation (repeated operation under a certain condition) was performed in a pattern similar to Example 2. However, at the first start-up, after performing nitrogen gas substitution on both the anode electrode side and the cathode electrode side including the inside of the pipe, the battery operation was started after introducing air into both the anode electrode side and the cathode electrode side.
  • the three-way solenoid valve is switched during the open circuit maintenance mode so that air is supplied to the anode-side hydrogen atmosphere.
  • the gas was replaced by hydrogen to air (flow rate 2400 cc / min, held for 20 seconds), and then the three-way solenoid valve was switched to introduce hydrogen gas to the anode electrode side at a flow rate of 300 cc / min.
  • the 1.0 V (constant) load by the electronic load device from the outside is an operation for improving the reproducibility of the condition setting.
  • Specific operation modes are: (s1) cell voltage 1.0 V (constant) holding operation (20 seconds), (s2) holding operation at a current density of 0.1 A / cm 2 for 5 minutes, (s3) current density 0. 3 min holding operation at 2 A / cm 2 , (s4) 3 min holding operation at a current density of 0.3 A / cm 2 , (s5) 5 min holding operation at a current density of 0.4 A / cm 2 , and (s6 ) Repetition of holding for 20 seconds in an open circuit state (a state where no load is applied to the battery by an external power source).
  • the evaluation operation time is 1000 hours, and the number of mode repetitions is 3600 cycles.
  • Table 4 summarizes the types of steel materials used for the anode-side and cathode-side separators of each cell and the measurement results.
  • the performance difference is not clear at 100 hours after the start of operation, but is clear at the cell voltage and cell resistance value after 1000 hours. If the cell voltage is 0.75 V or higher, it is judged that the performance is good. Test No. of the present invention example using a ferritic stainless steel material containing Sn only for the separator on the anode side. In 75-78 and 81-84, the performance degradation is small, and it can be judged that it is preferable as a combination of separator materials.
  • test No. of a comparative example using Sn-containing ferritic stainless steel material for both the anode electrode side and cathode electrode side separators In 73, 74, 79 and 80, the increase in cell resistance is clear. It is judged that the elution (corrosion) of the stainless steel substrate and the generation of tin oxide that inevitably proceed on the cathode electrode side, which is an oxidizing atmosphere, are remarkable, and the surface contact resistance is increased. Even in the disassembly after the evaluation, tin oxide adhesion was significant on the cathode electrode separator surface including the MEA surface (diffusion layer).
  • test No. of a comparative example using a stainless steel material not containing Sn for the separator on the anode electrode side From 85 to 101, a clear cell voltage drop was confirmed.
  • test No. of the comparative example. 103-108 test no. Compared to 102, the cell voltage drop is larger. In the gold plating process, it is judged that there is an influence of the matrix corrosion from the plating defects that inevitably remain. It can be judged that galvanic corrosion from plating defects has progressed.
  • the superiority or inferiority can also be confirmed from the MEA analysis results after the evaluation.
  • the battery performance deterioration due to the polymer film deterioration has not yet become apparent, and it has been determined that the cell voltage decrease due to the catalyst performance deterioration due to the carbon corrosion on the cathode side is the main.
  • Fuel Cell Stack 2 Solid Polymer Electrolyte Membrane 3 Fuel Electrode Membrane (Anode) 4 Oxidant electrode membrane (cathode) 5a, 5b Separator 6a, 6b Channel 10 Solid polymer fuel cell 11 Anode electrode side cell component 12 Cathode electrode side cell component 13 Anode electrode side fuel gas channel 14 Cathode electrode side gas channel 15, 16 Diffusion Layers 17 and 18 Catalyst layer 19 Polymer membrane 20 MEA

Abstract

L'invention concerne une cellule 10 pour une pile à combustible à polymère solide qui est équipée d'un élément constitutif de cellule côté anode 11 et d'un élément constitutif de cellule côté cathode 12 : l'élément constitutif de cellule côté anode 11 comprenant un matériau en acier inoxydable ferritique, et l'élément constitutif de cellule côté cathode 12 comprenant un matériau en acier inoxydable; le matériau d'acier inoxydable ferritique qui constitue l'élément constitutif de cellule côté anode 11 ayant une composition chimique dans laquelle la teneur en Sn est de 0,02 à 2,50 % en masse, et ayant un précipité en son sein qui contient un borure M2B précipité et finement dispersé; une partie du précipité se projetant à partir de la surface du matériau en acier inoxydable ferritique; et le matériau en acier inoxydable constituant l'élément constitutif de cellule côté cathode 12 ayant une composition chimique dans laquelle la teneur en Sn est inférieure à 0,02 % en masse.
PCT/JP2017/011554 2016-03-29 2017-03-22 Cellule pour pile à combustible à polymère solide, et empilement de piles à combustible à polymère solide WO2017170066A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017535113A JP6278157B1 (ja) 2016-03-29 2017-03-22 固体高分子形燃料電池用セルおよび固体高分子形燃料電池スタック

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016065851 2016-03-29
JP2016-065851 2016-03-29

Publications (1)

Publication Number Publication Date
WO2017170066A1 true WO2017170066A1 (fr) 2017-10-05

Family

ID=59964462

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/011554 WO2017170066A1 (fr) 2016-03-29 2017-03-22 Cellule pour pile à combustible à polymère solide, et empilement de piles à combustible à polymère solide

Country Status (2)

Country Link
JP (1) JP6278157B1 (fr)
WO (1) WO2017170066A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008021647A (ja) * 2006-06-27 2008-01-31 Gm Global Technology Operations Inc Ｐｅｍ型燃料電池用の低コスト双極板被覆
WO2009157557A1 (fr) * 2008-06-26 2009-12-30 住友金属工業株式会社 Matériau en acier inoxydable pour séparateur de pile à combustible à polymère solide et pile à combustible à polymère solide l’utilisant
JP2015128064A (ja) * 2013-12-12 2015-07-09 ジーエム・グローバル・テクノロジー・オペレーションズ・エルエルシー 非理想的な動作による燃料電池電極腐食を緩和するための層設計
WO2016017692A1 (fr) * 2014-07-29 2016-02-04 新日鐵住金ステンレス株式会社 Matériau d'acier inoxydable ferritique pour pile à combustible, et son procédé de production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008021647A (ja) * 2006-06-27 2008-01-31 Gm Global Technology Operations Inc Ｐｅｍ型燃料電池用の低コスト双極板被覆
WO2009157557A1 (fr) * 2008-06-26 2009-12-30 住友金属工業株式会社 Matériau en acier inoxydable pour séparateur de pile à combustible à polymère solide et pile à combustible à polymère solide l’utilisant
JP2015128064A (ja) * 2013-12-12 2015-07-09 ジーエム・グローバル・テクノロジー・オペレーションズ・エルエルシー 非理想的な動作による燃料電池電極腐食を緩和するための層設計
WO2016017692A1 (fr) * 2014-07-29 2016-02-04 新日鐵住金ステンレス株式会社 Matériau d'acier inoxydable ferritique pour pile à combustible, et son procédé de production

Also Published As

Publication number Publication date
JPWO2017170066A1 (ja) 2018-04-05
JP6278157B1 (ja) 2018-02-14

Similar Documents

Publication Publication Date Title
JP3365385B2 (ja) 固体高分子型燃料電池のセパレータ用ステンレス鋼材の製造方法
JP4078966B2 (ja) 固体高分子型燃料電池のセパレータ用ステンレス鋼および固体高分子型燃料電池
JP5591302B2 (ja) 燃料電池用ステンレス鋼分離板及びその製造方法
JP5971446B1 (ja) フェライト系ステンレス鋼材と、これを用いる固体高分子形燃料電池用セパレータおよび固体高分子形燃料電池
JP5979331B1 (ja) フェライト系ステンレス鋼材と、これを用いる固体高分子形燃料電池用セパレータおよび固体高分子形燃料電池
JP5218612B2 (ja) 燃料電池セパレータ用ステンレス鋼
JP2018534416A (ja) 燃料電池分離板用ステンレス鋼およびその製造方法
WO2018043285A1 (fr) Acier inoxydable ferritique, séparateur, cellule et pile à combustible
JP2006233282A (ja) 電気伝導性および耐食性に優れた通電電気部品用ステンレス鋼及びその製造方法
JP2013093299A (ja) 燃料電池セパレータ用ステンレス鋼の製造方法、燃料電池セパレータ用ステンレス鋼、燃料電池セパレータ、ならびに燃料電池
JP5152193B2 (ja) 固体高分子型燃料電池セパレータ用ステンレス鋼材および固体高分子型燃料電池
JP2012177157A (ja) 固体高分子形燃料電池セパレータ用ステンレス鋼およびその製造方法
JP6057033B1 (ja) フェライト系ステンレス鋼材、セパレータ、固体高分子形燃料電池、および、セパレータの製造方法
WO2013018322A1 (fr) Acier inoxydable pour séparateur de pile à combustible
JP2007027032A (ja) 固体高分子型燃料電池用ステンレス鋼製セパレータ及び燃料電池
KR20190096434A (ko) 연료 전지의 세퍼레이터용 강판의 기재 스테인리스 강판 및 그 제조 방법
US10622643B2 (en) Carbon separator for solid polymer fuel cell, solid polymer fuel cell, and solid polymer fuel cell stack
JP6278158B1 (ja) 固体高分子形燃料電池用セルおよび固体高分子形燃料電池スタック
JP6278157B1 (ja) 固体高分子形燃料電池用セルおよび固体高分子形燃料電池スタック
JP3397168B2 (ja) 固体高分子型燃料電池セパレータ用フェライト系ステンレス鋼および固体高分子型燃料電池
JP6278172B1 (ja) フェライト系ステンレス鋼材、セパレーター、セルおよび燃料電池
KR20210134831A (ko) 스테인리스 강재, 구성 부재, 셀 및 연료 전지 스택
JP2019502816A (ja) 親水性および接触抵抗が向上した高分子燃料電池の分離板用ステンレス鋼およびその製造方法
JP2006233281A (ja) 電気伝導性および耐食性に優れた通電電気部品用ステンレス鋼及びその製造方法
JP2006302731A (ja) 固体高分子型燃料電池用ステンレス鋼製セパレータ及び固体高分子型燃料電池

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2017535113

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17774607

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17774607

Country of ref document: EP

Kind code of ref document: A1