WO2006082734A1 - 燃料電池用セパレータおよびその製造方法 - Google Patents
燃料電池用セパレータおよびその製造方法 Download PDFInfo
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- WO2006082734A1 WO2006082734A1 PCT/JP2006/301048 JP2006301048W WO2006082734A1 WO 2006082734 A1 WO2006082734 A1 WO 2006082734A1 JP 2006301048 W JP2006301048 W JP 2006301048W WO 2006082734 A1 WO2006082734 A1 WO 2006082734A1
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- fuel cell
- intermediate layer
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- 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
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- 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
-
- 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
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
-
- 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
-
- 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
-
- 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
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
-
- 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
-
- 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
- H01M8/021—Alloys based on iron
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12729—Group IIA metal-base component
Definitions
- the present invention relates to a fuel cell separator, and more particularly to a separator suitable for a polymer electrolyte fuel cell used for a power source for automobiles, a power source for portable devices, a distributed power source and the like.
- a fuel cell is a power generator that takes out electric energy by causing an electrochemical reaction between hydrogen, which is a fuel, and oxygen.
- fuel cells can be solid oxide fuel cells (SOFC), molten carbonate fuel cells (MCFC), phosphoric acid fuel cells (PAFC), polymer electrolyte fuel cells ( PEFC) and direct methanol fuel cell (DMF C).
- SOFC solid oxide fuel cells
- MCFC molten carbonate fuel cells
- PAFC phosphoric acid fuel cells
- PEFC polymer electrolyte fuel cells
- DMF C direct methanol fuel cell
- the polymer electrolyte fuel cell (PEFC) and direct methanol fuel cell (DMFC) are highly efficient in power generation even at an operating temperature of about 70-90 ° C, which is lower than that of other types of fuel cells. In particular, it is expected to be applied to automobiles and mobile devices!
- PEFC polymer electrolyte fuel cell
- Fig. 3 (a) is a perspective view schematically showing the structure of a cell (battery) portion, which is the smallest structural unit of a polymer electrolyte fuel cell (PEFC), and Fig. 3 (b) It is a schematic diagram showing the principle of PEFC.
- PEFC polymer electrolyte fuel cell
- the cell of the fuel cell has an ion exchange membrane (solid polymer membrane) 11 at the center, and a fuel electrode (hydrogen electrode, anode side) 12 on both sides thereof. And two electrodes, an air electrode (or an oxygen electrode, a power sword side) 13 are arranged.
- the ion exchange membrane 11 is a membrane for moving protons (H +) from the fuel electrode 12 to the air electrode 13.
- the ion-exchange membrane 11 and the electrode catalyst layers 14a and 14b, which often have electrode catalyst layers 14a and 14b on both sides, are collectively referred to as a membrane 'electrode assembly (MEA) 20 Called.
- MEA membrane 'electrode assembly
- Fuel electrode 12 and air electrode 13 Separators 16a and 16b are arranged on the outer side of gaskets 15a and 15b, respectively. Hydrogen (anode side) moves between MEA20 and separator 16a, and between MEA20 and separator 16b. Oxygen (force sword side) moves (see Fig. 3 (b)). On the surfaces of the separators 16a and 16b, grooves through which hydrogen or oxygen reactive gas passes are formed.
- H becomes H + by the reaction of the following formula (1), passes through the ion exchange membrane 11 and is
- oxygen (O) is supplied through a groove on the surface of the separator 16b and is uniformly spread to the electrode catalyst layer 14b by the air electrode 13.
- the separator is required to efficiently supply a reaction gas such as oxygen or hydrogen to the electrode catalyst layer 14a.
- a cell (unit cell) having the above-described configuration is used in the form of a stack in which a plurality of layers are stacked according to the amount of power.
- the separator acts as a partition plate between the unit cells, the fuel electrode gas (hydrogen) and the air electrode gas (oxygen) are not mixed between the cells. , And so on to be asked! /
- separators are required to have low gas permeability, excellent conductivity, low contact resistance, and excellent corrosion resistance.
- a need for corrosion resistance and conductivity recently, increasingly are strong summer, as a measure of corrosion resistance, "the ⁇ does not occur even 1000-hour immersion the separator P H of about 1 sulfuric acid solution" Is listed.
- Patent Documents 1 and 2 a method has been proposed in which a metal material that is easy to process and low in processing cost is used as a separator material instead of a carbon material.
- Patent Document 1 discloses a separator in which a conductive ceramic film such as tantalum carbide is provided on the surface of a metal substrate. According to Patent Document 1, a separator having excellent conductivity in the operating environment of a fuel cell (temperature range from room temperature to around 150 ° C, water vapor atmosphere) can be obtained.
- Patent Document 2 discloses a separator in which the Cr concentration on the surface of the metal substrate is increased to 13% or more or 20% or more in a polymer electrolyte fuel cell in which a conductive film is formed on the surface of the metal substrate. Has been. According to Patent Document 2, a separator having excellent corrosion resistance in a battery operating environment (about 80 ° C. under saturated water vapor) can be obtained.
- a separator in which a metal film such as a platinum group element or gold is plated on stainless steel has also been proposed. Specifically, after completely removing the passive film formed on the surface of stainless steel (the oxide film in which Cr contained in the steel is combined with oxygen in the atmosphere), a metal such as Ni is included as necessary. After forming the undercoat layer, the metal film is attached to make a separator. This is because it is very difficult to form a noble metal film directly on the surface of stainless steel because the passive film is poor in adhesion with a metal film having a large contact resistance.
- Patent Document 1 Japanese Patent Laid-Open No. 11-162479
- Patent Document 2 JP 2002-313355 A
- Patent Document 3 Japanese Patent Laid-Open No. 10-68071
- the high corrosion resistance and high conductivity characteristics required for the force separator described by taking the solid polymer fuel cell separator as an example are not limited to the solid polymer fuel cell, This is also commonly required for other fuel cells.
- the present invention has been made in view of the above circumstances, and its purpose is to provide corrosion resistance and conductivity.
- An object of the present invention is to provide a fuel cell separator that is extremely excellent in performance.
- the fuel cell separator of the present invention includes a base material formed of steel containing 10.5 mass% or more of Cr, a metal film formed on the surface of the base material, and the base material and the metal film. And an intermediate layer containing oxygen formed between the metal layer and the metal film is made of at least one metal element selected from the group consisting of Ta, Nb, and ⁇ , Fe and Cr contained in the steel and at least one metal element selected from the group consisting of Ta, Nb, and TU constituting the metal film.
- the profile in the depth direction showing the content of oxygen contained in the intermediate layer has a maximum value.
- the profile in the depth direction showing the content of at least one metal element selected from the group force consisting of Ta, Nb, and Ti contained in the intermediate layer is the metal
- the steel further contains 5 to 16% by mass of Ni, and the intermediate layer constitutes the metal film with Fe, Cr, and Ni contained in the steel.
- Ta, Nb, and TU group power including at least one metal element selected.
- the profile in the depth direction indicating the content of at least one metal element selected from the group force consisting of Ta, Nb, and TU contained in the intermediate layer is from the metal film side.
- the profile in the depth direction which decreases toward the base material side and indicates the content of Fe, Cr, and Ni contained in the intermediate layer, is directed from the metal film side to the base material side.
- the intermediate layer has a thickness of 0.000020 ⁇ m or more.
- the metal film has a thickness of 0.30 ⁇ m or more.
- the steel is stainless steel.
- the steel is an austenitic stainless steel or an austenite-ferritic stainless steel.
- it further has a noble metal film covering at least a part of the surface of the metal film, and the noble metal film has a Pt or Au force.
- the fuel cell is a polymer electrolyte fuel cell.
- a fuel cell of the present invention includes the fuel cell separator described above.
- a method for producing a fuel cell separator according to the present invention includes a base material, a metal film formed on the surface of the base material, and oxygen formed between the base material and the metal film.
- the method includes a step of forming an intermediate layer containing the contained elements and an element constituting the metal film, and a step of depositing the metal film on the intermediate layer by a vapor deposition method.
- the ion bombardment treatment removes a portion having a depth of 0.0001 m or more from the surface of the oxide layer and leaves a portion having a thickness of 0.0015 m or more.
- the step of forming the intermediate layer alternately performs a step of depositing a metal film and a step of performing ion bombardment.
- the vapor deposition method is a sputtering method or an ion plating method.
- an intermediate layer containing oxygen is formed between the base material formed from steel containing 10.5 mass% or more of Cr and the metal film, Because an intermediate layer containing Fe and Cr (and Ni) and at least one kind of metal element that forms the group force of Ta, Nb, and TU constituting the metal film is formed, Excellent corrosion resistance and electrical conductivity.
- FIG. 1 is a cross-sectional view schematically showing the configuration of a fuel cell separator according to the present invention.
- FIG. 2 is a diagram for explaining the element distribution in the depth direction of the intermediate layer in the intermediate layer forming process in the separator manufacturing method according to the embodiment of the present invention, and (a) is a process for forming the intermediate layer (B) is a graph showing the element distribution in the depth direction of the FeZCrZNi oxide layer remaining in step 2; and (b) is a graph showing the element distribution in the depth direction of the FeZCrZNi oxide layer obtained in step 1. (C) is a graph showing the element distribution in the depth direction of the intermediate layer obtained in step 3.
- FIG. 3 (a) is a perspective view schematically showing the structure of a cell (battery) part, which is the smallest structural unit of a polymer electrolyte fuel cell (PEFC), and (b) is the principle of PEFC. It is the schematic diagram which shows
- the present inventor has made various studies in order to improve the corrosion resistance of a conventional separator in which a metal film is plated on stainless steel. Specifically, we used Ta, Nb, and Ti, which have excellent corrosion resistance, as the elements that make up the metal film.
- the separator obtained by this method does not satisfy the corrosion resistance standard. It became clear by the examination result.
- As a standard for the corrosion resistance for example, generation of wrinkles is not observed even when the separator is immersed in a strongly acidic solution for 1000 hours or more. This is because the corrosive liquid penetrates into the inside through pinholes formed in the metal film and exposes a part of the surface of the stainless steel after long-term use.
- the local battery is formed by the potential difference between the stainless steel and the elements composing the metal film, and it is considered that the dissimilar metal contact corrosion (galvanic corrosion) proceeds.
- the present inventor has found that the above metal is formed on the passive film based on the idea that "the use of the passive film is indispensable for obtaining the desired corrosion resistance".
- the method of depositing the membrane was further examined.
- “A part of the passive film (FeZCrZNi oxide layer) formed on the surface of the stainless steel was removed by ion bombardment (thus part of the passive film remains without being removed).
- the present invention has been achieved.
- this intermediate layer contains elements that constitute the metal film in addition to the elements contained in the passive film, and is extremely excellent in adhesion to the metal film.
- a separator having such an intermediate layer exhibits both excellent corrosion resistance due to a passive film and excellent corrosion resistance and conductivity due to a metal element, and also has excellent adhesion between the intermediate layer and the metal film. . As a result, even when the separator is immersed in a sulfuric acid solution having a pH of about 1 for 1000 hours or more, no generation of wrinkles is observed, and extremely excellent corrosion resistance can be maintained for a long time.
- the present invention has the technical idea of "utilizing excellent corrosion resistance due to the passive film formed on the surface of stainless steel”. It is different from the conventional method of “removing completely”.
- Patent Document 1 discloses a separator in which a conductive ceramic film of tantalum carbide is deposited on the surface of stainless steel, but the intermediate layer characterizing the present invention is not formed. Absent.
- the above-described ceramic film is formed by an ion plating method. “After removing a part of the FeZCrZNi oxide layer by ion bombardment and leaving a part, etching of the underlayer is performed. Alternating with metal film deposition This is because a method unique to the present invention of “to perform” is not disclosed. Further, even if Patent Document 1 is scrutinized, the technical idea of the present invention that “a part of the passive film is left to enhance the corrosion resistance” is not disclosed.
- FIG. 1 is a cross-sectional view schematically showing the configuration of the fuel cell separator according to the present embodiment.
- the fuel cell separator according to the present embodiment includes a base material 1 formed of steel containing 10.5 mass% or more of Cr, and a metal film 3 formed on the surface of the base material 1.
- An intermediate layer 2 formed between the base material 1 and the metal film 3 is provided.
- the substrate 1 is made of steel containing 10.5 mass% or more of Cr (chromium).
- Cr chromium
- the fuel cell separator of the present invention utilizes the excellent corrosion resistance due to the passive film formed on the surface of stainless steel, such as Cr oxides.
- Steel containing at least Cr is used as a corrosion resistant element.
- the Cr content is increased, the corrosion resistance is improved. If the amount is excessively added, the caking property is lowered. Therefore, it is generally preferable to suppress the content to 27% by mass or less. Preferably it is 13 mass% or more and 25 mass% or less
- Ni nickel
- Ni nickel
- Cu copper
- Cu copper
- Mo mobdenum
- C carbon
- the steel used in the present embodiment preferably contains the above elements, with the balance being Fe (iron) and inevitable impurities.
- examples of the stainless steel not containing Ni include ferritic stainless steel and martensitic stainless steel.
- Hue Light stainless steel about 0.12 mass C 0/0 or less, a steel of about 16-18 wt 0/0 containing Cr, typically, such as SUS430 (JIS standard) 18Cr- low carbon Stainless steel can be mentioned.
- 18Cr—lMo stainless steel such as SUS434 (JIS standard) and 18Cr—2Mo—TiZNbZZr—extremely low (C, N) stainless steel such as SUS444 (JIS standard) are also listed.
- Martensitic stainless steel is a steel containing approximately from 0.1 to 0.4 mass 0/0, Cr about 12 to 18 wt% of C, and typically, SUS410 CFIS standard) such 13Cr- low Examples include carbon stainless steel and 18Cr—high carbon stainless steel such as SUS440 (JIS standard).
- Ni-containing stainless steel examples include austenitic stainless steel and duplex (austenite ferrite) stainless steel.
- Austenitic stainless steel is a steel containing about 0.15 mass% or less of C, about 16 to 20 mass% of Cr, and about 18 mass% or more of Ni.
- 18Cr-8Ni— Examples include low carbon stainless steel and 18Cr-12Ni—2.5Mo stainless steel such as SU S316.
- duplex stainless steel examples include 25Cr-4.5Ni-2Mo stainless steel such as SUS329J1.
- Ni-containing martensitic stainless steel examples include 16Cr-2Ni stainless steel such as SUS431.
- austenitic stainless steel containing Ni in the steel and austenitic stainless steel preferred by duplex stainless steel are more preferable.
- the intermediate layer 2 contains oxygen, and further contains a metal element mainly contained in the steel and a metal element constituting the metal film 3.
- the metal elements mainly contained in the steel are Fe and Cr when the steel contains Cr and substantially no Ni, but when the steel contains Cr and Ni, Fe, Cr, and Ni.
- the metal element constituting the metal film 3 is at least one metal element selected from the group force consisting of Ta, Nb, and Ti. Of these, Fe and Cr (and Ni) are considered to mainly produce Fe oxide and Cr oxide (and Ni oxide), respectively, by binding to oxygen. It is done.
- the oxide-containing layer corresponds to a passive film formed on the surface of stainless steel.
- the layer containing the above-described oxide may be collectively referred to as “FeZCrZNi oxide layer”.
- the separator of the present invention performs ion bombardment before depositing the metal film 3 to remove a part of the Fe / CrZNi oxide layer and leave a part thereof.
- the intermediate layer 2 is used for alternately depositing the metal film and removing the underlayer by changing the source voltage within a predetermined range. At least one metal element selected from the group consisting of Ta, Nb, and TU constituting the metal film is deposited. Ta, Nb, and TU contained in the intermediate layer At least one metal element selected exists in the form of an oxide.
- the profiles in the depth direction showing the contents of the elements contained in the intermediate layer 2 are as follows. First, the profile in the depth direction indicating the oxygen content has a maximum value, and decreases toward the metal film 3 side and the base material 1 side, respectively. On the other hand, the profile in the depth direction indicating the content of Fe and Cr (and also Ni) increases from the metal film 3 side to the substrate 1 side, and is a group consisting of Ta, Nb, and TU. The profile in the depth direction showing the content of at least one kind of metal element for which force is also selected decreases from the metal film 3 side toward the substrate 1 side.
- a base material on which SUS 304 steel was also formed was prepared and heated in the atmosphere at 800 ° C for 12 minutes.
- a FeZCrZNi oxide layer having a thickness of 0.084 / zm was formed on the surface of the substrate (step 1).
- a substrate Sani ⁇ is formed above was placed in the arc type ion plating apparatus, it was evacuated until reaching a vacuum of 2 X 10- 3 Torr. Then, while introducing Ar gas and applying Ta ion as a target and applying a bias voltage of 300 V, the portion of the FeZCrZNi oxide layer with a surface force depth of 0.070 m was removed. As a result, an FeZCrZNi oxide layer having a thickness of 0.015 m remained on the surface of the substrate (step 2).
- the substrate was heated to 200 ° C, Ta was deposited by setting the bias voltage to -80V, and a part of the underlayer was removed by setting the bias voltage to 180V. This Since the deposition of the Ta film and the removal of the underlayer are performed alternately, an intermediate layer with a thickness of 0.06 ⁇ m (0.028 ⁇ m thick) was obtained (Step 3). .
- the elemental distribution in the depth direction of each layer obtained by the above steps 1 to 3 was measured by photoelectron spectroscopy analysis (E; sCA). Specifically, using the ESCA-850 manufactured by Shimadzu Corporation, the above layers were measured by irradiating MgKa (8. OkV, 30 mA), which is the characteristic X-ray of Mg (ion gun Ar, 2. OkV). , 20mA) o
- the horizontal axis represents the thickness (A) in the depth direction of the layers obtained in steps 1 to 3, and the vertical axis represents Fe, Cr, Ni, and 0 constituting the layers.
- (Oxygen) content (% by mass).
- Fig. 2 (c) the profile in the depth direction showing the O content and the Fe content from the point on the surface side where the depth profile showing the O content intersects the horizontal axis are shown.
- the distance to the point where the profile in the depth direction intersects was defined as the “intermediate layer thickness”.
- the method for producing a separator according to the present invention includes a step of depositing a Ta film to a predetermined thickness by a vapor deposition method after step 3, and the intermediate layer after this step is applied. Since the elemental distribution in the depth direction is almost the same as the elemental distribution in the intermediate layer obtained in step 3, the Ta film deposition step is omitted here.
- FIG. 2 (a) is a graph showing the element distribution in the depth direction of the FeZCrZNi oxide layer obtained in step 1. By heating, a Cr oxide is mainly formed near the surface of the oxide layer.
- FIG. 2 (b) is a graph showing the element distribution in the depth direction of the FeZCrZNi oxide layer left after step 2.
- FIG. 2 (c) is a graph showing the element distribution in the depth direction of the intermediate layer obtained in step 3.
- the profile in the depth direction indicating the oxygen content has a maximum value and decreases toward the metal film 3 side and the substrate 1 side, respectively.
- the profile in the depth direction indicating the contents of Fe, Cr, and Ni and the profile in the depth direction indicating the content of Ta show a contradictory tendency, and the former is from the metal film 3 side. In the latter case, the force on the substrate 1 side increases and the force on the metal film 3 side also decreases on the substrate 1 side.
- an intermediate layer containing the element contained in the oxide layer and Ta is formed.
- Such an intermediate layer is excellent in corrosion resistance, and also has good adhesion to the Ta film deposited thereafter, so that the fuel cell separator including the intermediate layer is extremely excellent in corrosion resistance.
- the intermediate layer 2 having such a configuration preferably has a thickness of 0.000020 m or more. If the thickness of the intermediate layer 2 is less than 0.0010 m, sufficient corrosion resistance cannot be obtained. More preferably, it is 0.010 / z m or more, more preferably 0.015 / z m or more, and still more preferably 0.020 / z m or more. The greater the thickness of the intermediate layer 2, the more the corrosion resistance is improved. If the thickness is too large, it takes a long time to form the intermediate layer, which is not practical. Therefore, the upper limit of the thickness of the intermediate layer can be determined in consideration of productivity rather than the viewpoint of corrosion resistance, and for example, it preferably has a thickness of 0.1 ⁇ m or less.
- the metal film 3 has a thickness of 0.30 ⁇ m or more! /.
- a more preferable thickness of the metal film 3 is 0.40 m or more, and a more preferable thickness is 0.50 m or more.
- metal If the thickness of the film 3 is less than 0, the desired corrosion resistance cannot be obtained. The thicker the metal film 3, the better the corrosion resistance. However, if the metal film 3 is too thick, it takes a long time to form the metal film 3, which is not practical. Therefore, the upper limit of the thickness of the metal film 3 can be determined in consideration of productivity, not from the viewpoint of corrosion resistance, and is preferably set to 1.5 m, for example. In order to obtain excellent corrosion resistance when used as a separator, it is preferable that at least the portion in contact with the electrolyte is covered with the metal film 3.
- the metal film 3 having excellent adhesion to the intermediate layer 2 can be obtained.
- At least a part of the surface of the metal film 3 is preferably covered with a noble metal film of Pt (platinum) or Au (gold) (hereinafter sometimes simply referred to as "noble metal film”).
- a noble metal film of Pt (platinum) or Au (gold) (hereinafter sometimes simply referred to as "noble metal film”).
- Pt or Au is excellent in corrosion resistance and conductivity, the corrosion resistance and conductivity of the separator are further improved by covering a part of the metal film 3 with a noble metal film composed of these noble metal elemental forces.
- These noble metal elements are contained in the noble metal film in the form of metal elements, not in the form of acids or the like. Since Pt is an expensive metal, it is most preferable in consideration of cost.
- U is the noble metal.
- the noble metal film preferably has a thickness of 0.03 ⁇ m or more. If the thickness of the noble metal film is less than 0.03 / z m, desired corrosion resistance cannot be obtained. More preferably, it is 0.05 / z m or more. The greater the thickness of the noble metal film, the better the corrosion resistance. However, if it is too thick, it takes a long time to form the noble metal film, which is not practical. Therefore, the upper limit of the thickness of the noble metal film can be determined in consideration of productivity, not the viewpoint of corrosion resistance, and preferably has a thickness of 1.00 m or less, for example. In order to obtain excellent corrosion resistance when used as a separator, it is preferable that at least a portion in contact with the electrolyte is covered with a noble metal film.
- the production method of the present invention is formed from steel containing 10.5 mass% or more of Cr (further, Ni may be contained. Hereinafter, it may be referred to as "CrZNi-containing steel").
- a step of preparing a base material in which an FeZCrZNi oxide layer is formed on at least a part of the surface of the base material, and a part of the FeZCrZNi oxide layer are removed by ion bombardment to remove the above-mentioned acid solution.
- Part of the cocoon layer And a step of forming an intermediate layer including an element included in the oxide layer and an element constituting the metal film, and a step of depositing the metal film on the intermediate layer by a vapor deposition method.
- the "evaporation method” broadly includes a method of depositing a material to be deposited (noble metal in the present invention) in a gas state, and includes physical vapor deposition and CVD (chemical vapor deposition). Including the law. In the present invention, it is more preferable to use a physical vapor deposition method as the vapor deposition method. In particular, since the film formed by ion plating and sputtering is generally dense, the metal film is more preferably formed by ion plating or sputtering!
- examples of the ion plating method include an activated reaction vapor deposition method, a high frequency excitation method, a hollow cathode discharge method, an arc evaporation method (an arc ion plating method), and the like.
- a DC sputtering apparatus an RF sputtering apparatus, a magnetron sputtering apparatus, an ion beam sputtering apparatus, or the like can be used.
- a base material in which an FeZCr, Ni oxide layer is formed on at least a part of the surface of the base material formed from CrZNi-containing steel is prepared.
- a substrate may be a commercially available product, or a substrate formed from CrZNi-containing steel may be heated to form an FeZCrZNi oxide layer.
- ion bombardment is performed on the FeZCrZNi oxide layer.
- ion bombardment is performed so that a part of the Fe ZCrZNi oxide layer is removed but a part remains. As a result, the excellent corrosion resistance of the FeZCrZNi oxide layer can be effectively exhibited.
- Ion bombardment is a type of film removal (etching) performed to obtain a thin film with good adhesion, and metal ions (in this embodiment, Ta, Nb, and at least one kind of metal ion (which also selects the group force of TU) are collided.
- metal ions in this embodiment, Ta, Nb, and at least one kind of metal ion (which also selects the group force of TU) are collided.
- the ion bombardment process is performed as follows. First, about 1 to 3 X 10- 3 Torr (about 133 ⁇ 399Pa) Ar gas was introduced into the vacuum vessel was adjusted to a range of, the deposited material (in this case, a base material FeZCrZNi oxide layer is formed) When a negative bias voltage (approx. 150 to -180 or higher) is applied to the noble metal element, the target (force sword) force of the noble metal element (Pt or Au) is also evaporated to generate a noble metal cation. . The ions collide with the material to be deposited by the negative noise voltage applied to the material to be deposited, and the surface of the material to be deposited is sputtered.
- a noise voltage applied to the substrate is selected so that a portion having a depth of about 0.0001 m or more is removed from the surface of the FeZCrZNi oxide layer and a portion having a thickness of 0.0001 m or more remains. It is preferable to process while paying attention to the above.
- the bias voltage is thought to have a significant effect on the removal rate (etching rate) of the FeZCrZNi oxide layer and the surface properties after ion bombardment, and as a result, the Fe / Cr / Ni oxide layer and the metal film It is also the force that changes the adhesion. If the noise voltage is less than about 1150 V, the acid layer cannot be removed efficiently.
- the upper limit of the bias voltage is not particularly limited, and can be set appropriately depending on the device to be used.
- Patent Document 3 The outline of the ion bombardment process is described in detail in, for example, Patent Document 3, and the details of the apparatus and the like can be referred to Patent Document 3.
- Patent Document 3 the entire disclosure of Patent Document 3 is incorporated herein by reference.
- an intermediate layer containing an element included in the FeZCrZNi oxide layer and an element constituting the metal film (Ta, Nb, and at least one metal element whose TU group force is also selected) is formed.
- the intermediate layer uses the same apparatus as that used for the above-described ion bombardment process to deposit the metal film and perform the ion bombard process to form the base layer. It is formed by alternately performing the etching process. Specifically, it is preferable to form the intermediate layer by changing the bias voltage as follows. First
- the bias voltage in the range of about -75 to 85V for about 10 to 20 seconds, and collect Ta, Nb, and TU. After depositing at least one selected metal element, the bias voltage is about 150V. Apply to the larger range for about 5 to 15 seconds, and apply at least one kind of underlayer (selected from the group consisting of Ta, Nb, and TU deposited as described above) It is preferable to remove a part of the metal element). By repeating this series of operations, preferably a plurality of times (about 3 to 10 times), a desired intermediate layer thickness can be obtained. When the above operation is repeated a plurality of times, the bias voltage when etching a part of the underlying layer may be changed every time within the above range. For example, the bias voltage may be successively reduced to about 170 V during the first etching, 160 V during the second etching, and 150 V during the third etching.
- the vapor deposition material is heated to a temperature of about 150 to 250 ° C in advance.
- the detailed film forming conditions vary depending on the type of vapor deposition method used.
- a method of depositing a metal film using the arc ion plating method is as follows.
- the bias voltage applied to the vapor deposition material is smaller than that during the ion bombardment process, so that a metal film is deposited on the surface of the vapor deposition material.
- the bias voltage to be applied is preferably 60 to 70 V, and this allows the metal film to be deposited efficiently. If the noise voltage is less than –60V, the metal film cannot be deposited efficiently. On the other hand, when the bias voltage exceeds 70V, the surface roughness becomes remarkably large, resulting in surface defects such as pinholes.
- At least a part of the surface of the metal film 3 is precious metal for the purpose of further improving the corrosion resistance and conductivity. You may coat
- a negative bias voltage is applied to the material to be deposited (here, the above metal film), and arc discharge is performed to evaporate the cathode material.
- the bias voltage applied to the vapor deposition material be smaller than that during the ion bombardment process, so that a noble metal film is deposited on the surface of the vapor deposition material.
- the bias voltage to be applied is preferably 60 V to 170 V, so that the metal film can be deposited efficiently. If the bias voltage is less than –60V, the metal film cannot be deposited efficiently. On the other hand, when the noise voltage exceeds 170V, the surface roughness becomes remarkably large, resulting in surface defects such as pinholes.
- the fuel cell separator of the present invention thus produced is particularly preferably used for a polymer electrolyte fuel cell.
- the surface resistance of each material was measured using “196 System DMM” manufactured by KEITHLEY.
- excellent conductivity! / Means that the surface resistance of the material measured by the above method satisfies the range of 0.01 to 0.03 ⁇ .
- the surface force of the base material on which the stainless steel force was also formed FeZCrZNi oxide layer and the intermediate layer containing Ta and Ta (thickness 0.015 111), and the Ding & membrane (thickness 0.7) Material coated with ⁇ m) was produced.
- a base material (length 80 mm x width 80 mm x thickness 1. Omm) formed of SUS 304 steel was prepared and heated in the atmosphere at 800 ° C for 4 minutes. As a result, a 0.028 ⁇ m thick Fe, Cr, Ni oxide layer was formed on the surface of the substrate.
- the base material on which the oxide layer was formed was placed in an arc ion plating apparatus and evacuated.
- Ar gas was introduced at a gas pressure of 2 X 10- 3 Torr (approximately 266 X 10- 3 Pa), using Ta as a target, by performing the ion bombard treatment by applying a bias voltage of 300 V, FeZCrZNi A portion having a depth of 0.018 m was removed from the surface of the oxide layer.
- an FeZCrZNi oxide layer having a thickness of 0.0010 m remained on the surface of the substrate.
- the substrate was heated to 200 ° C, the bias voltage was set to –80V, applied for 15 seconds to deposit Ta, and the bias voltage was set to –200V and applied for 5 seconds. Part of the formation was removed. Thereby, Ta film deposition and underlayer removal are performed alternately. This series of operations was performed a total of 6 times. As a result, an intermediate layer on which Ta having a thickness of 0.06 / z m was deposited was obtained (intermediate layer thickness 0.015 / ⁇ ⁇ ).
- an FeZCrZNi oxide layer having a thickness of 0.028 ⁇ m was formed on the surface of a base material on which SUS304 steel strength was also formed by the same method as in Experimental Example 1.
- the surface of the base material formed from stainless steel is changed to the elements that make up the FeZCrZNi oxide layer and the metal elements that make up the metal film (Ta and Ti).
- a material coated with an intermediate layer (thickness: 0.021 ⁇ m) containing Ta and Ti and a composite film of Ta (Ti: 0.5 m) was prepared.
- Example 4 In this experimental example, by modifying the method of Experimental Example 1, the surface of the base material made of stainless steel has an intermediate layer (thickness: 0.005 m) containing the elements constituting the FeZCrZNi oxide layer and Ta. ), Ta film (thickness 0.5 m), and Au film (thickness 0.1 m).
- a bias voltage of 67 V was applied, and a 0.5 ⁇ m thick Ta film was deposited.
- Stainless steel was treated in the same manner as in Experimental Example 1 except that the deposition time was shortened to 0.36 hours, 0.12 hours, and a Ta film with a thickness of 0.28 m was deposited.
- Surface force of the base material formed from an element covered with an FeZCrZNi oxide layer and an intermediate layer containing Ta (thickness 0.015 1! 1) and 13 ⁇ 4 film (thickness 0.28 m) The material was made.
- Table 1 summarizes the results of the corrosion resistance and conductivity of each material.
- the surface force of the base material formed with stainless steel force
- All of the materials in Experimental Example 4 in which the film was coated with a noble metal film with an appropriate thickness were separators. Satisfies the standards of corrosion resistance required for The materials of Experimental Examples 1 and 2 and 4 are extremely excellent in corrosion resistance with no occurrence of wrinkles even when the immersion time is increased to 1500 hours. These materials are all excellent in conductivity.
- Comparative Examples 1 to 3 in which the FeZCrZNi oxide layer was completely removed, Comparative Example 4 in which the thickness of the intermediate layer was less than the preferred range, and the thickness range of the metal film were preferred.
- Comparative Examples 5 none of the corrosion resistance standards required for the separator was satisfied, and generation of spots and peeling of the metal film were observed. Moreover, the conductivity of any of the comparative examples was lowered.
- the force with which the metal film was deposited using the arc ion plating process is not limited to this, and it has been confirmed by experiments that the same result can be obtained by other vapor deposition methods. .
- the fuel cell separator of the present invention is excellent in corrosion resistance and electrical conductivity, and therefore can be widely used for power supplies for automobiles, power supplies for portable devices, distributed power supplies, and the like.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/883,502 US8338058B2 (en) | 2005-02-01 | 2006-01-24 | Separator for fuel cell having intermediate layer and method for manufacturing same |
EP06712264A EP1848054B1 (en) | 2005-02-01 | 2006-01-24 | Separator for fuel cell and method for manufacturing same |
DE602006011578T DE602006011578D1 (de) | 2005-02-01 | 2006-01-24 | Trennelement für eine brennstoffzelle und verfahren zu seiner herstellung |
JP2007501537A JP5226302B2 (ja) | 2005-02-01 | 2006-01-24 | 燃料電池用セパレータの製造方法 |
CA2596409A CA2596409C (en) | 2005-02-01 | 2006-01-24 | Separator for fuel cell and method for manufacturing same |
KR1020077006642A KR101195180B1 (ko) | 2005-02-01 | 2006-01-24 | 연료 전지용 세퍼레이터 및 그 제조 방법 |
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JP2005-024800 | 2005-02-01 | ||
JP2005024800 | 2005-02-01 |
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WO2006082734A1 true WO2006082734A1 (ja) | 2006-08-10 |
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PCT/JP2006/301048 WO2006082734A1 (ja) | 2005-02-01 | 2006-01-24 | 燃料電池用セパレータおよびその製造方法 |
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US (1) | US8338058B2 (ja) |
EP (1) | EP1848054B1 (ja) |
JP (1) | JP5226302B2 (ja) |
KR (1) | KR101195180B1 (ja) |
CN (1) | CN100550489C (ja) |
CA (1) | CA2596409C (ja) |
DE (1) | DE602006011578D1 (ja) |
WO (1) | WO2006082734A1 (ja) |
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CA2596409A1 (en) | 2006-08-10 |
EP1848054B1 (en) | 2010-01-06 |
US20080138691A1 (en) | 2008-06-12 |
JPWO2006082734A1 (ja) | 2008-06-26 |
KR101195180B1 (ko) | 2012-10-29 |
KR20070099517A (ko) | 2007-10-09 |
CN101032047A (zh) | 2007-09-05 |
CA2596409C (en) | 2013-04-23 |
US8338058B2 (en) | 2012-12-25 |
EP1848054A1 (en) | 2007-10-24 |
EP1848054A4 (en) | 2008-03-12 |
CN100550489C (zh) | 2009-10-14 |
DE602006011578D1 (de) | 2010-02-25 |
JP5226302B2 (ja) | 2013-07-03 |
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