WO2009118991A1 - Séparateur de pile à combustible - Google Patents

Séparateur de pile à combustible Download PDF

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Publication number
WO2009118991A1
WO2009118991A1 PCT/JP2009/000616 JP2009000616W WO2009118991A1 WO 2009118991 A1 WO2009118991 A1 WO 2009118991A1 JP 2009000616 W JP2009000616 W JP 2009000616W WO 2009118991 A1 WO2009118991 A1 WO 2009118991A1
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WO
WIPO (PCT)
Prior art keywords
metal
fuel cell
metal substrate
carbon
carbon layer
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Application number
PCT/JP2009/000616
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English (en)
Inventor
Tomokatsu Himeno
Atsushi Miyazawa
Motoki Yaginuma
Keisuke Yamamoto
Yasue Tanaka
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Nissan Motor Co., Ltd.
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Application filed by Nissan Motor Co., Ltd. filed Critical Nissan Motor Co., Ltd.
Publication of WO2009118991A1 publication Critical patent/WO2009118991A1/fr

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204Non-porous and characterised by the material
    • H01M8/0223Composites
    • H01M8/0228Composites in the form of layered or coated products
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204Non-porous and characterised by the material
    • H01M8/0206Metals or alloys
    • H01M8/0208Alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204Non-porous and characterised by the material
    • H01M8/0213Gas-impermeable carbon-containing materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204Non-porous and characterised by the material
    • H01M8/0223Composites
    • H01M8/0226Composites in the form of mixtures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M2008/1095Fuel cells with polymeric electrolytes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Definitions

  • the present invention relates to a fuel cell separator having a good resistance to corrosion while keeping high electrical conductivity.
  • a polymer electrolyte fuel cell is configured by stacking each cell (single cell) in layers.
  • the single cell includes a solid polymer electrolyte membrane, electrode catalyst layers provided on both sides of the polymer electrolyte membrane, and gas diffusion layers provided on further both sides of the electrode catalyst layers and dispersing supply gas.
  • the single cell includes separators on the outer sides of the gas diffusion layers.
  • each of fuel gas (such as hydrogen gas) and oxidant gas (such as air, oxygen) is supplied to a positive electrode and a negative electrode, respectively. Then, electricity is generated by bringing about the following electrochemical reactions in each of the positive electrode and the negative electrode.
  • fuel gas such as hydrogen gas
  • oxidant gas such as air, oxygen
  • the separator used under such a condition should have both good electrical conductivity and high corrosion resistance.
  • cut graphite and a carbon material such as a mixture of carbon and resin have been mainly used.
  • the separator produced by the carbon material has difficulty reducing the thickness because of inferiority in mechanical strength.
  • a fuel cell separator in which a film made of electrically conductive graphite is formed on a surface of a metal substrate, is disclosed (refer to Patent Citation 1). Also, a fuel cell separator, in which a certain separator substrate is coated with an electrical conductive hard carbon film having a good corrosion resistance, is disclosed (refer to Patent Citation 2). Further, a method for manufacturing a fuel cell separator in which a carbon film is formed on a surface of a separator substrate by dry film-forming method, while applying a negative high voltage to the separator substrate (refer to Patent Citation 3).
  • a defect such as cracks and pinholes may be caused in the carbon layer formed on the metal substrate because of load when stacking cells.
  • the above-mentioned defect may be caused at press-forming for forming a gas passage and the like.
  • the corrosion resistance of the carbon layer itself is maintained, whereas oxidation corrosion on the surface of the metal substrate is caused due to acid water penetration.
  • corrosion of the metal substrate caused a problem that a contact resistance of the separator was increased.
  • the carbon layer itself has the high corrosion resistance
  • metal such as stainless steel and aluminum used as a metal substrate is easily corroded. Therefore, the obtained separator shows a low contact resistance in the early stage, while an oxide film is gradually formed on the metal substrate. Thus, it results in the increase of the contact resistance.
  • An object of the present invention is to provide a fuel cell separator having high electrical conductivity, corrosion resistance and adhesion.
  • a fuel cell separator including: a metal substrate that has a gas passage through which a reactant gas flows; and a carbon layer that is formed on a surface of the metal substrate and contains a number of metal particles and electrical conductive carbon.
  • Fig. 1 is a schematic view showing a structure of a fuel cell including a separator according to an embodiment of the present invention.
  • Fig. 2 is a schematic view showing a cross section of the structure of the separator in Fig. 1.
  • Fig. 3 is a graph showing a relationship between a contact resistance of a carbon layer and I D /I G .
  • Fig. 4 is a schematic view showing a cross section of a structure of a separator according to another embodiment of the present invention.
  • Fig. 5 is a schematic view showing a constitution at a measurement of a contact resistance.
  • Fig. 6 is a graph showing a contact resistance value of a separator in Examples 1, 2 and Comparative Example 1 before immersion in acid water.
  • Fig. 1 is a schematic view showing a structure of a fuel cell including a separator according to an embodiment of the present invention.
  • Fig. 2 is a schematic view showing a cross section of the structure of the separator in Fig. 1.
  • FIG. 7 is a graph showing a contact resistance value of the separator in Examples 1, 2 and Comparative Example 1 after immersion in acid water.
  • Fig. 8 is a graph showing a contact resistance value of a separator in Examples 3 to 5 and Comparative Example 2 before immersion in acid water.
  • Fig. 9 is a graph showing a contact resistance value of the separator in Examples 3 to 5 and Comparative Example 2 after immersion in acid water.
  • FIG. 1 is a schematic view showing a basic structure of a polymer electrolyte fuel cell, which is one of the fuel cells provided with a separator of the embodiment of the present invention.
  • Catalyst layers 3 anode catalyst layer and cathode catalyst layer
  • gas diffusion layers 4 anode-side gas diffusion layer and cathode-side gas diffusion layer
  • MEA membrane electrode assembly
  • the MEA 10 is eventually held between a pair of separators 5 having electrical conductivity so as to compose a single cell of the polymer electrolyte fuel cell.
  • gas seals are interposed between the separators 5 and the electrolyte membrane 2, and between a fuel cell 1 and another fuel cell adjacent to the fuel cell 1.
  • the gas seals are omitted in Fig. 1.
  • reactant gas passages 5a and coolant passages 5b are formed by pressing 0.5 mm or less of a thin plate.
  • the separator 5 includes the gas passages 5a and manifolds through which the reactant gas (fuel gas and oxidant gas) flows, and the coolant passages 5b through which the coolant flows.
  • the separator 5 has a function to electrically connect each MEA 10 in series.
  • the separator 5 also has a function to maintain mechanical strength of stacks.
  • Fig. 2 is a schematic view showing a cross section of a surface structure of the separator 5 in Fig. 1.
  • the separator 5 includes a metal substrate 6 and a carbon layer 9 including metal particles 7 and an electrical conductive carbon 8.
  • the carbon layer 9 is formed on the metal substrate 6.
  • the electrical conductive carbon 8 and the metal particles 7 relatively oxidized easily in the carbon layer 9 together, the metal particles 7 are oxidized prior to a metal element composing the metal substrate 6.
  • the metal particles 7 and the electrical conductive carbon 8 are present in mixed condition in the carbon layer 9, internal stress of the carbon layer 9 itself is reduced.
  • high adhesion between the carbon layer 9 and the metal substrate 6 as a base can be obtained. Therefore, a resistance value of the fuel cell is lowered, and long-term stability can be ensured.
  • the following are details of each component of the separator 5.
  • the material composing the metal substrate 6 is preferably selected based on the relationship with the metal particles 7 discussed below. Specifically, the material of the metal substrate 6 is preferably composed of a metal element equivalent to the metal particles 7, or composed of a metal element resistant to oxidation compared to the metal particles 7 in view of oxidizing tendency. More preferably, the material is composed of at least one of the metal element equivalent to the metal particles 7 and the metal element more noble than the metal particles 7.
  • the material composing the metal substrate 6 aluminum (Al) or an aluminum alloy, stainless steel, and titanium or magnesium, and the like are included. Especially, stainless steel, aluminum or the aluminum alloy, and titanium are preferable. Further, aluminum or the aluminum alloy, and stainless steel are more preferable.
  • aluminum purity is 97 % or more, more preferably 99 % or more.
  • an element in the aluminum alloy other than aluminum is composed of at least one of the metal element equivalent to the metal particles 7 and the metal element more noble than the metal particles 7 as described above.
  • the element other than aluminum copper, manganese, silicon, magnesium, zinc, nickel, and the like are included.
  • pure aluminum series As the aforementioned aluminum alloy, pure aluminum series, aluminum-manganese series, aluminum-magnesium series, and the like are included.
  • pure aluminum series A1050P standardized according to Japanese Industrial Standards is included.
  • aluminum-manganese series A3003P and A3004P are included.
  • aluminum-magnesium series A5052P and A5083P are included.
  • a content ratio of iron (Fe) in stainless steel is 60 to 84 % by mass, more preferably 65 to 72 % by mass.
  • a content ratio of chromium (Cr) in the stainless steel is 16 to 20 % by mass, more preferably 16 to 18 % by mass.
  • austenite series As the aforementioned stainless steel, austenite series, martensite series, ferrite series, austenite-ferrite series, precipitation hardening series, and the like are included.
  • austenite series SUS201, SUS202, SUS301, SUS302, SUS303, SUS304, SUS305, SUS316 and SUS317 standardized according to Japanese Industrial Standards are included.
  • austenite-ferrite series SUS329J1 is included.
  • martensite series SUS403 and SUS420 are included.
  • ferrite series SUS405, SUS430 and SUS430LX are included.
  • precipitation hardening series SUS630 is included. Especially, it is more preferable to use stainless steel of austenite series of SUS304, SUS316, and the like.
  • a thickness of the metal substrate 6 is 50 micrometers to 500 micrometers, more preferably 80 micrometers to 200 micrometers in view of workability and the mechanical strength.
  • the element composing the metal particles 7 is preferably selected based on the relationship with the material (metal element) composing the metal substrate 6 as discussed above.
  • the metal particles 7 are preferably composed of the metal element equivalent to the metal substrate 6, or composed of the metal element easier to be oxidized than the metal substrate 6 in view of oxidizing tendency. More preferably, the metal particles 7 are composed of at least one of the metal element equivalent to the metal substrate 6 and the element less noble than the metal substrate 6. In such a case, the metal particles 7 are oxidized prior to the material composing the metal substrate 6. Therefore, it is possible to prevent the oxide film from being formed on the surface 6a of the metal substrate 6 so as to suppress the increase of the contact resistance of the separator.
  • the metal particles 7 and the element composing the metal substrate 6 aluminum and/or titanium for the metal particles 7 and stainless steel for the metal substrate 6 are preferable in view of ionization tendency.
  • the metal particles 7 are composed of aluminum and/or magnesium and the metal substrate 6 is composed of aluminum or the aluminum alloy. In such a combination, it is possible to suppress the increase of the contact resistance more remarkably.
  • the above-mentioned stainless steel can be used for the material of the metal substrate 6 in the separator.
  • aluminum (Al) and/or titanium (Ti) can be used as a material less noble than stainless steel and forming a stable oxide.
  • aluminum (Al) or aluminum alloy is used for the material of the metal substrate 6 as described above, aluminum (Al) and/or magnesium (Mg), which is equivalent to or less noble than the metal substrate 6 to form the stable oxide, can be used for the metal particles 7.
  • Al (Al) and/or magnesium (Mg) can be used for the metal particles 7.
  • the metal particles 7 are oxidized prior to the surface 6a of the metal substrate 6.
  • aluminum (Al) or the aluminum alloy is convenient because of lightness in weight and flexibility compared to other metals, and has good electrical conductivity, it is a great advantage of using aluminum (Al) or the aluminum alloy for the metal substrate 6. Therefore, it is possible to suppress the increase of the contact resistance, keeping the low contact resistance in the early stage so as to improve the corrosion resistance.
  • the metal particles 7 are preferably dispersed into the carbon layer 9 as less noble metal, that is, lower standard electrode potential metal, than the metal substrate 6.
  • the metal particles 7 are oxidized in the carbon layer 9 in advance of the oxide film formed on the surface of the metal substrate 6.
  • the metal particles 7 are composed of metal more noble than the metal substrate 6 because noble metal promotes oxidation of metal composing the metal substrate 6.
  • the metal particles 7 have an effect of lowering the internal stress of the carbon layer 9. Therefore, it is possible to improve adhesion between the carbon layer 9 and the metal substrate 6 as a base and suppress the contact resistance of the separator remarkably.
  • the internal stress of the carbon layer 9 itself is lowered when the metal particles 7 and the electrical conductive carbon 8 are present in the carbon layer 9 in a mixed state. Therefore, it is possible to obtain high adhesion between the metal substrate 6 as a base and the carbon layer 9, and also ensure the reduction of the resistance value of the fuel cell and long-term stability.
  • an average particle diameter of the meal particles 7 is smaller than a thickness of the carbon layer 9 as described below. Specifically, it is 0.2 nm to 20 nm, more preferably 0.5 nm to 10 nm, further preferably 0.5 nm to 5 nm.
  • the average particle diameter is 0.2 nm or more, sacrificial oxidation of the metal particles 7 is easily caused and the generation of the oxide film on the surface of the metal substrate 6 is suppressed more efficiently so as to improve the durability of the fuel cell. While, when the average particle diameter is 20 nm or less, the possibility that the oxide is formed not only outside but also inside of the metal particles 7 increases when the metal particles 7 are oxidized.
  • the "particle diameter” in the description of the present invention represents the maximum length of lines connecting two certain points on the circumference of the particle.
  • the value calculated as an average value of the particle diameters observed in several views to several tens of views is adopted, by use of an observation method such as a scanning electron microscope (SEM) and transmission electron microscope (TEM).
  • a content ratio of the metal particles 7 in the carbon layer 9 is 1 to 50 % by mass, more preferably 5 to 20 % by mass.
  • the content ratio of the metal particles 7 is 1 % by mass or more, the sacrificial oxidation of the metal particles 7 is caused prior to oxidation at the interface between the carbon layer 9 and the metal substrate 6. Therefore, it is possible to efficiently suppress the increase of the contact resistance of the separator.
  • the content ratio of the metal particles 7 is 50 % by mass or less, it is possible to form the oxide of the metal particles 7 in the carbon layer 9 without disturbing electrical conductivity of the carbon layer 9 itself.
  • the carbon material usable for the electrical conductive carbon 8 is not particularly limited as long as the contact resistance of the separator is not increased.
  • an intensity ratio (R value) of the carbon layer 9 measured by Raman spectroscopy is within a predetermined range, it is possible to suppress the increase of the above-mentioned contact resistance remarkably.
  • the carbon material used as the electrical conductive carbon 8 is preferably selected so that the carbon layer 9 has the intensity ratio within the predetermined range.
  • Raman spectroscopy is to analyze a structure of a sample by analyzing Raman spectrum.
  • peaks usually appear in the vicinity of 1350 cm -1 and 1584 cm -1 .
  • High crystallinity graphite has a single peak in the vicinity of 1584 cm -1 , which is usually described as G-band. While, as the crystallinity is lowered, in the other words, as the defect of the crystal structure is increased and the structure of graphite is disordered, a peak in the vicinity of 1350 cm -1 appears, which is usually described as D-band. Precisely, the peak of diamond is 1333 cm -1 , which is distinct from D-band.
  • the intensity ratio R (I D /I G ) of D-band and G-band represents a size of a graphite cluster of the carbon material, a disordered level of the graphite structure (defect of the crystal structure), and an sp 2 bond ratio. That is, the ratio can be regarded as an index of the contact resistance of the separator, and used as a film parameter controlling electrical conductivity of the carbon layer 9.
  • the R value is calculated by measuring Raman spectrum of the carbon material by use of Micro-Raman spectroscopy. Specifically, the value is obtained by calculating the relative intensity ratio, that is, a peak area ratio (I D /I G ), between the peak intensity (I D ) of 1300 to 1400 cm -1 described as D-band and the peak intensity (I G ) of 1500 to 1600 cm -1 described as G-band. Each I D and I G may be described as the D-band peak intensity and the G-band peak intensity, respectively.
  • the value obtained by the following Raman spectrum measurement can be adopted as the peak area.
  • separators including carbon layers with various R values were prepared.
  • solid graphite is used as a raw material of the electrical conductive carbon 8.
  • V acceleration voltage
  • the R values were obtained by measuring Raman spectrum and calculating the peak area ratios of D-band and G-band. The measurements of Raman spectrum were performed five times at room temperature with 30 minutes exposure by use of Holo Lab 5000R made by Kaiser Optical System Inc. as a measuring device under the following conditions.
  • Excitation wavelength second-harmonic generation of a Nd:YAG laser, 532 nm Laser output: 3 mW Spot size: up to 1 micrometer
  • Detector Charge-coupled device detector
  • the contact resistance of the separators including carbon layers with the various R values (I D /I G ) was measured.
  • the layer of gas diffusion layer-separator-gas diffusion layer is held between a pair of copper electrode bars facing each other, the voltage value when applying certain current is read, and the penetration resistance is calculated.
  • the half of the measured value is considered as the contact resistance.
  • the resistance includes a bulk resistance of the gas diffusion layers and the metal substrate in the separator. However, the value of the bulk resistance is so low that it can be ignored in this case.
  • Fig. 3 shows the relationship between the R value and the contact resistance.
  • a vertical axis represents a ratio of the relative contact resistance value with respect to the lowest contact resistance value.
  • the intensity ratio (R value) of the carbon layer 9 is within the predetermined range, the sp 2 bond ratio of the carbon atoms in the carbon layer 9 increases, so that electrical conductivity in the carbon layer 9 is improved and the contact resistance is further lowered.
  • the above-mentioned predetermined range of the R value (I D /I G ) of the carbon layer 9 is 1.4 or more, more preferably 1.4 to 2.0.
  • the carbon layer 9 with high electrical conductivity can be obtained. While, when 2.0 or less, it is possible to suppress the decrease of the graphite content and also suppress the increase of the internal stress of the carbon layer 9 itself so as to further improve adhesion to the metal substrate 6 as a base.
  • the electrical conductive carbon 8 carbon black, graphite, fullerene, carbon nanotube, carbon nanofiber, carbon nanohorn, carbon fibril, and the like are included.
  • carbon black As the specific examples of carbon black, Ketjen black, acetylene black, channel black, lamp black, oil furnace black or thermal black, and the like are included.
  • a graphite treatment may be performed on carbon black.
  • graphite or carbon nanotube In view of the decrement of the contact resistance between the carbon layer 9 and the metal substrate 6 due to the structure and configuration of the electrical conductive carbon 8, graphite or carbon nanotube is preferable.
  • the carbon material may be used individually, or in combination with two kinds or more.
  • An average particle diameter when the material of the electrical conductive carbon 8 is in a particle state is not particularly limited, but preferably 1 nm to 100 nm, more preferably 5 nm to 20 nm in view of reducing the thickness of the carbon layer 9.
  • a diameter when the material of the electrical conductive carbon 8 is in a fibrous state such as carbon nanotube is not particularly limited, but preferably 0.4 nm to 100 nm, more preferably 1 nm to 20 nm.
  • a length when in the above-mentioned fibrous state is not particularly limited, but preferably 5 nm to 200 nm, more preferably 10 nm to 100 nm.
  • An aspect ratio when in a fibrous state is not particularly limited, but preferably 1 to 500, more preferably 2 to 100. When within the above-mentioned range, it is possible to optimally reduce the thickness of the carbon layer 9.
  • the content ratio of the electrical conductive carbon 8 in the carbon layer 9 is 50 to 99 % by mass, more preferably 80 to 98 % by mass, most preferably 80 to 95 % by mass.
  • the separator to be obtained has high electrical conductivity, corrosion resistance and adhesion altogether keeping a good balance each other.
  • the carbon layer 9 may be formed at least on one surface of the metal substrate 6. However, the carbon layers are preferably formed on both surfaces of the metal substrate 6 so as to further achieve the desired effect of the present invention.
  • a film thickness of the carbon layer 9 is 0.005 micrometers to 1 micrometer, more preferably 0.01 micrometers to 0.2 micrometers.
  • a film thickness of the carbon layer 9 is 0.005 micrometers to 1 micrometer, more preferably 0.01 micrometers to 0.2 micrometers.
  • the film thickness of the carbon layer 9 is 0.005 micrometers or more, a surface coverage ratio of the carbon layer 9 with respect to the metal substrate 6 is increased. Therefore, it is possible to form the carbon layer 9 as an even and continuous layer and suppress roughness on the surface of the metal substrate 6. In addition, it is possible to prevent the metal particles 7 in the carbon layer 9 from coming up to the outer surface of the carbon layer 9 and forming the oxide film on the surface of the metal substrate 6. Therefore, an electrical conduction path in the carbon layer 9 as a whole is increased, and it results in the further decrease of the contact resistance.
  • the film thickness of the carbon layer 9 is 1 micrometer or less, it is possible to prevent from developing the film stress (internal stress) of the carbon layer 9, and possible to improve adhesion to the metal substrate 6 remarkably. Moreover, it is capable of lowering the initial resistance itself in the thickness direction. It is also capable of preventing from causing cracks and the like without developing the internal stress of the carbon layer 9 caused by the reduced film thickness. Thus, it results in the promotion of the contact resistance reduction.
  • the carbon layer 9 is mainly formed of the metal particles 7 and the electrical conductive carbon 8 as described above, the carbon layer 9 may include other materials.
  • a water-repellent material such as polytetrafluoroethylene (PTFE) is included as the other material.
  • PTFE polytetrafluoroethylene
  • the carbon layer may be formed of only the electrical conductive carbon and the metal particles. That is, the carbon layer 9 can comprise, consist essentially of, or consist of the metal particles 7 and the electrical conductive carbon 8.
  • the carbon layer 9 is formed at least on a region contacting with the gas diffusion layer. More preferably, the carbon layer 9 is formed in the whole of the metal substrate 6 in order to maintain the high corrosion resistance.
  • a middle layer 11 composed of more than one selected from the group consisting of metal, metal nitride and metal carbide may be provided between the metal substrate 6 and the carbon layer 9. Due to the middle layer 11 provided between the metal substrate 6 and the carbon layer 9, adhesion of the carbon layer 9 can be improved. When the metal substrate 6 is directly coated with the carbon layer 9, optimum adhesion may not be obtained. Specifically, when the R value exceeds the upper limit of the above-mentioned preferable range, the metal substrate 6 as a base and the carbon layer 9 may not optimally adhere to each other. Therefore, by inserting the middle layer 11 in such a case, preferable adhesion between the metal substrate 6 and the carbon layer 9 can be ensured.
  • a material composing the middle layer 11 is not particularly limited as long as the material can provide for adhesion as mentioned above.
  • little ion elution metal such as chromium (Cr), tungsten (W), titanium (Ti), molybdenum (Mo), niobium (Nb) and hafnium (Hf), metal nitride and metal carbide of these, metal carbonitride of these are included.
  • little ion elution metal such as chromium (Cr) and titanium (Ti), and metal nitride and metal carbide of these are preferable.
  • the corrosion resistance of the separator 15 can be improved.
  • a thickness of the middle layer 11 is not particularly limited, but preferably 5 nm to 1000 nm, more preferably 10 nm to 200 nm. Then, it is possible to reduce the size of the laminated body of the fuel cell due to the reduced thickness of the separator 15.
  • the middle layer 11 is provided between the metal substrate 6 and the carbon layer 9. Therefore, the material (metal) composing the middle layer 11 is preferably oxidized prior to oxidation of the surface of the metal substrate 6 similar to the metal particles 7 in the carbon layer 9.
  • the material composing the middle layer 11 is preferably composed of at least one of the metal element equivalent to the metal substrate 6 and the metal element less noble than the metal substrate 6, and also composed of at least one of the metal element equivalent to the metal particles 7 and the metal element more noble than the metal particles 7.
  • the metal particles 7 are composed of aluminum (Al) and/or titanium (Ti)
  • the middle layer 11 is composed of chromium (Cr), titanium (Ti) and aluminum (Al)
  • the metal substrate 6 is composed of stainless steel.
  • the metal particles 7 are preferably composed of aluminum (Al) and/or magnesium (Mg)
  • the middle layer 11 is preferably composed of chromium (Cr), titanium (Ti), aluminum (Al) and magnesium (Mg)
  • the metal substrate 6 is preferably composed of aluminum (Al) or the aluminum alloy.
  • the middle layer 11 may be formed at least on one surface of the metal substrate 6. However, the middle layers are preferably formed on both surfaces of the metal substrate 6 so as to further achieve the desired effect of the present invention. Note that, when the middle layers 11 are provided on both surfaces of the metal substrate 6, the carbon layers 9 are also provided on each middle layer 11.
  • the carbon layer 9 can be formed on the metal substrate 6 targeting a target material formed of the element composing the metal particles 7 and a target material formed of the electrical conductive carbon 8.
  • a physical vapor deposition (PVD) method such as a sputtering method or an arc ion plating method, or an ion beam vapor deposition method such as a filtered cathodic vacuum arc (FCVA) method is preferably used.
  • a magnetron sputtering method, an unbalanced magnetron sputtering (UBMS) method, a dual magnetron sputtering method and the like are included. Due to such a method for forming the carbon layer 9, the carbon layer 9 with a small amount of hydrogen can be formed. Therefore, it is possible to increase the sp 2 bond ratio between the carbon atoms so as to obtain good electrical conductivity.
  • the metal substrate 6 preliminarily provided with the reactant gas passages 5a, the manifolds, and coolant passages 5b through which the coolant flows is prepared by a well-known method.
  • a treatment to degrease and wash on the surface of the metal substrate 6 is performed by use of a proper solvent.
  • ethanol, ether, acetone, isopropyl alcohol, trichloroethylene, caustic alkaline agent and the like can be used.
  • ultrasonic cleaning and the like are included. With regard to conditions of ultrasonic cleaning, the treatment time is approximately for 1 to 10 minutes, the frequency is approximately 30 to 50 kHz, and electricity is approximately 30 to 50 W.
  • the oxide film formed on the (both) surfaces of the metal substrate 6 is removed.
  • an acid treatment, a dissolution treatment with applying an electric potential, an ion bombard treatment or the like may be included.
  • the carbon layer 9 is subsequently formed by use of the sputtering method and the like as described above.
  • the target material composed of the electrical conductive carbon such as solid graphite, and the target material composed of the element composing the metal particles such as aluminum (Al) are used for targeting.
  • the carbon layer 9 having the desired thickness formed by dispersing the aluminum particles on both surfaces of the metal substrate 6 is formed while applying a negative bias voltage to the substrate at preferably 50 to 300 V.
  • the fuel cell separator of the present invention can be obtained.
  • One of the characteristics of the fuel cell separator of the present invention is the relationship between the carbon layer 9 and the metal substrate 6 of the components.
  • the carbon layer 9 is formed by depositing the electrical conductive carbon 8 and the metal particles 7 on the metal substrate 6 at the atomic level in vacuum.
  • the interface between the carbon layer 9 and the metal substrate 6 directly adhered each other and the periphery of the interface can exert adhesion due to an intermolecular force and the entry of a small amount of carbon atoms, and thus adhesion can be maintained for long periods.
  • the carbon layer 9 with extremely high hardness compared to the metal substrate 6 When the metal substrate 6 is directly coated with the carbon layer 9 with extremely high hardness compared to the metal substrate 6, the internal stress may be caused in the carbon layer 9, and exfoliation between the carbon layer 9 and the metal substrate 6 may be caused easily. Therefore, the carbon layer 9 with relatively similar hardness to the metal element composing the metal substrate 6 is preferably used for coating.
  • the treatments to degrease, wash, and remove the oxide film on the surface of the metal substrate 6 are performed similarly to the first example.
  • little ion elution metal such as chromium (Cr), tungsten (W), titanium (Ti), molybdenum (Mo), niobium (Nb) and hafnium (Hf), and metal nitride and metal carbide of these are targeted.
  • the middle layer 11 is formed on the surface of the metal substrate 6 using the targets by use of the magnetron sputtering method, the unbalanced magnetron sputtering (UBMS) method and the like.
  • the carbon layer 9 is formed on the middle layer 11 similarly to the first example.
  • the metal substrate that the reactant gas passages, the manifolds, coolant passages and the like are not preliminarily provided is prepared.
  • the treatments to degrease, wash, and remove the oxide film on the surface of the metal substrate 6 are performed similarly to the first example.
  • the carbon layer 9 is formed similarly to the first example, followed by forming the reactant gas passages, the manifolds, coolant passages and the like by means of a well-known press forming. Since the carbon layer 9 of the present invention has high adhesion to the metal substrate 6, the carbon layer 9 is not exfoliated even when the reactant gas passages and the like are formed after the carbon layer 9.
  • the metal substrate that the reactant gas passages, the manifolds, coolant passages and the like are not preliminarily provided is prepared.
  • the treatments to degrease, wash, and remove the oxide film on the surface of the metal substrate 6 are performed similarly to the first example.
  • the middle layer 11 and the carbon layer 9 are formed similarly to the second example, followed by forming the reactant gas passages, the manifolds, coolant passages and the like by means of a well-known press forming.
  • the fuel cell separator of the present invention can be used for various kinds of fuel cells such as a polymer electrolyte fuel cell (PEFC), a phosphoric acid fuel cell (PAFC), a molten carbonate fuel cell (MCFC), a solid oxide fuel cell (SOFC) or an alkaline fuel cell (AFC).
  • PEFC polymer electrolyte fuel cell
  • PAFC phosphoric acid fuel cell
  • MCFC molten carbonate fuel cell
  • SOFC solid oxide fuel cell
  • AFC alkaline fuel cell
  • PEFC polymer electrolyte fuel cell
  • the present invention is characterized by the separator, while well-known components can be used for composing the fuel cell except for the separator.
  • electrolyte membrane As an electrolyte membrane, well-known electrolyte membranes can be used. However, the polymer electrolyte membrane is preferable.
  • the polymer electrolyte membrane is broadly divided into a fluorine polymer electrolyte membrane and a hydrocarbon polymer electrolyte membrane depending on the type of ion-exchange resin as a constituent material.
  • a perfluorocarbon sulfonic acid polymer such as Nafion (registered trademark, made by DuPont Corporation), Aciplex (registered trademark, made by Asahi Kasei Corporation), and Flemion (registered trademark, made by Asahi Glass Co., Ltd.), a perfluorocarbon phosphonic acid polymer, a trifluorostyrene sulfonic acid polymer, an ethylene tetrafluoroethylene-g-styrene sulfonic acid polymer, an ethylene-tetrafluoroethylene copolymer, a polyvinylidene fluoride-perfluorocarbon sulfonic acid polymer, and the like are included.
  • Nafion registered trademark, made by DuPont Corporation
  • Aciplex registered trademark, made by Asahi Kasei Corporation
  • Flemion registered trademark, made by Asahi Glass Co., Ltd.
  • fluorine polymer electrolyte membranes are preferably used in view of electric generation performance such as heat resistance and chemical stability.
  • the fluorine polymer electrolyte membrane composed of the perfluorocarbon sulfonic acid polymer is preferably used.
  • hydrocarbon polymer electrolyte membrane sulfonated polyether sulfone (S-PES), sulfonated polyaryl ether ketone, polybenzimidazole-alkyl sulfonic acid, polybenzimidazole-alkylphosphonic acid, sulfonated polystyrene, sulfonated polyether ether ketone (S-PEEK), sulfonated polyphenylene (S-PPP) and the like are included.
  • S-PES sulfonated polyether sulfone
  • S-PEEK sulfonated polyether ether ketone
  • S-PPP sulfonated polyphenylene
  • These hydrocarbon polymer electrolyte membranes are preferably used in view of manufacturing reasons such as inexpensiveness of raw materials, ease of manufacture, and high selectivity of materials.
  • the above-mentioned ion-exchange resin may be used individually, or in combination with two kinds or more
  • a thickness of the polymer electrolyte membrane is not limited, and may be appropriately determined in view of the characteristics of the fuel cell to be obtained, however it is usually about 5 micrometers to 300 micrometers. When the thickness is within the above-mentioned range, the balance of intensity during the formation, durability in use, and output property in use may be controlled appropriately.
  • the catalyst layers include a catalyst component, an electrical conductive catalyst carrier supporting the catalyst component, and an electrolyte.
  • the catalyst component used for the anode catalyst layer is not particularly limited as long as it has a catalytic function for an oxidizing reaction of hydrogen, and a well-known catalyst may be used.
  • the catalyst component used for the cathode catalyst layer is also not particularly limited as long as it has a catalytic function for a reductive reaction of oxygen, and a well-known catalyst may be used.
  • the catalyst component may be selected from platinum, ruthenium, iridium, rhodium, palladium, osmium, tungsten, lead, iron, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium and aluminum, alloys of these, and the like.
  • the component at least containing platinum is preferably used in order to enhance catalytic activity, poisoning resistance to carbon monoxide and the like, heat resistance, and the like.
  • a composition of the alloy when used as the anode catalyst it is preferable that platinum be 30 to 90 atom% and the alloyed metal be 10 to 70 atom%, although the composition depends on the type of metal formed into the alloy.
  • platinum it is preferable that platinum be 30 to 90 atom% and the alloyed metal be 10 to 70 atom%, although the composition depends on the type of metal formed into the alloy.
  • an alloy is generally composed of a metal element, and one or more of different metal elements or nonmetal elements added thereto, and is a general term of elements having a metallic property.
  • a constitution of the alloy there are mentioned, for example, an eutectic alloy as a so-called mixture in which component elements become individual crystals, a solid solution in which the component elements are completely blended together, and a compound in which the component elements compose an intermetallic compound or a compound of a metal and nonmetal.
  • the present invention may adopt any of those.
  • the catalyst components for use in the anode catalyst layer and the catalyst component for use in the cathode catalyst layer can be appropriately selected from the above-mentioned ones.
  • the similar definition between the anode catalyst layer and the cathode catalyst layer will be made with regard to the catalyst components, which are referred to as a "catalyst component" in a lump.
  • the catalyst component for the anode catalyst layer and the cathode catalyst layer may be the same.
  • the catalyst component may be appropriately selected so as to exert such desired functions as described above.
  • a shape and size of the catalyst component is not particularly limited, and can be similar to these of a well-known catalyst component.
  • the catalyst component is preferably granular.
  • the average particle diameter of the catalyst particles is 1 nm to 30 nm in this case.
  • the balance of catalyst utilization efficiency and ease of supporting may be controlled appropriately.
  • the "average particle diameter of catalyst particles" in the present invention may be measured as a crystallite diameter obtained from a full width at half maximum of a diffraction peak of the catalyst component in an X-ray diffraction, or measured as an average value of the particle diameters of the catalyst component investigated by the transmission electron microscope.
  • the catalyst carrier functions as a carrier for supporting the above-mentioned catalyst component, and functions as an electrical conduction path involved in communicating electrons with the catalyst component.
  • the catalyst component has only to have a sufficient surface area for supporting the catalyst component in a desired dispersed state, and have sufficient electron conductivity.
  • the catalyst carrier contains carbon as a main component. Specifically, carbon particles composed of carbon black, activated carbon, coke, natural graphite, artificial graphite, and the like are included.
  • containing carbon as a main component denotes that carbon atoms are contained as a main component, and includes concepts that the carbon material is composed only of the carbon atoms, and also that the carbon material is substantially composed of the carbon atoms. Depending on the situation, elements other than the carbon atoms may be contained in order to enhance the characteristics of the fuel cell.
  • being substantially composed of the carbon atoms denotes that inclusion of impurities with approximately 2 to 3 % by mass or less may be permitted.
  • a BET specific surface area of the catalyst carrier has only to have an area enough to support the catalyst component in a highly dispersed state.
  • the area is 20 to 1600 m 2 /g, more preferably 80 to 1200 m 2 /g.
  • the specific surface area of the catalyst carrier is within the above-mentioned range, the balance of dispersibility of the catalyst component and effective utilization efficiency of the catalyst component on the catalyst carrier may be controlled appropriately.
  • a size of the catalyst carrier is not particularly limited, but preferably 5 nm to 200 nm of an average particle diameter, more preferably 10 nm to 100 nm, in view of ease of supporting, catalyst utilization efficiency, controlling the thickness of the catalyst layer within an appropriate range, and the like.
  • a supported amount of the catalyst component is preferably 10 to 80 % by mass, more preferably 30 to 70 % by mass, with respect to the total amount of the electrode catalyst.
  • the supported amount of the catalyst component is within the above-mentioned range, the balance of dispersibility of the catalyst component and catalyst performance in the catalyst carrier may be controlled appropriately.
  • the supported amount of the catalyst component may be measured by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES).
  • the catalyst layer includes the ion conductive polymer electrolyte in addition to the electrode catalyst.
  • the polymer electrolyte is not particularly limited, and it is possible to appropriately refer to the conventional knowledge.
  • the above-mentioned ion-exchange resin composing the polymer electrolyte membrane may be added to the catalyst layer as the polymer electrolyte.
  • the anode and cathode may have the gas diffusion layers in addition to the above-mentioned catalyst layers.
  • the gas diffusion layer is provided on one side of the catalyst layer opposite to the side that the electrolyte membrane is in contact with.
  • the catalyst layer may be formed on the gas diffusion layer.
  • the catalyst layer may be formed in a part of the gas diffusion layer.
  • the electrode that the catalyst component and electrolyte are included in a desired region of the gas diffusion layer described later, and the like may be included.
  • the gas diffusion layer is not particularly limited, and the well-known gas diffusion layer can be used.
  • a sheet-like gas diffusion layer having electrical conductivity and porousness such as carbon-made fabric, finished paper, felt, and nonwoven fabric, may be included.
  • a thickness of the gas diffusion layer may be appropriately determined in view of the property of the gas diffusion layer to be obtained, it can be approximately 30 micrometers to 50 micrometers.
  • the gas diffusion layer may include a water-repellent for the purpose of ensuring higher water repellency so as to prevent from flooding and the like.
  • a fluorine polymer material such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyhexafluoropropylene, and a tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polypropylene, polyethylene, and the like are included.
  • the gas diffusion layer can include a carbon particle layer composed of a carbon particle assembly containing the water-repellent.
  • the carbon particle layer may be provided on the region in contact with the catalyst layer in the gas diffusion layer.
  • the carbon particles which are not particularly limited, can be conventionally common carbon such as carbon black, graphite and exfoliated graphite.
  • carbon black such as oil furnace black, channel black, lamp black, thermal black and acetylene black is preferable due to good electrical conductivity and largeness of a specific surface area.
  • a water-repellent used in the carbon particle layer may be similar to that used in the gas diffusion layer.
  • the fluorine polymer material is preferably used due to high water repellency, corrosion resistance at the electrode reaction, and the like.
  • the mixture ratio between the carbon particles and the water-repellent in the carbon particle layer it can be said that expected water repellency cannot be obtained if the carbon particles are excessive, or that sufficient electron conductivity cannot be obtained if the amount of the water-repellent is excessive. In view of these points, it is preferable that the mixture ratio between the carbon particles and the water-repellent in the carbon particle layer be approximately 90:10 to 40:60 by mass ratio.
  • a thickness of the carbon particle layer may be appropriately determined in view of water repellency of the gas diffusion layer to be obtained, but preferably 10 micrometers to 1000 micrometers, more preferably 50 micrometers to 500 micrometers.
  • a method for manufacturing the fuel cell of the present invention is not particularly limited. It is possible to manufacture the fuel cell by appropriately referring to the conventional knowledge in the field of fuel cells.
  • a type of a fuel for the fuel cell may include hydrogen, methanol, ethanol, 1-propanol, 2-propanol, n-butanol, sec-butanol, tert-butanol, dimethyl ether, diethyl ether, ethylene glycol and diethylene glycol.
  • hydrogen and methanol are preferable in view of an availability of a high output power.
  • a stack in which a plurality of the membrane electrode assemblies is connected in series via the separators may be formed so that the fuel cell can be obtained a desired voltage and the like.
  • a shape and the like of the fuel cell which are not particularly limited, can be appropriately determined so as to obtain the fuel cell property such as a desired voltage.
  • the fuel cell using the fuel cell separator of the present invention can be installed in a vehicle.
  • a purpose of the fuel cell of the present invention is not particularly limited, the fuel cell is preferably used as a driving power supply in the vehicle such as an automobile in view of excellent generating performance.
  • EXAMPLE 1 A separator plate (metal substrate) formed of stainless steel (SUS316L) with a thickness of 100 micrometers was used. An ultrasonic cleaning was performed on the separator plate in ethanol for three minutes as a pretreatment. Then, the metal substrate was placed in a vacuum chamber, and an ion bombard treatment with argon gas was performed so as to remove an oxide film on the surface. Both of the pretreatment and the ion bombard treatment were performed on both sides of the metal substrate.
  • SUS316L stainless steel
  • EXAMPLE 2 The separator plate (metal substrate) formed of stainless steel (SUS316L) with the thickness of 100 micrometers was used, and the pretreatment and the ion bombard treatment were performed similarly to Example 1.
  • chromium (Cr) was used as a target, and chromium films (middle layers) with a thickness of 0.2 micrometers were formed on both sides of the metal substrate.
  • carbon layers with a thickness of 0.2 micrometers were formed on the middle layers similarly to Example 1.
  • An R value (I D /I G ) of the carbon layers was 1.5.
  • a content ratio of the metal particles in the carbon layers was 10 % by mass, and a content ratio of electrical conductive carbon in the carbon layers was 90 % by mass.
  • EXAMPLE 3 A separator plate (metal substrate) formed of aluminum alloy (A1050) with a thickness of 200 micrometers was used, and the pretreatment and the ion bombard treatment were performed similarly to Example 1.
  • solid graphite and magnesium (Mg) were used as a target, and a negative bias voltage with 150 V was applied to the metal substrate. While applying the voltage, carbon layers with a thickness of 0.2 micrometers into which Mg particles (15 nm of average particle size) were dispersed were formed on both sides of the metal substrate. An R value (I D /I G ) of the carbon layers was 1.4. A content ratio of the metal particles in the carbon layers was 10 % by mass, and a content ratio of electrical conductive carbon in the carbon layers was 90 % by mass.
  • Example 2 carbon layers with a thickness of 0.2 micrometers were formed similarly to Example 1.
  • An R value (I D /I G ) of the carbon layers was 1.5.
  • a content ratio of the metal particles in the carbon layers was 10 % by mass, and a content ratio of electrical conductive carbon in the carbon layers was 90 % by mass.
  • chromium films (middle layers) with a thickness of 0.2 micrometers and carbon layers with a thickness of 0.2 micrometers were formed similarly to Example 2.
  • An R value (I D /I G ) of the carbon layers was 1.5.
  • a content ratio of the metal particles in the carbon layers was 10 % by mass, and a content ratio of electrical conductive carbon in the carbon layers was 90 % by mass.
  • the separator plate formed of stainless steel (SUS316L) with the thickness of 100 micrometers was used, and the pretreatment and the ion bombard treatment were performed similarly to Example 1.
  • the separator of the present invention containing predetermined metal particles in the carbon layer had superior at least corrosion resistance and electrical conductivity to the conventional separators. The results will be explained in detail below.
  • the conventional separator (for example, Comparative Examples 1 and 2) has the configuration in which the film (carbon layer) including only electric conductive carbon is directly formed on the metal substrate. While, good adhesion between the metal substrate and the electrical conductive carbon layer cannot be obtained, and the contact resistance value in the early stage is high. Furthermore, corrosion at the interface between the metal substrate and the electrical conductive carbon layer is easily developed.
  • the conventional separator may be provided with the middle layer composed of the electrically conductive material such as chromium (Cr) so that adhesion between the metal substrate and the electrical conductive carbon layer is improved.
  • the middle layer composed of the electrically conductive material such as chromium (Cr) so that adhesion between the metal substrate and the electrical conductive carbon layer is improved.
  • Cr chromium
  • the conventional separator had difficulty preventing the contact resistance from degrading (increasing) as a separator since oxidation corrosion on the surface of the metal substrate was caused by acid water in the fuel cell when the cracks and scratches were caused by stacking load and press forming.
  • the fuel cell separator of the present invention is characterized by the configuration in which the carbon layer includes predetermined metal particles. Even if the cracks and scratches are caused by stacking load and press forming due to such a configuration, the acid component in the fuel cell forms the oxide by reacting with the predetermined metal particles in the carbon layer before reaching the metal substrate. Thus, the acid component is, namely, "trapped". Therefore, according to the present invention, it is possible to effectively suppress the resistance increase between the metal substrate and the surface of the separator without causing the problem that the acid component reaches the surface of the metal substrate to form the oxide film.
  • the easily-oxidized metal particles are dispersed into the carbon layer in advance. Therefore, it is possible that the oxide of the metal particles is easily formed before acid water reaches the metal substrate so as to prevent the oxide film from being formed on the surface of the metal substrate. Moreover, due to the introduction of the metal particles into the carbon layer, the film stress is reduced and adhesion between the carbon layer and the metal substrate is also improved.

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Abstract

L'invention porte sur un séparateur de pile à combustible qui inclut un substrat métallique comportant un passage de gaz dans lequel un gaz réactif circule ; et une couche de carbone qui est formée sur une surface du substrat métallique et contient un certain nombre de particules métalliques et du carbone électriquement conducteur. En conséquence, il est possible qu'un oxyde des particules métalliques soit facilement formé avant que de l'eau acide n'atteigne le substrat métallique, de façon à empêcher le film d'oxyde d'être formé sur la surface du substrat métallique.
PCT/JP2009/000616 2008-03-26 2009-02-17 Séparateur de pile à combustible WO2009118991A1 (fr)

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CA2750783C (fr) 2008-11-25 2015-10-13 Nissan Motor Co., Ltd. Element conducteur et pile a combustible a polymere solide l'utilisant
JP2011134653A (ja) * 2009-12-25 2011-07-07 Toyota Motor Corp 燃料電池用セパレータ、燃料電池用ガス流路層とこれらの製造方法
KR102595151B1 (ko) * 2022-12-29 2023-10-27 (주)제이 앤 엘 테크 연료전지용 금속분리판 및 그 제조방법

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US9493883B2 (en) 2012-02-23 2016-11-15 Treadstone Technologies, Inc. Corrosion resistant and electrically conductive surface of metal

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