WO2017188793A1 - Ensemble membrane-électrodes de pile à combustible - Google Patents

Ensemble membrane-électrodes de pile à combustible Download PDF

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Publication number
WO2017188793A1
WO2017188793A1 PCT/KR2017/004602 KR2017004602W WO2017188793A1 WO 2017188793 A1 WO2017188793 A1 WO 2017188793A1 KR 2017004602 W KR2017004602 W KR 2017004602W WO 2017188793 A1 WO2017188793 A1 WO 2017188793A1
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Prior art keywords
electrode
catalyst
catalyst layer
membrane
fuel cell
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PCT/KR2017/004602
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English (en)
Korean (ko)
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민명기
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코오롱인더스트리 주식회사
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Priority to CN201780025490.2A priority Critical patent/CN109075362B/zh
Priority to EP17789977.0A priority patent/EP3451428B1/fr
Priority to JP2018556808A priority patent/JP6889735B2/ja
Priority to US16/096,801 priority patent/US11114684B2/en
Priority claimed from KR1020170055486A external-priority patent/KR102236159B1/ko
Publication of WO2017188793A1 publication Critical patent/WO2017188793A1/fr

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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the fuel cell include a polymer electrolyte fuel cell (PEMFC), a direct oxidation fuel cell, and the like.
  • PEMFC polymer electrolyte fuel cell
  • DMFC direct methanol fuel cell
  • the direct oxidation fuel cell has a lower energy density than the polymer electrolyte fuel cell, but it is easy to handle fuel and has a low operating temperature, and thus can be operated at room temperature. In particular, the fuel cell does not require a fuel reforming device.
  • the polymer electrolyte fuel cell has advantages of high energy density and high output.
  • a stack that substantially generates electricity may include several unit cells including a membrane-electrode assembly (MEA) and a separator (also called a bipolar plate). It has a stacked structure of dozens.
  • the membrane-electrode assembly is called an anode electrode (also called “fuel electrode” or “oxidation electrode”) and a cathode electrode (also called “air electrode” or “reduction electrode”) with a polymer electrolyte membrane containing a hydrogen ion conductive polymer therebetween. ) Is located.
  • the principle of generating electricity in a fuel cell is that fuel is supplied to an anode electrode, which is a fuel electrode, adsorbed to a catalyst of the anode electrode, and the fuel is oxidized to generate hydrogen ions and electrons. Reaching the cathode electrode, hydrogen ions pass through the polymer electrolyte membrane and are delivered to the cathode electrode. An oxidant is supplied to the cathode, and the oxidant, hydrogen ions, and electrons react on the catalyst of the cathode to generate electricity while generating water.
  • the gas composition of the anode electrode may be composed of oxygen and hydrogen at start-up / shut-down or fuel starvation. This causes the voltage to rise by 1.6V or more.
  • the present invention is to provide a fuel cell membrane-electrode assembly that improves cell performance by preventing corrosion of a carrier and improving water distribution in a low current region to have high activity and stability.
  • the present invention provides a cathode electrode and an anode electrode which are located facing each other; And a polymer electrolyte membrane positioned between the cathode electrode and the anode electrode, wherein the cathode electrode and the anode electrode are each an electrode substrate; A microporous layer positioned on the electrode substrate; And a first catalyst layer positioned on the microporous layer, wherein at least one second catalyst layer is positioned between the first catalyst layer and the polymer electrolyte membrane, and the second catalyst layer includes a reaction inducing material.
  • the material is a metal or alloy selected from Ir, Ru, Ir a Ru b , Ir c Ru d M e , Ir f M g , Ru f M g , and combinations thereof, or IrO x , RuO x , Ir a Ru b
  • a membrane-electrode assembly for a fuel cell which is an oxide selected from O x , Ir c Ru d M e O x , Ir f M g O x , Ru f M g O x , and a combination thereof.
  • M is Fe, Co, Mn, Cu, Ni, Zn, Ti, V, Cr, Pd, Ag, Cd, In, Sn, Au, Os, W, Re, Rh or a combination thereof, and
  • the ratio is 0.3 to 3.5
  • the ratio of c / (d + e) is 0.3 to 3.5
  • the ratio of d / e is 0.5 to 25
  • the ratio of f / g is 3 to 20
  • x is 0.5 to 2. Is an integer.
  • the reaction inducing material may be a three-way catalyst of Ir c Ru d M e or Ir c Ru d M e O x .
  • the reaction inducing material may be selected from Ir 8 Ru 2 FeO x , IrRuO x , IrRu 2 O x , Ir 2 RuO x , and combinations thereof.
  • the thickness of the second catalyst layer may be 0.1 ⁇ m to 5 ⁇ m.
  • the second catalyst layer may further include a carrier supporting the reaction inducing material.
  • the reaction inducing substance may be included in an amount of 20 to 99 wt% based on the total amount of the reaction inducing substance and the carrier.
  • the second catalyst layer may further include an additive selected from SiO 2 , TiO 2 , WO x, and ZrO 2 .
  • the second catalyst layer may further include a carrier supporting the reaction inducing substance and the additive.
  • the total content of the reaction inducing substance and the additive may be included in an amount of 20 wt% to 99 wt% with respect to the total amount of the reaction inducing substance, the additive and the carrier.
  • the additive may be included in an amount of 0.5 wt% to 5 wt% based on the total amount of the reaction inducing substance, the additive, and the carrier.
  • the carrier may be graphite, denka black, ketjen black, acetylene black, carbon nanotubes, carbon nanofibers, carbon nanowires, carbon nanoballs, activated carbon, stabilized carbon, indium tin oxide (ITO), TiO 2 , WO, SiO 2 And the like or a combination thereof.
  • ITO indium tin oxide
  • the membrane-electrode assembly for fuel cell can be implemented to improve the cell performance by preventing corrosion of the carrier and improving the distribution of water in the low current region to have high activity and stability.
  • FIG. 1 is a schematic diagram illustrating a membrane-electrode assembly (MEA) for a fuel cell according to one embodiment.
  • MEA membrane-electrode assembly
  • FIG. 2 is a schematic view showing a membrane-electrode assembly (MEA) for a fuel cell according to another embodiment.
  • MEA membrane-electrode assembly
  • FIG. 3 is a schematic diagram illustrating a membrane-electrode assembly (MEA) for a fuel cell according to another embodiment.
  • MEA membrane-electrode assembly
  • FIG. 4 is an exploded perspective view illustrating a stack of a fuel cell according to an embodiment.
  • FIG. 5 is a graph showing current density according to the start-stop cycle of the membrane-electrode assemblies prepared in Comparative Examples 1 and 2;
  • FIG. 6 shows a cyclic voltage-current graph of the catalyst layers of Comparative Example 1 and Example 6.
  • FIG. 7 shows a cyclic voltage-current graph according to the number of start-stop cycles of the catalyst layer of Example 6.
  • the membrane-electrode assembly for a fuel cell includes a cathode electrode and an anode electrode which are located facing each other; And a polymer electrolyte membrane positioned between the cathode electrode and the anode electrode, wherein the cathode electrode and the anode electrode are each an electrode substrate; A microporous layer positioned on the electrode substrate; And a first catalyst layer positioned on the microporous layer, wherein at least one second catalyst layer is positioned between the first catalyst layer and the polymer electrolyte membrane, and the second catalyst layer includes a reaction inducing material.
  • the material is a metal or alloy selected from Ir, Ru, Ir a Ru b , Ir c Ru d M e , Ir f M g , Ru f M g , and combinations thereof, or IrO x , RuO x , Ir a Ru b Oxides selected from O x , Ir c Ru d M e O x , Ir f M g O x , Ru f M g O x , and combinations thereof (wherein M is Fe, Co, Mn, Cu, Ni, Zn, Ti, V, Cr, Pd, Ag, Cd, In, Sn, Au, Os, W, Re, Rh or a combination thereof, and the ratio of a / b is 0.3 to 3.5, and c / (d + e) The ratio is 0.3 to 3.5, the ratio of d / e is 0.5 to 25, the ratio of f / g is 3 to 20, x is an integer of 0.5
  • the membrane-electrode assembly for a fuel cell includes a cathode electrode and an anode electrode which are located facing each other; And a polymer electrolyte membrane positioned between the cathode electrode and the anode electrode.
  • the cathode electrode and the anode electrode is an electrode substrate, respectively; A microporous layer positioned on the electrode substrate; And a first catalyst layer positioned on the microporous layer, wherein at least one second catalyst layer is positioned between the first catalyst layer and the polymer electrolyte membrane.
  • the second catalyst layer includes a reaction inducing material, and the reaction inducing material is selected from Ir, Ru, Ir a Ru b , Ir c Ru d M e , Ir f M g , Ru f M g , and a combination thereof.
  • Metal or an alloy or an oxide selected from IrO x , RuO x , Ir a Ru b O x , Ir c Ru d M e O x , Ir f M g O x , Ru f M g O x , and combinations thereof Can be.
  • M is Fe, Co, Mn, Cu, Ni, Zn, Ti, V, Cr, Pd, Ag, Cd, In, Sn, Au, Os, W, Re, Rh or a combination thereof, and
  • the ratio is 0.3 to 3.5
  • the ratio of c / (d + e) is 0.3 to 3.5
  • the ratio of d / e is 0.5 to 25
  • the ratio of f / g is 3 to 20
  • x is an integer from 0.5 to 2.
  • the fuel cell membrane-electrode assembly will be described in more detail below with reference to FIGS. 1 to 3.
  • FIGS. 1 to 3 are schematic diagrams illustrating a membrane-electrode assembly (MEA) for a fuel cell according to an embodiment of the present invention.
  • MEA membrane-electrode assembly
  • the membrane-electrode assembly 10, 20, 30 for a fuel cell includes a cathode electrode 11 and an anode electrode 11 ′ positioned opposite to each other. And a polymer electrolyte membrane 15 positioned between the cathode electrode 11 and the anode electrode 11 ', each of the cathode electrode 11 and the anode electrode 11' being an electrode.
  • a fuel cell membrane-electrode assembly 10 is positioned between the first catalyst layer 14 and the polymer electrolyte membrane 15 included in the cathode electrode 11.
  • a second catalyst layer 16 may be further included.
  • the fuel cell membrane-electrode assembly 20 includes a first catalyst layer 14 ′ and the polymer electrolyte membrane 15 included in the anode electrode 21 ′. It may further include a second catalyst layer 16 ′ positioned between.
  • the membrane-electrode assembly 30 for a fuel cell may include a first catalyst layer 14 included in the cathode electrode 31 and the anode electrode 31 ′, respectively. 14 ') and the second catalyst layers 16 and 16' positioned between the polymer electrolyte membrane 15 may be further included.
  • the second catalyst layer 16 including the reaction inducing material is positioned between the first catalyst layer 14 and the polymer electrolyte membrane 15 included in the cathode electrodes 11 and 31.
  • OER oxygen evolution reaction
  • the membrane-electrode assembly (10, 20, 30) electrode is deteriorated phenomenon that the carbon carrier of the platinum catalyst is continuously oxidized in the high potential region, which is a polymer electrolyte fuel cell This is because it is thermodynamically unstable under operating conditions of (Polymer Electrolyte Membrane Fuel Cell, PEMFC) and corrodes as shown in Equation (1) below.
  • the oxidation reaction is generally known to proceed slowly, but when a high potential is applied to the membrane-electrode assembly 10, 20, 30, deterioration is further accelerated, resulting in a sharp drop in catalyst performance.
  • the oxygen generation reaction (OER) catalyst which decomposes water generated through electrochemical reaction to generate oxygen prevents corrosion of the carrier by first decomposing water before the carbon carrier is corroded in the high potential region. (See equation (2)).
  • the OER catalysts include Ir, Ru, Ir a Ru b , Ir c Ru d M e , Ir f M g , Ru f M g , IrO x , RuO x , Ir a Ru b O x , Ir c Ru d M e O x , Ir f M g O x , and Ru f M g O x .
  • RuO x may be easily used as the oxygen generation reaction (OER) catalyst, but it has a problem of being easily decomposed in an acid atmosphere and a high voltage.
  • Ir c Ru d M e or Ir c Ru d M e O x which is a ternary alloy oxygen evolution reaction (OER) catalyst including RuO x and IrO x together, does not occur as described above. It can be used and by using it can improve both activity and stability.
  • OER ternary alloy oxygen evolution reaction
  • the electrochemical reaction is actively generated at the interface where the polymer electrolyte membrane 15 and the electrode in the membrane electrode assembly (10, 20, 30) is known to generate a lot of water, wherein the carbon carrier is produced Corrosion is more severely caused by water.
  • the first catalyst layer 14 'and the polymer in which the second catalyst layer 16' including the reaction-inducing substance are included in the anode electrodes 21 'and 31' are included.
  • corrosion of the carrier by the generated water can be suppressed.
  • the catalyst layer prepared by simply mixing the oxygen generation reaction (OER) catalyst has a simple inhibitory effect on the corrosion of the carrier by the water decomposition reaction, but the electrochemical in the electrode of the membrane-electrode assembly (10, 20, 30) There is a problem of reducing the output performance of the membrane electrode assembly (10, 20, 30) by acting as a resistance to ion transfer necessary for the reaction.
  • OER oxygen generation reaction
  • the membranes 15 By being located between the membranes 15, it is possible to prevent the breakdown of the anode catalyst layers (first catalyst layers) 14, 14 'due to cell-reversal (reverse potential) which may occur at low temperature startup of the vehicle.
  • the reaction-inducing substance in the second catalyst layer 16' decomposes water instead of carbon in the anode electrodes 21 'and 31' so as to cover an electric current. , 14 ') can be safe.
  • the second catalyst layers 16 and 16 ' are positioned in front of the polymer electrolyte membrane 15 separately from the first catalyst layers 14 and 14' to prevent hydrogen crossover, and the polymer electrolyte The generation of H 2 O 2 which accelerates the deterioration of the film 15 can be suppressed.
  • the reaction-inducing substance in the second catalyst layers 16 and 16 ′ has excellent water-containing property, the water-distribution near the polymer electrolyte membrane 15 in the low current region is improved to improve the membrane-electrode assembly 10, 20. , 30) can improve performance.
  • the second catalyst layers 16 and 16 ' can be easily formed by the same method as the first catalyst layers 14 and 14', for example, a transfer coating method, slurry viscosity that can be generated by adding a reaction inducing substance. It can be prepared by transferring on the first catalyst layer (14, 14 ') or on the polymer electrolyte membrane 15 without considering the degree of change in I / C ratio (ionomer / carbon).
  • the atomic ratio of Ir and Ru that is, the ratio of a / b or the ratio of c / (d + e) may be 0.3 to 3.5, specifically, 0.5 to 2.
  • the atomic ratio of Ru and M that is, the ratio of d / e is 0.5 to 25
  • the atomic ratio of Ir or Ru and M that is, the ratio of f / g, may be 3 to 20.
  • the atomic ratio can improve the battery performance as it has a high water decomposition activity and excellent stability at high voltage.
  • x may be an integer of 0.5 to 2, specifically 1 to 2.
  • x satisfies an integer within the above range, stable performance may be exhibited at high voltage without changing water decomposition activity.
  • the oxide may comprise the form of nanoparticles, nanorods, core-shells, or a combination thereof. Oxides having this form may have high dispersibility.
  • the average particle diameter (D50) of the oxide may be 1 nm to 6 nm, specifically 2 nm to 5 nm.
  • the dispersibility is further improved to obtain high activity using a small amount of oxide.
  • reaction-inducing substance may be selected from, for example, Ir 8 Ru 2 FeO x , IrRuO x , IrRu 2 O x , Ir 2 RuO x , and combinations thereof.
  • the second catalyst layers 16 and 16 ′ may have a thickness of 0.1 ⁇ m to 5 ⁇ m, specifically 0.1 ⁇ m to 3 ⁇ m, and most specifically 0.1 ⁇ m to 2 ⁇ m.
  • the thicknesses of the second catalyst layers 16 and 16 ' are within the above ranges, the durability of the carrier layer is improved without reducing the performance of the catalyst layer, and the water distribution is improved near the polymer electrolyte membrane 15 in the low current region.
  • the performance of the membrane-electrode assembly 10, 20, 30 can be improved.
  • the second catalyst layers 16 and 16 ′ may further include a carrier supporting the reaction inducing substance.
  • the reaction-inducing substance may be used alone or in a form supported on a carrier.
  • the reaction inducing substance may be used in a form supported on the carrier.
  • the carrier may be graphite, denka black, ketjen black, acetylene black, carbon nanotubes, carbon nanofibers, carbon nanowires, carbon nanoballs, activated carbon, stabilized carbon, indium tin oxide (ITO), TiO 2 , WO, SiO 2 And the like or a combination thereof.
  • ITO indium tin oxide
  • the stabilized carbon may be formed by heat treating the Ketjen black at 1500 ° C to 3000 ° C, for example, at 2000 ° C to 2800 ° C.
  • the surface area of the stabilized carbon may be 50 m 2 / g to 700 m 2 / g, for example, 70 m 2 / g to 400 m 2 / g.
  • the reaction inducing substance may be included in an amount of 20 to 99 wt% based on the total amount of the reaction inducing substance and the carrier, for example, 30 to 80 wt% and 30 to 70 wt%.
  • the reaction inducing substance is supported within the content range, it is possible to improve the dispersibility of the catalyst while ensuring high stability.
  • the second catalyst layers 16 and 16 ′ may further include additives selected from SiO 2 , TiO 2 , WO x, and ZrO 2 in addition to the reaction inducing material.
  • the additive may retain water and may serve as a water decomposition initiator.
  • the additive may be included in an amount of 0.5 to 5% by weight, specifically 1 to 3% by weight, based on the total amount of the reaction-inducing substance, the additive, and the carrier.
  • the water decomposition reaction is started at a lower voltage, thereby further preventing corrosion of the carrier while ensuring high activity and stability of the fuel cell catalyst.
  • the second catalyst layers 16 and 16 ' may be used as the reaction-inducing substance and the additives themselves, or may be used in a form supported on a carrier.
  • the second catalyst layers 16 and 16 ' may be manufactured by the following method.
  • the metal (M) precursor selected may be mixed to have an Ir / (Ru + M) atomic ratio of 0.3 to 3.5, optionally further mixed with a carrier, to which SiO 2 is added to obtain a mixture, and then the mixture is After the first heat treatment, the first heat treated mixture may be prepared by second heat treatment, and then at least a part of the SiO 2 is removed from the second heat treated mixture.
  • the iridium precursor may include iridium chloride (H 2 IrCl 6 ), and the like, and the ruthenium precursor may include ruthenium chloride (RuCl 3 ), and the like, and the metal precursor may be iron nitrate (Fe (NO 3 ) 3 9H 2 O. ), And the like.
  • the first heat treatment may be performed at a temperature of 150 °C to 500 °C under a hydrogen atmosphere, for example, may be carried out at a temperature of 200 °C to 400 °C.
  • the second heat treatment may be performed at a temperature of 200 °C to 500 °C, specifically, at a temperature of 225 °C to 300 °C.
  • the removal of SiO 2 may be performed using a base such as NaOH, KOH, or HF acid.
  • the active substance may be used together.
  • the active material may comprise a metal.
  • the metal may specifically include a platinum-based metal.
  • the platinum-based metal is specifically platinum, ruthenium, osmium, platinum-M alloy (M is Ga, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Mo, W, Rh, Ru, At least one metal selected from Os and Pd), or a combination thereof.
  • the platinum-based metal is more specifically, Pt, Pt-Ru alloy, Pt-W alloy, Pt-Ni alloy, Pt-Sn alloy, Pt-Mo alloy, Pt-Pd alloy, Pt-Fe alloy, Pt-Cr alloy , Pt-Co Alloy, Pt-Co-Ni Alloy, Pt-Co-Fe Alloy, Pt-Co-S Alloy, Pt-Fe-S Alloy, Pt-Co-P Alloy, Pt-Fe-S Alloy, Pt- Fe-Ir alloy, Pt-Co-Ir alloy, Pt-Cr-Ir alloy, Pt-Ni-Ir alloy, Pt-Au-Co alloy, Pt-Au-Fe alloy, Pt-Au-Fe alloy, Pt-Au -Ni alloys, Pt-Ru-W alloys, Pt-Ru-Mo alloys, Pt-Ru-V alloys, Pt-Ru-Rh-
  • the active material may further include a carrier supporting the metal.
  • the metal may be used alone as the active material, or may be used in a form supported on the carrier.
  • the carrier may be graphite, denka black, ketjen black, acetylene black, carbon nanotubes, carbon nanofibers, carbon nanowires, carbon nanoballs, activated carbon, stabilized carbon, indium tin oxide (ITO), TiO 2 , WO, SiO 2 And the like or a combination thereof.
  • ITO indium tin oxide
  • the metal When the metal is used in a form supported on the carrier, the metal may be included in 10 to 80% by weight, specifically 20 to 65% by weight relative to the total amount of the metal and the carrier. When the metal is supported within the content range, it is possible to secure a high-activity fuel cell and to facilitate production of a catalyst layer.
  • the reaction inducing substance may be included in an amount of 0.5 to 10 parts by weight, for example, 1 to 7.5 parts by weight, based on 100 parts by weight of the total amount of the active material, specifically the metal and the carrier.
  • the reaction-inducing substance is included in the content range, it is possible to obtain a catalyst for a fuel cell having excellent stability at high voltage through high water decomposition activity, and existing membrane-electrode assembly (10, 20, 30) even with a small amount of precious metals. It can have a high activity without inhibiting the performance of.
  • the electrode substrates 12 and 12 ′ serve to support the electrode and diffuse fuel and oxidant to the first catalyst layers 14 and 14 ′ to help the fuel and oxidants easily access the catalyst layers.
  • the electrode substrates 12 and 12 use a conductive substrate, specifically, carbon paper, carbon cloth, carbon felt, or metal cloth (fibrous metal cloth)
  • a conductive substrate specifically, carbon paper, carbon cloth, carbon felt, or metal cloth (fibrous metal cloth)
  • the metal film is formed on the surface of the cloth formed of a porous film or polymer fibers) may be used, but is not limited thereto.
  • the electrode substrates 12 and 12 ' may be water-repellent treated with a fluorine-based resin. In this case, the reactant diffusion efficiency may be prevented from being lowered by water generated when the fuel cell is driven.
  • fluorine resin examples include polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, polyperfluoroalkyl vinyl ether, polyperfluorosulfonyl fluoride, alkoxy vinyl ether, and fluorinated ethylene propylene. (fluorinated ethylene propylene), polychlorotrifluoroethylene or copolymers thereof can be used.
  • microporous layers 13 and 13 ' are positioned on the electrode substrates 12 and 12'.
  • microporous layers 13 and 13 ' serve to enhance the diffusion effect of the reactants on the electrode substrates 12 and 12'.
  • the microporous layers 13 and 13 ' are generally conductive powders having a small particle diameter, for example, carbon powder, carbon black, acetylene black, activated carbon, carbon fiber, fullerene, carbon nanotubes, and carbon nanowires. It may include a carbon nano-horn (carbon nano-horn) or a carbon nano ring (carbon nano ring).
  • First catalyst layers 14 and 14 ' are positioned on the microporous layers 13 and 13'.
  • the first catalyst layers 14, 14 ′ catalyze the associated reactions (oxidation of fuel and reduction of oxidant) and include a catalyst.
  • the catalyst may participate in the reaction of the fuel cell, and any that can be used as the catalyst may be used, and specifically, a platinum-based catalyst may be used.
  • a platinum-based catalyst platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy, platinum-M alloy (M is Ga, Ti, V, Cr, Mn, Fe, Co, Ni, A catalyst selected from the group consisting of Cu, Zn, Sn, Mo, Ru, W, Rh, Ru, and combinations thereof), and mixtures thereof.
  • the anode electrodes 11 ', 21', 31 'and the cathode electrodes 11, 21, 31 may use the same material, but in a direct oxidation fuel cell, catalyst poisoning by CO generated during the anode electrode reaction In order to prevent this as the phenomenon occurs, a platinum-ruthenium alloy catalyst is more preferable as the anode electrode catalyst.
  • Such a catalyst may be used as the catalyst itself (black), or may be used on a carrier.
  • This carrier is as described above.
  • the first catalyst layers 14, 14 ′ may also further include ionomers to improve adhesion of the catalyst layers and transfer hydrogen ions.
  • the ionomer may be a polymer resin having hydrogen ion conductivity, and specifically, all polymer resins having at least one cation exchange group selected from a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, and derivatives thereof in a side chain thereof Can be used. More specifically, fluorine polymer, benzimidazole polymer, polyimide polymer, polyetherimide polymer, polyphenylene sulfide polymer, polysulfone polymer, polyether sulfone polymer, polyether ketone polymer, poly At least one polymer resin selected from ether-ether ketone polymers and polyphenylquinoxaline polymers may be used.
  • the polymer resin having hydrogen ion conductivity may substitute H with Na, K, Li, Cs, or tetrabutylammonium in a cation exchange group at the side chain terminal.
  • H Na in the side chain terminal ion exchanger
  • NaOH is substituted for the preparation of the catalyst composition
  • tetrabutylammonium hydroxide is substituted for tetrabutylammonium
  • K, Li or Cs may be substituted with appropriate compounds. It can be substituted using. Since this substitution method is well known in the art, detailed description thereof will be omitted.
  • the ionomer may be used in the form of a single substance or a mixture, and may also be optionally used with a nonconductive compound for the purpose of further improving adhesion to the polymer electrolyte membrane 15.
  • the amount of the nonconductive compound is preferably adjusted to suit the purpose of use.
  • non-conductive compound examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoro alkyl vinyl ether copolymer (PFA), and ethylene / tetrafluoro Ethylene / tetrafluoroethylene (ETFE), ethylenechlorotrifluoro-ethylene copolymer (ECTFE), polyvinylidene fluoride, copolymer of polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), dode At least one selected from silbenzenesulfonic acid and sorbitol can be used.
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • PFA tetrafluoroethylene-perfluoro alkyl vinyl ether copo
  • the ionomer may be included in an amount of 15 to 50% by weight, specifically 20 to 40% by weight, based on the total amount of the catalyst layer.
  • the ionomer is included in the above range, the adhesion of the catalyst layer is improved and the transfer efficiency of the hydrogen ions is increased.
  • a polymer electrolyte membrane 15 is positioned between the cathode electrodes 11, 21, 31 and the anode electrodes 11 ′, 21 ′, 31 ′.
  • the polymer electrolyte membrane 15 is a solid polymer electrolyte having a thickness of 10 ⁇ m to 200 ⁇ m, and the hydrogen ions generated in the catalyst layers of the anode electrodes 11 ′, 21 ′, 31 ′ are cathode electrodes 11, 21, 31. It has a function of ion exchange to move to the catalyst layer of.
  • the polymer electrolyte membrane 15 is generally used as a polymer electrolyte membrane in a fuel cell, and any one made of a polymer resin having hydrogen ion conductivity may be used.
  • a polymer resin having hydrogen ion conductivity may be used.
  • the high molecular resin which has at least 1 cation exchange group chosen from a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, and derivatives thereof in a side chain is mentioned.
  • the polymer resin include fluorine polymer, benzimidazole polymer, polyimide polymer, polyetherimide polymer, polyphenylene sulfide polymer, polysulfone polymer, polyether sulfone polymer, polyether ketone At least one selected from a polymer, a polyether-etherketone-based polymer and a polyphenylquinoxaline-based polymer, and more specific examples thereof include poly (perfluorosulfonic acid) (commercially available as Nafion) and poly (perfluoro Carboxylic acid), copolymers of tetrafluoroethylene and fluorovinyl ether containing sulfonic acid groups, defluorinated sulfide polyether ketones, aryl ketones, poly [(2,2'-m-phenylene) -5,5 At least one selected from '-bibenzimidazole] [poly (2,2'-(m-phenylene) -5,5'-
  • the fuel cell includes a stack in which supplied hydrogen gas causes an electrochemical reaction with an oxidant to generate electrical energy.
  • the stack will be described with reference to FIG. 4.
  • FIG. 4 is an exploded perspective view illustrating a stack of a fuel cell according to an embodiment.
  • the stack 130 includes a plurality of unit cells 131 which induce an oxidation / reduction reaction between the supplied hydrogen gas and the supplied oxidant to generate electrical energy.
  • Each unit cell 131 refers to a cell of a unit for generating electricity, and includes a membrane-electrode assembly 132 for oxidizing / reducing oxygen in hydrogen gas and an oxidant, and a membrane-electrode assembly for hydrogen gas and an oxidant.
  • a separator also known as a bipolar plate
  • the membrane-electrode assembly 132 is as described above.
  • the separator 133 is disposed on both sides of the membrane-electrode assembly 132. In this case, the separators 133 respectively positioned on the outermost side of the stack 130 may be referred to as end plates.
  • the end plate of the separator 133 is provided with a pipe-shaped first supply pipe for injecting hydrogen gas and a pipe-shaped second supply pipe for injecting oxygen gas, and the other end plate includes a plurality of units.
  • a first catalyst (TEC36F52 manufactured by Tanaka) was prepared in which 48 wt% of carbon was loaded with 52 wt% of Pt 3 Co alloy.
  • the first catalyst layer composition was coated on a fluorinated ethylene propylene (FEP) film, and dried sufficiently in a convection oven at a temperature of 90 ° C. for 5 hours to prepare a first catalyst layer, and the first catalyst layer constituted the cathode electrode. It was used as an anode catalyst layer which comprises a cathode catalyst layer and an anode electrode.
  • FEP fluorinated ethylene propylene
  • the second catalyst layer composition is coated on the fluorinated ethylene propylene (FEP) film coated with the first catalyst layer, and dried sufficiently in a convection oven at a temperature of 90 ° C. for 5 hours to coat the second catalyst layer on the first catalyst layer.
  • FEP fluorinated ethylene propylene
  • Prepared multi-coating layer was prepared. In this case, Ir 8 Ru 2 FeO x (0.5 ⁇ x ⁇ 2 ) was included at 5 parts by weight based on 100 parts by weight of the first catalyst.
  • the cathode catalyst layer and the anode catalyst layer multi-coated with the first catalyst layer and the second catalyst layer were transferred to a fluorine-based film, and the FEP film was removed to prepare a membrane-catalyst layer assembly.
  • the catalyst layer thus prepared is shown in FIG. 1.
  • a membrane-electrode assembly was manufactured using the prepared membrane-catalyst layer assembly and SGL's 35BC diffusion layer.
  • SiO 2 a mixture of iridium chloride (H 2 IrCl 6 ) and ruthenium chloride (RuCl 3 ) in a ratio of Ir and Ru of 1: 1, and Ketjen Black was heat-treated at 2250 ° C.
  • H 2 IrCl 6 iridium chloride
  • RuCl 3 ruthenium chloride
  • IrRuO x A second catalyst was prepared in which 42 wt% (0.5 ⁇ x ⁇ 2) and 2 wt% SiO 2 were supported on 56 wt% of stabilized carbon. In this case, IrRuO x (0.5 ⁇ x ⁇ 2) was included at 5 parts by weight based on 100 parts by weight of the first catalyst.
  • a membrane-electrode assembly was manufactured in the same manner as in Example 1, except that the second catalyst was used instead of the second catalyst of Example 1.
  • a membrane-electrode assembly was manufactured in the same manner as in Example 1, except that the second catalyst was used instead of the second catalyst of Example 1.
  • a membrane-electrode assembly was manufactured in the same manner as in Example 1, except that the second catalyst was used instead of the second catalyst of Example 1.
  • a membrane-electrode assembly was manufactured in the same manner as in Example 1, except that the second catalyst was used instead of the second catalyst of Example 1.
  • IrRuO x (0.5 ⁇ x ⁇ 2) was included at 5 parts by weight based on 100 parts by weight of the first catalyst.
  • the membrane-electrode assembly was manufactured in the same manner as in Example 1, except that Ir 8 Ru 2 FeO x (0.5 ⁇ x ⁇ 2 ) of the second catalyst was included at 2.5 parts by weight based on 100 parts by weight of the first catalyst. Prepared.
  • a membrane-electrode assembly was manufactured in the same manner as in Example 2, except that IrRuO x (0.5 ⁇ x ⁇ 2) of the second catalyst was included at 2.5 parts by weight based on 100 parts by weight of the first catalyst.
  • a membrane-electrode assembly was manufactured in the same manner as in Example 3, except that IrRu 2 O x (0.5 ⁇ x ⁇ 2 ) of the second catalyst was included at 2.5 parts by weight based on 100 parts by weight of the first catalyst. .
  • a membrane-electrode assembly was manufactured in the same manner as in Example 4, except that Ir 2 RuO x (0.5 ⁇ x ⁇ 2 ) of the second catalyst was included at 2.5 parts by weight based on 100 parts by weight of the first catalyst. .
  • a membrane-electrode assembly was manufactured in the same manner as in Example 5, except that IrRuO x (0.5 ⁇ x ⁇ 2) of the second catalyst was included at 2.5 parts by weight based on 100 parts by weight of the first catalyst.
  • a membrane-electrode assembly was manufactured in the same manner as in Example 1, except that the second catalyst layer was not used in Example 1.
  • the membrane-electrode assembly was prepared in the same manner as in Comparative Example 1 by simply mixing 2.5 parts by weight of Ir 8 Ru 2 FeO x (0.5 ⁇ x ⁇ 2 ) used in the second catalyst layer in Example 6 with respect to 100 parts by weight of the first catalyst. Prepared.
  • Second catalyst 1st catalyst 2nd catalyst weight ratio IrRuMO x (* part by weight) Ir: Ru: M atomic ratio IrRuMO x : SiO 2 : C Weight Ratio Example One 8: 2: 1 94: 6: 0 92.6: 7.4 5 2 1: 1: 0 42: 2: 56 92.6: 7.4 5 3 1: 2: 0 42: 2: 56 92.6: 7.4 5 4 2: 1: 0 42: 2: 56 92.6: 7.4 5 5 1: 1: 0 24: 2: 74 92.6: 7.4 5 6 8: 2: 1 94: 6: 0 96.2: 3.8 2.5 7 1: 1: 0 42: 2: 56 96.2: 3.8 2.5 8 1: 2: 0 42: 2: 56 96.2: 3.8 2.5 9 2: 1: 0 42: 2: 56 96.2: 3.8 2.5 10 1: 1: 0 24: 2: 74 96.2: 3.8 2.5 Comparative example One - - 100: 0 - 2 8: 2:
  • Start-stop repeated experiments the relative humidity of 100% of N 2 200 CCM, and the anode electrode of the relative humidity of 100% H 2 to a cathode electrode of the MEA sloppy to 100 CCM, while maintaining the unit cell temperature at 65 °C 1.0 ⁇ 1.5
  • the experiment was repeated to start-stop at a speed of 500 mV / s up to V.
  • Current-voltage performance was measured at each 1000 cycles and electrochemical analysis was performed. The results of performing the start-stop repeated experiments are shown in FIG. 5.
  • FIG. 5 is a graph showing current density according to the start-stop cycle of the membrane-electrode assemblies prepared in Comparative Examples 1 and 2;
  • the unit cell cell temperature was maintained at 65 ° C.
  • the anode was supplied with N 2 having a relative humidity of 100%
  • the anode electrode Cyclic voltammetry (CV) was carried out while supplying H 2 with a relative humidity of 100%.
  • the scan range of the voltage was extended from 0V to 1.5V to the region where water decomposition takes place. The results are shown in FIGS. 6 and 7.
  • FIG. 6 shows cyclic voltage-current graphs of the catalyst layers of Comparative Examples 1 and 6, and FIG. 7 shows cyclic voltage-current graphs according to the number of start-stop cycles of the catalyst layers of Example 6.
  • FIG. 7 shows cyclic voltage-current graphs according to the number of start-stop cycles of the catalyst layers of Example 6.
  • the current rapidly increases near 1.4V. From this, it can be seen that an oxygen generation reaction occurs in which water is decomposed to generate oxygen. Accordingly, when the fuel cell catalyst includes the second catalyst layer, water is decomposed prior to corrosion of carbon to stabilize the fuel cell catalyst. It can be seen that can increase.
  • the voltage loss value of the film-electrode assembly prepared according to Examples 1 to 5 was lower than that of the film-electrode assembly prepared according to Comparative Example 1.
  • the durability of the membrane-electrode assembly prepared by Examples 1 to 5 is improved compared to the durability of the membrane-electrode assembly prepared by Comparative Example 1.
  • the loss voltage of Examples 6 to 10 in which a second catalyst layer including an oxygen evolution reaction (OER) catalyst is placed between the electrolyte membrane and the first catalyst layer, includes only a single catalyst layer without the oxygen evolution reaction catalyst. As compared with the loss voltage of Comparative Example 2 including only a single catalyst layer in which only Comparative Example 1 and the oxygen evolution reaction catalyst were simply mixed, it was confirmed that the loss values of Examples 6 to 10 were significantly low.
  • OER oxygen evolution reaction
  • This result is generally known as a large amount of water generated by the electrochemical reaction at the interface where the polymer electrolyte membrane (PEM) and the catalyst layer meets, the second catalyst layer containing an oxygen evolution reaction (OER) catalyst Positioning between the electrolyte membrane and the first catalyst layer can accelerate the water decomposition reaction to suppress corrosion of the carbon carrier, thereby improving carrier durability of the fuel cell membrane-electrode assembly (MEA), and consequently the membrane-electrode. It is expected to improve the output performance of the assembly.
  • OER oxygen evolution reaction
  • the membrane-electrode assembly for a fuel cell of the present invention is characterized in that Ir, Ru, Ir a Ru b , Ir c Ru d M e , Ir f M g , Ru f M g , and combinations thereof are provided between the first catalyst layer and the polymer electrolyte membrane.

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Abstract

L'invention porte sur un ensemble membrane-électrodes de pile à combustible comprenant : une électrode de cathode et une électrode d'anode positionnées de manière à se faire face ; et une membrane électrolytique polymère positionnée entre l'électrode de cathode et l'électrode d'anode, l'électrode de cathode et l'électrode d'anode comprenant respectivement : un substrat d'électrode ; une couche microporeuse positionnée sur le substrat d'électrode ; et une première couche de catalyseur positionnée sur la couche microporeuse, au moins une seconde couche de catalyseur étant positionnée entre la première couche de catalyseur et la membrane électrolytique polymère, la seconde couche de catalyseur comprenant une substance induisant une réaction, la substance induisant une réaction étant un métal ou un alliage choisi parmi Ir, Ru, IraRub, IrcRudMe, IrfMg, RufMg et leurs combinaisons, ou étant un oxyde choisi parmi IrOx, RuOx, IraRubOx, IrcRudMeOx, IrfMgOx, RufMgOx et leurs combinaisons (M, a, b, c, d, e, f, g et x sont identiques à ceux décrits dans la description).
PCT/KR2017/004602 2016-04-28 2017-04-28 Ensemble membrane-électrodes de pile à combustible WO2017188793A1 (fr)

Priority Applications (4)

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CN201780025490.2A CN109075362B (zh) 2016-04-28 2017-04-28 燃料电池用膜电极组件
EP17789977.0A EP3451428B1 (fr) 2016-04-28 2017-04-28 Ensemble membrane-électrodes de pile à combustible
JP2018556808A JP6889735B2 (ja) 2016-04-28 2017-04-28 燃料電池用膜−電極アセンブリ
US16/096,801 US11114684B2 (en) 2016-04-28 2017-04-28 Fuel cell membrane-electrode assembly

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KR1020170055486A KR102236159B1 (ko) 2016-04-28 2017-04-28 연료전지용 막-전극 어셈블리
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