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WO2019167437A1 - Pile à combustible - Google Patents

Pile à combustible Download PDF

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Publication number
WO2019167437A1
WO2019167437A1 PCT/JP2019/000491 JP2019000491W WO2019167437A1 WO 2019167437 A1 WO2019167437 A1 WO 2019167437A1 JP 2019000491 W JP2019000491 W JP 2019000491W WO 2019167437 A1 WO2019167437 A1 WO 2019167437A1
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WO
WIPO (PCT)
Prior art keywords
cathode
anode
fuel cell
side separator
current collector
Prior art date
Application number
PCT/JP2019/000491
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English (en)
Japanese (ja)
Inventor
千尋 平岩
奈保 水原
光靖 小川
博匡 俵山
孝浩 東野
真嶋　正利
Original Assignee
住友電気工業株式会社
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Publication of WO2019167437A1 publication Critical patent/WO2019167437A1/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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0232—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • H01M8/0245—Composites in the form of layered or coated products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • 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

  • a fuel cell is a device that generates electricity by an electrochemical reaction between a fuel gas such as hydrogen and air (oxygen), and has high power generation efficiency because it can directly convert chemical energy into electricity.
  • a solid oxide fuel cell hereinafter referred to as SOFC
  • SOFC solid oxide fuel cell
  • MEA Membrane Electrode Assembly, membrane-electrode assembly
  • a metal oxide having oxygen ion conductivity such as yttrium-stabilized zirconia (YSZ) is used.
  • the operating temperature of SOFC using oxygen ion conductive YSZ as an electrolyte is a high temperature of 750 ° C. to 1000 ° C. From the viewpoint of reducing the energy consumption required for heating and the selectivity of materials having high temperature resistance, development of SOFCs operating in the middle temperature range of 400 ° C to 600 ° C that can use inexpensive general-purpose stainless steel is underway. .
  • Perovskite oxides such as BaCe 0.8 Y 0.2 O 2.9 (BCY) and BaZr 0.8 Y 0.2 O 2.9 (BZY) exhibit high proton conductivity in the middle temperature range. It is expected as a solid electrolyte for type fuel cells.
  • a plurality of MEAs are usually stacked and an interconnector (separator) that separates fuel gas and air is disposed between the MEAs.
  • the interconnector also has a current collecting function for taking out the generated current to the outside.
  • a fuel cell requires a gas flow path adjacent to the MEA in order to supply fuel gas or air to the MEA.
  • a gas flow path adjacent to the MEA in order to supply fuel gas or air to the MEA.
  • Patent Document 1 Japanese Patent Laid-Open No. 2007-250297
  • Patent Document 2 International Publication No. 2003/12903 pamphlet teaches a method of forming dimples serving as gas flow paths in an interconnector by etching or the like.
  • a fuel cell according to the present disclosure includes a cell structure including a cathode, an anode, and a solid electrolyte layer interposed between the cathode and the anode, a cathode-side separator facing the cathode, and an anode facing the anode A side separator, wherein the cell structure is sandwiched between the cathode side separator and the anode side separator, the cathode side separator and the anode side separator have gas flow paths, and the anode side separator and the anode Or at least one of the cathode side separator and the cathode is provided with a current collector, and the current collector is a metal mesh knitted with a wire, and the wire has a corrosion-resistant layer.
  • a current collector is a metal mesh knitted with a wire, and the wire has a corrosion-resistant layer.
  • FIG. 1 is a cross-sectional view schematically showing a configuration of a fuel cell according to an embodiment.
  • FIG. 2 is a cross-sectional view schematically showing a cell structure included in the fuel cell of FIG.
  • FIG. 3 is an SEM photograph of an example of a corrosion-resistant layer including a Ni—Sn layer.
  • FIG. 4 is a graph showing a change with time in accordance with an increase in the number of operation of the voltage between the anode side separator and the cathode side separator of the fuel cell as a change in voltage decrease rate (deterioration rate).
  • FIG. 5 is a graph showing a change with time in accordance with an increase in the number of operation times of the voltage between the anode side separator and the cathode side separator of the fuel cell as a change in voltage decrease rate (deterioration rate).
  • Electrons flowing to the cell are collected via a metallic material that contacts the anode and / or cathode. At this time, if there are few metal materials which contact an anode and / or a cathode, it will become difficult to flow an electron and resistance will become high.
  • the expanded metal arranged for securing the gas flow path also plays a role as a current collector. However, since the expanded metal has a large hole diameter, the internal resistance during operation tends to be high.
  • the present disclosure has been made in view of the above circumstances, and an object thereof is to provide a fuel cell with reduced internal resistance during operation.
  • the present inventors first considered a configuration in which a material having a main role of current collection and a material having a main role of gas diffusibility are separately arranged.
  • a metal material (current collector) having a current collecting function as a main role is arranged between the cell and the interconnector.
  • an SOFC operating at a high temperature of 700 ° C. to 1000 ° C. is exposed to a wide temperature change from room temperature to 1000 ° C. when it is repeatedly operated and stopped. For this reason, a high thermal shock resistance is required for the current collector disposed between the cell and the interconnector. Further, the current collector is preferably a material having excellent corrosion resistance in a high temperature environment.
  • the fuel cell of the present disclosure is: A cell structure including a cathode, an anode, and a solid electrolyte layer interposed between the cathode and the anode; A cathode separator facing the cathode, and an anode separator facing the anode, The cell structure is sandwiched between the cathode side separator and the anode side separator, Each of the cathode side separator and the anode side separator has a gas flow path, A current collector is provided between at least one of the anode side separator and the anode or between the cathode side separator and the cathode, The current collector is a metal mesh knitted with wire, The wire has a corrosion resistant layer.
  • the current collector composed of the metal mesh has high heat resistance and thermal shock resistance. Moreover, since the corrosion-resistant layer is formed in the wire which comprises a metal mesh, the said electrical power collector also has high oxidation resistance. Therefore, according to the fuel cell, the internal resistance during operation of the fuel cell is reduced. In particular, in the case of a high fuel utilization rate, an increase in internal resistance during operation is more effectively suppressed.
  • the corrosion resistant layer preferably contains Ni and Sn. Thereby, a corrosion-resistant layer can be further excellent in heat resistance. Sn easily forms an alloy with the metal constituting the metal mesh, and easily forms a corrosion-resistant layer. Especially, the alloy of Ni and Sn can have high heat resistance and high corrosion resistance (oxidation resistance).
  • the corrosion-resistant layer includes a first phase and a second phase having different concentrations of Sn with respect to Ni, and the concentration of Sn in the first phase is higher than the concentration of Sn in the second phase.
  • a corrosion-resistant layer can ensure corrosion resistance, heat resistance, and favorable electrical conductivity.
  • the current collector can be provided between the anode separator and the anode.
  • the current collector provided between the anode-side separator and the anode is appropriately referred to as “anode-side current collector”.
  • anode-side current collector At the anode, a reaction of oxidizing a fuel such as hydrogen and releasing protons and electrons proceeds.
  • the atmosphere around the anode and the anode-side current collector is basically a reducing atmosphere because it contains hydrogen gas.
  • the amount of water (water vapor) increases on the anode side, and the atmosphere around the anode-side current collector tends to be oxidizing.
  • the anode-side current collector when a porous nickel sintered body or a metal mesh made of only nickel is used as the anode-side current collector, nickel is easily oxidized during operation at a high temperature and a high fuel utilization rate. Internal resistance tends to increase. On the other hand, since the metal mesh has a corrosion resistant layer, the oxidation resistance is improved. For this reason, by using a metal mesh for the anode side current collector, the metal mesh is hardly oxidized even during operation at a high temperature and a high fuel utilization rate, thereby suppressing an increase in internal resistance.
  • the solid electrolyte layer may have oxygen ion conductivity.
  • protons and oxide ions react to produce water. Therefore, the atmosphere around the anode-side current collector tends to be an oxidizing atmosphere. According to the present disclosure, an increase in internal resistance can be suppressed even in this case.
  • the operating temperature of the fuel cell may be 800 ° C. or higher.
  • the atmosphere around the anode-side current collector tends to be a highly oxidizing atmosphere, but according to the present disclosure, an increase in internal resistance can be suppressed even in this case.
  • the fuel utilization rate may be 75% or more.
  • the atmosphere around the anode-side current collector tends to be a highly oxidizing atmosphere, but according to the present disclosure, an increase in internal resistance can be suppressed even in this case.
  • the fuel utilization rate refers to the ratio of the amount of fuel actually used for cell reaction out of the amount of fuel supplied to the fuel cell via the fuel flow path.
  • the fuel utilization rate can be calculated based on the amount of current flowing through the fuel cell and the flow rate of the fuel gas supplied via the fuel flow path.
  • the current collector can be provided between the cathode separator and the cathode.
  • the current collector provided between the cathode side separator and the cathode is appropriately referred to as a “cathode side current collector”.
  • the oxidant (oxygen) introduced from the oxidant flow path is dissociated to generate oxide ions. For this reason, the periphery of the cathode and the cathode-side current collector is exposed to a high temperature and highly oxidizing atmosphere.
  • the oxidation-resistant cathode-side current collector for example, lanthanum strontium cobalt ferrite (LSCF), which is also used as a cathode material, is used.
  • LSCF lanthanum strontium cobalt ferrite
  • the metal mesh has high heat resistance and thermal shock resistance, and has oxidation resistance by forming a corrosion-resistant layer on at least the surface layer of the metal mesh wire. For this reason, by using a metal mesh for the cathode current collector, it is possible to suppress an increase in internal resistance when the fuel cell is operated.
  • the operating temperature of the fuel cell is preferably 700 ° C. or lower.
  • a metal mesh provided with at least a corrosion-resistant layer as a cathode current collector.
  • the SOFC using the above-described materials having proton conductivity such as BCY and BZY as the solid electrolyte layer operates in the middle temperature range of 400 ° C. to 600 ° C.
  • the above metal mesh is preferably used as the cathode side current collector. be able to.
  • the metal mesh is used as the cathode current collector.
  • the cathode current collector can be preferably used.
  • Metal mesh The metal mesh is formed by weaving a wire made of metal into a mesh, and the wire has a corrosion-resistant layer.
  • a metal mesh may be processed into a mesh by braiding a wire in which a corrosion-resistant layer has been formed in advance, or after forming the wire into a mesh, a treatment for forming a corrosion-resistant layer on the mesh surface may be performed. .
  • the formation of the corrosion resistant layer is preferably performed by plating.
  • vapor deposition, chemical vapor deposition (CVD), plasma CVD, sputtering, or other vapor phase methods, or metal paste may be applied.
  • the plating process, the vapor deposition process, and the sputtering process can be performed by a known method according to the material of the corrosion-resistant layer.
  • any metal or alloy material such as Cu, Fe, Ni, Ag, Zn, brass, ferrochrome (an alloy of Fe and Cr), stainless steel (SUS), or the like can be used.
  • the metal constituting the mesh is selected in consideration of the affinity with the corrosion resistant layer. Especially, it is preferable to employ Ni in terms of low resistivity, heat resistance, and cost for use as a current collector.
  • the corrosion-resistant layer preferably contains Ni and Sn. This is because such a layer is excellent in both characteristics of corrosion resistance (oxidation resistance) and heat resistance. Especially, the alloy of Ni and Sn can have high corrosion resistance and high heat resistance. Therefore, an alloy layer of Ni and Sn (hereinafter referred to as “Ni—Sn layer” as appropriate) can be preferably employed as the corrosion resistant layer.
  • an Ni—Sn layer is formed on the surface of the metal mesh by performing electrolytic plating using a plating solution containing stannous chloride, nickel chloride, and potassium pyrophosphate on the surface of the wire. be able to.
  • the Ni—Sn layer can be formed, for example, by plating a wire made of Ni with a Sn layer or a layer made of an alloy of Ni and Sn. That is, the surface of the Ni wire is coated with a Sn layer or a layer made of an alloy of Ni and Sn using a plating process or the like, and then heat-treated in a reducing atmosphere. As a result, Sn diffuses inside the wire, and the Ni—Sn layer can be changed from the surface layer of the wire to a region having a certain depth.
  • an Sn plating layer is formed on the underlying Ni wire by an electrolytic plating process using a plating solution containing sulfuric acid and stannous sulfate. To do. Thereafter, Sn can be diffused into the Ni wire by heat treatment in a reducing atmosphere at 800 to 1000 ° C. From the viewpoint of easily forming the Ni—Sn alloy layer, it is preferable to employ Ni as the wire.
  • the corrosion-resistant layer includes a first phase and a second phase having different concentrations of Sn with respect to Ni, and the concentration of Sn in the first phase is higher than the concentration of Sn in the second phase.
  • a configuration is easy when the corrosion-resistant layer is the above-described Ni—Si layer. According to this corrosion-resistant layer, corrosion resistance, corrosion resistance, heat resistance and good electrical conductivity can be ensured. The reason is as follows.
  • Ni and Sn are present in the form of an intermetallic compound (for example, Ni 3 Sn).
  • the second phase is a phase containing Ni as a main component, and it is considered that Sn is present in the form of a solid solution in Ni.
  • the first phase that is the intermetallic compound phase has higher corrosion resistance than the second phase.
  • the second phase has higher heat resistance and electrical conductivity than the first phase. For this reason, the corrosion-resistant layer having the first phase and the second phase can have corrosion resistance, heat resistance, and good electrical conductivity.
  • the composition ratio of Ni and Sn is set so that the ratio of Sn contained in the Ni—Sn layer is 100% by mass based on the total amount of Ni and Sn.
  • the content is preferably 4% by mass or more, and more preferably 5% by mass or more.
  • the higher the proportion of the first phase the relatively lower the proportion of the second phase, so there is a concern about the decrease in heat resistance and electrical conductivity.
  • the ratio of Sn contained in the Ni—Sn layer is 15% by mass or less with the total amount of Ni and Sn contained in the Ni—Sn layer being 100% by mass. It is preferable that it is 10% by mass or less.
  • the Ni—Sn layer has an intermetallic compound phase (first phase) containing Ni 3 Sn as a main component and Ni as the main component. And two phases of the phase in which Sn is dissolved in Ni (second phase) are observed at an appropriate ratio. In this case, higher corrosion resistance, higher heat resistance, and better electrical conductivity can be ensured.
  • FIG. 3 shows an SEM photograph of the cross section of the Ni—Sn layer.
  • FIG. 3 is a cross-sectional photograph of a porous metal body (Celmet) on which a Ni—Sn layer is formed.
  • This Ni—Si layer is composed of the first phase and the second phase described above.
  • the metal mesh having the Ni—Si alloy layer also shows the same composition distribution as in FIG. 3 at least in the surface layer.
  • the Ni—Sn layer has two phases, a portion indicated as Location 1 (first phase) and a darker gray portion (second phase) that is blacker than Location 1 and indicated as Location 2.
  • first phase a portion indicated as Location 1
  • second phase a darker gray portion
  • Sn sulfur
  • O oxygen
  • Ni, Sn, and O were contained in atomic fractions of 91 at%, 4 at%, and 5 at%, respectively. From this, it is considered that Sn is contained in a state of being dissolved in Ni in Location 2.
  • all of the wires constituting the metal mesh are Ni—Sn layers. That is, the wire itself is more preferably an alloy of Ni and Sn. In this case, not only the surface of the wire but also the wire itself can have the various characteristics described above.
  • a metal mesh in which Co or Mn is coated as an anticorrosion layer on an Fe—Cr alloy may be used.
  • the mesh size (opening) of the metal mesh is, for example, a square with sides of 0.5 mm to 1 mm.
  • the metal mesh on which the above corrosion-resistant layer is formed is used for an anode-side current collector or a cathode-side current collector of a solid oxide fuel cell (SOFC).
  • SOFC solid oxide fuel cell
  • FIG. 1 schematically shows the configuration of a fuel cell (solid oxide fuel cell) according to an embodiment.
  • the fuel cell 10 includes a cell structure 1.
  • An example of a schematic cross-sectional view of the cell structure is shown in FIG.
  • the cell structure 1 includes a cathode 2, an anode 3, and a solid electrolyte layer 4 interposed therebetween.
  • the anode 3 and the solid electrolyte layer 4 are integrated to form an electrolyte layer-electrode assembly 5.
  • the fuel cell 10 includes an oxidant channel 23 for supplying an oxidant to the cathode, a fuel channel 53 for supplying fuel to the anode, and a cathode, as shown in FIG.
  • the side separator 22 and the anode side separator 52 are provided.
  • the oxidant flow path 23 is formed by the cathode side separator 22, and the fuel flow path 53 is formed by the anode side separator 52. That is, the oxidant channel 23 is a gas channel that the cathode-side separator 22 has, and the fuel channel 53 is a gas channel that the anode-side separator 52 has.
  • the cell structure 1 is sandwiched between the cathode side separator 22 and the anode side separator 52.
  • the oxidant flow path 23 of the cathode side separator 22 is disposed to face the cathode 2 of the cell structure 1, and the fuel flow path 53 of the anode side separator 52 is disposed to face the anode 3.
  • the individual components of the fuel battery cell will be further described.
  • Solid electrolyte layer As the solid electrolyte layer, a layer having proton conductivity or oxygen ion conductivity in a predetermined temperature range is used. A known material can be used for the solid electrolyte layer. Examples of the metal oxide having oxygen ion conductivity include yttrium-stabilized zirconia (YSZ). In this case, the SOFC using YSZ as the electrolyte must be operated at a high temperature of 750 ° C. to 1000 ° C.
  • YSZ yttrium-stabilized zirconia
  • the metal oxide having proton conductivity examples include perovskite oxides such as BaCe 0.8 Y 0.2 O 2.9 (BCY) and BaZr 0.8 Y 0.2 O 2.9 (BZY). Is mentioned. Since BCY and BZY exhibit high proton conductivity in the middle temperature range of 400 ° C. to 600 ° C., BCY and BZY can be used as a solid electrolyte layer of a medium temperature fuel cell. These metal oxides can be formed, for example, by sintering and used as a solid electrolyte layer.
  • BCY and BZY can be used as a solid electrolyte layer of a medium temperature fuel cell.
  • the solid electrolyte layer 4 moves protons generated at the anode 3 to the cathode 2.
  • the solid electrolyte layer 4 moves oxide ions generated at the cathode 2 to the anode 3.
  • the thickness of the solid electrolyte layer is, for example, 1 ⁇ m to 50 ⁇ m, preferably 3 ⁇ m to 20 ⁇ m. When the thickness of the solid electrolyte layer is in such a range, it is preferable in that the resistance of the solid electrolyte layer can be kept low.
  • the solid electrolyte layer forms a cell structure together with the cathode and the anode and can be incorporated into the fuel cell.
  • the solid electrolyte layer is sandwiched between the cathode and the anode, and one main surface of the solid electrolyte layer is in contact with the anode, and the other main surface is in contact with the cathode.
  • the cathode has a porous structure.
  • a reaction oxygen reduction reaction
  • oxide ions are generated when the oxidant (oxygen) introduced from the oxidant flow path is dissociated.
  • a known material can be used as the cathode material.
  • the cathode material for example, a compound containing lanthanum and having a perovskite structure (ferrite, manganite, and / or cobaltite, etc.) is preferable, and among these compounds, a compound further containing strontium is more preferable.
  • the cathode may contain a catalyst such as Pt. When a catalyst is included, the cathode can be formed by mixing the catalyst and the above materials and sintering.
  • the cathode can be formed, for example, by sintering raw materials of the above materials. If necessary, a binder, an additive, and / or a dispersion medium may be used together with the raw material.
  • the thickness of the cathode is not particularly limited, but can be appropriately determined from 5 ⁇ m to 2 mm, for example, and may be about 5 ⁇ m to 40 ⁇ m.
  • the anode has a porous structure.
  • a reaction oxidation reaction of fuel
  • fuel such as hydrogen introduced from the fuel flow path and releases protons and electrons
  • an oxygen ion conductive solid electrolyte layer is used, a reaction (oxygen reduction reaction) between oxide ions and protons conducted through the solid electrolyte layer proceeds at the anode.
  • a known material can be used as the material for the anode.
  • a proton conductive solid electrolyte layer nickel oxide (NiO) as a catalyst component and proton conductors (yttrium oxide (Y 2 O 3 ), BCY, BZY constituting the solid electrolyte layer) Etc.) and the like.
  • NiO nickel oxide
  • Y 2 O 3 yttrium oxide
  • BCY BCY
  • Etc. yttrium oxide
  • an oxygen ion conductive solid electrolyte layer a composite oxide of nickel oxide (NiO) that is a catalyst and an electronic conductor component and an oxygen ion conductor (YSZ or the like) that constitutes the solid electrolyte layer can be used. .
  • the anode can be formed, for example, by sintering raw materials.
  • the anode can be formed by sintering a mixture of NiO powder and proton conductor powder.
  • the thickness of the anode can be appropriately determined from 10 ⁇ m to 2 mm, for example, and may be 100 ⁇ m to 600 ⁇ m.
  • the thickness of the anode 3 is larger than that of the cathode 2, and the anode 3 functions as a support for supporting the solid electrolyte layer 4 (and thus the cell structure 1).
  • the thickness of the anode 3 is not necessarily larger than that of the cathode 2.
  • the thickness of the anode 3 may be approximately the same as the thickness of the cathode 2.
  • the anode and the solid electrolyte layer are integrated.
  • the present invention is not limited to this, and the cathode and the solid electrolyte layer are integrated to form an electrolyte layer-electrode assembly. May be.
  • the oxidant flow path 23 has an oxidant inlet into which the oxidant flows and an oxidant discharge port through which water generated by the reaction, unused oxidant, and the like are discharged (both not shown).
  • the oxidizing agent include a gas containing oxygen.
  • the fuel flow path 53 has a fuel gas inlet through which fuel gas flows, and a fuel gas outlet through which unused fuel, H 2 O, N 2 , CO 2 and the like generated by the reaction are discharged (all not shown). ).
  • the fuel gas include gas containing gas such as hydrogen, methane, ammonia, carbon monoxide.
  • the fuel cell 10 includes a cathode-side current collector 21 disposed between the cathode 2 and the cathode-side separator 22, and an anode-side current collector 51 disposed between the anode 3 and the anode-side separator 52. You may prepare.
  • the cathode-side current collector 21 functions to diffuse and supply the oxidant gas introduced from the oxidant flow path 23 to the cathode 2.
  • the anode current collector 51 functions to diffuse and supply the fuel gas introduced from the fuel flow path 53 to the anode 3. Therefore, each current collector is preferably a structure having sufficient air permeability.
  • the metal mesh having the above-mentioned corrosion-resistant layer can be used as the anode-side current collector 51.
  • the metal mesh has sufficient heat resistance and oxidation resistance even when the operating temperature is 800 ° C. or higher, particularly when exposed to a high-temperature oxidizing atmosphere in which the fuel utilization rate is 75% or higher. .
  • the upper limit value of the operating temperature is not particularly limited, but can be set to 920 ° C. from the viewpoint of the stability of the first phase that is the intermetallic compound phase.
  • the upper limit value of the fuel utilization rate is theoretically 100%.
  • the anode-side current collector 51 may be, for example, silver, silver alloy, nickel, nickel alloy in addition to the metal mesh It is also possible to use a metal porous body containing a metal, a metal mesh (without a corrosion-resistant layer), a punching metal, an expanded metal, or the like. Especially, a metal porous body is preferable at the point of lightweight property or air permeability. In particular, a porous metal body having a three-dimensional network structure is preferable.
  • the three-dimensional network structure refers to a structure in which rod-like or fibrous metals constituting a metal porous body are three-dimensionally connected to form a network. For example, a sponge-like structure or a nonwoven fabric-like structure can be mentioned.
  • the metal porous body can be formed, for example, by coating a resin porous body having continuous voids with the metal as described above. When the internal resin is removed after the metal coating process, a cavity is formed inside the skeleton of the metal porous body, and the metal becomes hollow.
  • nickel “Celmet” manufactured by Sumitomo Electric Industries, Ltd. can be used as a commercially available metal porous body having such a structure.
  • the cathode-side current collector 21 is exposed to an oxidizing atmosphere higher than that of the anode side, a material having higher oxidation resistance than the anode-side current collector 51 is desired.
  • a material obtained by processing LSCF which is a material constituting the cathode, into a paste form can be used.
  • the metal mesh having the above-mentioned corrosion resistant layer is preferably used as the cathode current collector 21.
  • a metal mesh having a corrosion-resistant layer has higher thermal shock resistance than LSCF.
  • the lower limit of the operating temperature is not particularly limited, but can be 300 ° C. from the viewpoint of the activity of the catalyst.
  • the lower limit value of the fuel utilization rate is not particularly limited, but can be 10% from the viewpoint of appropriate utilization.
  • a fuel cell When a fuel cell is configured by stacking a plurality of cell structures, for example, the cell structure 1, the cathode side separator 22, and the anode side separator 52 are stacked as a unit.
  • the plurality of cell structures 1 may be connected in series by, for example, a separator having gas channels (oxidant channels and fuel channels) on both surfaces.
  • the material of the separator examples include heat-resistant alloys such as stainless steel, nickel-base alloy, and chromium-base alloy. Of these, stainless steel is preferable because it is inexpensive. In a proton conductive solid oxide fuel cell (PCFC), since the operating temperature is about 400 ° C. to 600 ° C., stainless steel can be used as a separator material. In the case of an SOFC that operates at a high temperature of about 800 ° C. or more, such as when an oxygen ion conductive solid electrolyte is used, a nickel-based alloy, a chromium-based alloy, or the like is used as a separator material.
  • PCFC proton conductive solid oxide fuel cell
  • the fuel cell can be manufactured by a known method except that the above cell structure is used.
  • Appendix 1 A cell structure including a cathode, an anode, and a solid electrolyte layer interposed between the cathode and the anode; An oxidant flow path for supplying an oxidant to the cathode, A fuel flow path for supplying fuel to the anode, An anode separator, and A cathode side separator, A current collector is provided between the anode separator and the anode, or at least one of the cathode separator and the cathode, The current collector is a metal mesh in which a wire is knitted, and includes a corrosion-resistant layer on at least a surface layer of the wire.
  • Example 1 A fuel cell using YSZ as a solid electrolyte layer was prepared and evaluated as follows.
  • metal mesh Ni mesh made by Taiyo Wire Mesh, mesh opening 0.5 mm
  • a plating solution containing stannous sulfate, sulfuric acid, cresolsulfonic acid, gelatin, and ⁇ -naphthol
  • electrolytic plating treatment is performed. went. Thereafter, heat treatment was performed in a hydrogen atmosphere at 1000 ° C. for 2 hours.
  • a metal mesh (Ni—Sn mesh) X1 provided with a Ni—Sn layer was obtained.
  • NiO was mixed with YSZ powder, which is a solid solution of ZrO 2 and Y 2 O 3 , so as to contain 70% by volume of NiO (catalyst raw material), and pulverized and kneaded by a ball mill.
  • the ratio (atomic composition ratio) between Zr and Y in YSZ was 90:10.
  • a slurry containing the obtained mixture (55% by volume) and a binder (PVB resin, 45% by volume) was processed into a 1.0 mm thick sheet by a doctor blade method to obtain an anode precursor sheet. .
  • a slurry containing the YSZ powder (55% by volume) and the binder (PVB resin, 45% by volume) is processed into a sheet having a thickness of 12 ⁇ m by a doctor blade method, and a precursor sheet for a solid electrolyte layer Got.
  • LSCF La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3- ⁇
  • organic solvent butyl carbitol acetate
  • the operating temperature was 900 ° C.
  • hydrogen was supplied as a fuel gas to the anode of the produced fuel cell at 0.3 L / min
  • air was supplied to the cathode at 1.0 L / min.
  • Each lead wire was connected to an electronic load device, and the current and voltage flowing between the anode side separator and the cathode side separator were measured.
  • the electronic load device was set so that the current flowing between the anode side separator and the cathode side separator would be 32 A so that the fuel utilization rate would be 75%.
  • V1 E ⁇ rI, where E is the electromotive force generated in the fuel cell, r is the internal resistance generated in the current collector, and I is the current between the anode side separator and the cathode side separator. Can do. Therefore, when the current I is constant, the voltage V1 decreases and the deterioration rate A increases as the internal resistance r increases.
  • Example 1 A fuel cell using an Ni metal mesh X2 in which a corrosion-resistant layer was not formed as an anode current collector was produced in the same manner as in Example 1 to obtain a fuel cell Y2. The deterioration rate of the fuel cell Y2 was evaluated in the same manner as in Example 1.
  • Example 2 Fabrication of fuel cell
  • a Ni metal mesh on which no corrosion-resistant layer is formed is laminated as an anode current collector on the surface of the anode of the cell structure.
  • a stainless steel anode-side separator was laminated.
  • a metal mesh X1 having a corrosion-resistant layer was laminated as a cathode current collector on the surface of the cathode, and a stainless steel cathode side separator having a gas flow path was further laminated. Except for this, a fuel cell Y3 was obtained in the same manner as the fuel cell Y1 of Example 1.
  • Example 2 A fuel cell using a Ni metal mesh X2 on which no corrosion-resistant layer was formed as a cathode current collector was produced in the same manner as in Example 2 to obtain a fuel cell Y4. The deterioration rate of the fuel cell Y4 was evaluated in the same manner as in Example 2.
  • the fuel cell Y5 by increasing the thickness of the cathode, a part of the cathode material located on the cathode side separator functions as a cathode current collector.
  • the thickness of the fired cathode was 50 ⁇ m.
  • the LSCF layer having a thickness of 40 ⁇ m on the side in contact with the cathode side separator corresponds to the cathode current collector.
  • the deterioration rate of the fuel cell Y5 was evaluated in the same manner as in Example 2.
  • the internal resistance increases greatly as the cumulative operation time becomes longer. This is because the operating temperature of the fuel cell is high (900 ° C.), and the fuel cell is operated at a high fuel utilization rate, so the area around the anode and the anode current collector is locally in an oxidizing atmosphere, This is probably because the surface of the Ni mesh used as the anode current collector was oxidized and the resistance increased.
  • the fuel cell Y1 an increase in internal resistance is suppressed even during a long cumulative operation. This is probably because the Ni—Sn mesh provided with the corrosion-resistant layer is used, so that the corrosion resistance and oxidation resistance are high, and the current collector is suppressed from being oxidized.
  • the fuel cells Y1 and Y2 after the evaluation were disassembled, the anode current collector was taken out, and the surface was observed.
  • the Ni metal mesh X2 was oxidized to form nickel oxide.
  • oxidation of nickel in the mesh X1 was not observed.
  • the internal resistance increases greatly as the cumulative operation time becomes longer. This is probably because the fuel cell Y4 has an oxidizing atmosphere around the cathode and the cathode current collector, so that the surface of the Ni mesh used as the cathode current collector was oxidized and the resistance increased. Regarding the fuel cell Y5, it is considered that a part of the LSCF functioning as the cathode current collector was broken and dropped due to thermal shock as the operation and the stop were repeated.
  • the metal mesh has a thermal shock resistance and is a Ni—Sn mesh provided with a corrosion resistant layer, so that the corrosion resistant layer suppresses oxidation of Ni.
  • the surface of the Ni metal mesh X2 was oxidized to form nickel oxide.
  • oxidation of nickel in the metal mesh X1 was not observed.
  • the fuel cell according to the present embodiment is suitable for use in SOFC and can realize SOFC with low internal resistance during operation.

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Abstract

L'invention concerne une pile à combustible comprenant : une structure de pile qui comprend une cathode, une anode et une couche d'électrolyte solide disposée entre la cathode et l'anode ; un séparateur côté cathode qui est opposé à la cathode ; et un séparateur côté anode qui est opposé à l'anode, la structure de pile étant maintenue entre le séparateur côté cathode et le séparateur côté anode, le séparateur côté cathode et le séparateur côté anode présentent chacun des trajets d'écoulement de gaz, un collecteur est disposé entre le séparateur côté anode et l'anode et/ou entre le séparateur côté cathode et la cathode, le collecteur est un treillis métallique formé à partir d'un fil tissé, et le fil a une couche résistante à la corrosion.
PCT/JP2019/000491 2018-02-27 2019-01-10 Pile à combustible WO2019167437A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002216807A (ja) * 2000-11-16 2002-08-02 Mitsubishi Materials Corp 固体電解質型燃料電池の空気極集電体
JP2012119126A (ja) * 2010-11-30 2012-06-21 Magunekusu Kk 固体酸化物燃料電池
JP2013093271A (ja) * 2011-10-27 2013-05-16 Sumitomo Electric Ind Ltd 多孔質集電体及びこれを用いた燃料電池
JP2015060643A (ja) * 2013-09-17 2015-03-30 住友電気工業株式会社 燃料電池
WO2015137102A1 (fr) * 2014-03-12 2015-09-17 住友電気工業株式会社 Collecteur poreux, pile à combustible et procédé de fabrication de collecteur poreux
WO2015151645A1 (fr) * 2014-03-31 2015-10-08 住友電気工業株式会社 Collecteur poreux et pile à combustible

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002216807A (ja) * 2000-11-16 2002-08-02 Mitsubishi Materials Corp 固体電解質型燃料電池の空気極集電体
JP2012119126A (ja) * 2010-11-30 2012-06-21 Magunekusu Kk 固体酸化物燃料電池
JP2013093271A (ja) * 2011-10-27 2013-05-16 Sumitomo Electric Ind Ltd 多孔質集電体及びこれを用いた燃料電池
JP2015060643A (ja) * 2013-09-17 2015-03-30 住友電気工業株式会社 燃料電池
WO2015137102A1 (fr) * 2014-03-12 2015-09-17 住友電気工業株式会社 Collecteur poreux, pile à combustible et procédé de fabrication de collecteur poreux
WO2015151645A1 (fr) * 2014-03-31 2015-10-08 住友電気工業株式会社 Collecteur poreux et pile à combustible

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