WO2017191787A1 - Method for manufacturing fuel cell, and fuel cell - Google Patents

Method for manufacturing fuel cell, and fuel cell Download PDF

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Publication number
WO2017191787A1
WO2017191787A1 PCT/JP2017/016466 JP2017016466W WO2017191787A1 WO 2017191787 A1 WO2017191787 A1 WO 2017191787A1 JP 2017016466 W JP2017016466 W JP 2017016466W WO 2017191787 A1 WO2017191787 A1 WO 2017191787A1
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WO
WIPO (PCT)
Prior art keywords
temperature
insulating member
fuel cell
power generation
cell
Prior art date
Application number
PCT/JP2017/016466
Other languages
French (fr)
Japanese (ja)
Inventor
村田　貴
Original Assignee
住友精密工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友精密工業株式会社 filed Critical 住友精密工業株式会社
Priority to JP2018515704A priority Critical patent/JP6605721B2/en
Publication of WO2017191787A1 publication Critical patent/WO2017191787A1/en

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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
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/2484—Details of groupings of fuel cells characterised by external manifolds
    • H01M8/2485—Arrangements for sealing external manifolds; Arrangements for mounting external manifolds around a stack
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a fuel cell manufacturing method and a fuel cell.
  • fuel cells are known.
  • a pair of interconnectors, a cell body provided between the pair of interconnectors, and an air flow path and a fuel flow path are joined to the upper surface of the outer edge of the cell body.
  • a fuel cell comprising a separator that shuts off the battery is disclosed.
  • plate-shaped gas seal portions are provided on the air electrode side and the fuel electrode side of the separator, respectively.
  • the gas seal part is comprised with the mica (mica), for example.
  • a fuel cell described in Japanese Patent Application Laid-Open No. 2013-20886 also discloses a fuel cell including a pair of interconnectors and a seal member and an electrolyte electrode assembly provided between the pair of interconnectors.
  • the seal member is made of mica, for example.
  • the present invention has been made to solve the above-described problems, and one object of the present invention is a fuel cell capable of suppressing cell deterioration caused by air entering from the outside during shutdown. And a fuel cell.
  • a method of manufacturing a fuel cell according to a first aspect of the present invention includes a cell having an anode formed on one surface and a cathode formed on the other surface, and surrounding the outside of the cell.
  • a plurality of power generation units each of which is provided and includes an insulating member having ceramic particles and amorphous glass, which suppresses mixing of fuel gas supplied to the anode and oxidant supplied to the cathode.
  • the fuel gas is provided so as to surround the outside of the cell, and the fuel gas supplied to the anode and the oxidant supplied to the cathode are mixed. And a step of laminating a plurality of power generation units including an insulating member having ceramic particles and amorphous glass.
  • the insulating member is configured to have ceramic particles and amorphous glass, the insulating member is not cleaved unlike the case where the insulating member is made of mica.
  • the insulating member has ceramic particles, the thickness of the insulating member is suppressed from becoming smaller than a predetermined thickness. Accordingly, it is possible to prevent the insulation from being unable to be ensured due to the reduction in the thickness of the insulating member, and it is possible to ensure the thickness so that the thickness of the power generation unit does not become too small. Moreover, even when the glass is softened by raising the temperature of the power generation unit, excessive flow of the glass can be suppressed by the ceramic particles. Moreover, since the insulating member has an amorphous glass, even when the insulating member has a crack, the crack is repaired by melting the glass by raising the temperature of the power generation unit. Can do. As a result, cracks can be eliminated.
  • the temperature of the plurality of stacked power generation units is raised to a second temperature lower than the first temperature prior to raising the temperature to the first temperature.
  • the method further includes the step of removing the binder from the insulating member before the temperature is raised to the first temperature. If comprised in this way, since it heats up or heats the laminated
  • the step of removing the binder includes a step of removing the binder contained in the insulating member before the temperature rise by maintaining a second temperature lower than the temperature at which the glass softens. If comprised in this way, since 2nd temperature is lower than the temperature which glass softens, a binder can be removed before glass softens.
  • the thermal decomposition start temperature or the burnout start temperature of the binder is lower than the temperature at which the glass softens. If comprised in this way, a binder can be easily removed before glass softens.
  • the step of removing the binder is performed on the insulating member after the step of removing the binder by removing the binder from the insulating member before raising the temperature to the first temperature.
  • the weight percent of the ceramic particles contained is 5 wt% or more and 30 wt% or less.
  • the weight percentage of the ceramic particles is too small, the flow of the glass becomes too large when the power generation unit is heated to soften the glass. That is, since the insulating member cannot withstand the load and the insulating member is crushed, the thickness adjusting member disposed below the anode of the cell is also crushed excessively.
  • the weight percentage of the ceramic particles is too large, even if the power generation unit is heated to soften the glass, the glass does not flow so much that cracks occur and it is difficult to adjust the thickness of the insulating member. Therefore, as described above, by setting the weight percent of the ceramic particles contained in the insulating member to 5 wt% or more and 30 wt% or less, excessive flow of the glass is suppressed, and therefore the insulating member is crushed. Excessive crushing of the thickness adjusting member to be performed can be suppressed. Moreover, generation
  • the method of manufacturing a fuel cell including the step of removing the binder, preferably provided between the step of adjusting the thickness of the insulating member and the step of removing the binder, while heating the plurality of stacked power generation units,
  • the method further includes a step of suppressing contraction of the insulating member by applying a second load smaller than the first load to a plurality of power generation units adjacent to each other in the stacking direction in a direction adjacent to each other. If comprised in this way, since a 2nd load is applied from the both sides of an insulating member, the deformation
  • the step of suppressing the shrinkage of the insulating member includes a step of applying a second load to the plurality of power generation units before the glass contained in the insulating member softens. If comprised in this way, since a 2nd load is applied before glass softens, the deformation
  • the power generation unit further includes a metal thickness adjusting member provided on the anode side of the cell, and after the step of removing the binder, The thickness of the oxidized thickness adjusting member is reduced by placing the thickness adjusting member under an atmosphere of reducing gas while raising the temperature to a third temperature that is higher than the first temperature and lower than the first temperature.
  • the method further includes a step of reducing the hardness of the adjustment member. If comprised in this way, since the hardness of a thickness adjustment member will become small, when adjusting the thickness of an insulating member by applying a 1st load, the thickness of a thickness adjustment member can also be adjusted. That is, the thickness of the power generation unit including the thickness adjusting member can be adjusted.
  • the particle size of the ceramic particles contained in the insulating member before the temperature rise is 10 ⁇ m or less. If comprised in this way, it can suppress that it becomes difficult to adjust the thickness of an insulating member resulting from the particle size of a ceramic particle being too large. That is, it becomes possible to prevent the thickness from being reduced.
  • a fuel cell according to a second aspect of the present invention includes a plurality of stacked power generation units, and the power generation unit includes a cell having an anode formed on one surface and a cathode formed on the other surface, and an outer side of the cell. And an insulating member having ceramic particles and amorphous glass that suppresses mixing of the fuel gas supplied to the anode and the oxidant supplied to the cathode.
  • the power generation unit is provided so as to surround the outside of the cell, and the fuel gas supplied to the anode and the oxidant supplied to the cathode are mixed. And an insulating member having ceramic particles and amorphous glass.
  • the insulating member is configured to have ceramic particles and amorphous glass, the insulating member is not cleaved unlike the case where the insulating member is made of mica.
  • the air passes through the insulating member from the outside of the fuel cell. never invade.
  • the insulating member has ceramic particles, it is possible to secure the thickness of the power generation unit, suppress excessive flow of glass, and repair cracks.
  • the insulating member preferably contains 5% by weight or more and 30% by weight or less of ceramic particles. If comprised in this way, since the excessive flow of glass is suppressed, the collapse of the thickness adjustment member resulting from a collapse of an insulating member can be suppressed. Moreover, generation
  • the power generation unit preferably further includes a metal thickness adjusting member provided on the anode side of the cell. If comprised in this way, the thickness of an electric power generation unit can be adjusted easily, ensuring the conduction
  • the elastic member is disposed on one end side in the stacking direction of the plurality of stacked power generation units and presses the cell toward the other end side in the stacking direction. Is further provided. If comprised in this way, since the contact failure with the cell each contained in the laminated
  • the insulating member preferably has a frame shape so as to surround the outside of the cell. If comprised in this way, an insulating member can be easily arrange
  • FIG. 1 is an exploded perspective view of a fuel cell according to an embodiment of the present invention. It is a disassembled perspective view of the electric power generation unit by one Embodiment of this invention. It is a disassembled perspective view of the separator by one Embodiment of this invention. It is typical sectional drawing of the fuel cell by one Embodiment of this invention. It is a typical sectional view of an insulating member by one embodiment of the present invention. It is typical sectional drawing of the insulating member before temperature rising by one Embodiment of this invention. It is a figure for demonstrating the manufacturing method of the fuel cell (cell stack) by one Embodiment of this invention.
  • the fuel cell 100 is a solid oxide fuel cell (SOFC).
  • SOFC solid oxide fuel cell
  • the fuel cell 100 is configured by stacking a plurality of power generation units 10.
  • the power generation unit 10 is configured to flow so that the fuel gas and the oxidant (air) face each other (counter flow).
  • the separator 20 As shown in FIG. 2, in the power generation unit 10, from the lower side (Z2 direction side), the separator 20, the insulating member 30, the foamed nickel 40 that is a metal porous body, the cell 50, and the cell presser 60 are They are stacked in this order.
  • the nickel foam 40 is an example of the “thickness adjusting member” in the claims.
  • the current collecting plate 21, the cathode plate 22, the separator body 23, the anode plate 24, and the cell holder 25 are stacked in this order from the lower side (Z2 direction side). Has been.
  • the current collecting plate 21 is configured to be in contact with the cathode 53 of the cell 50 (see FIG. 4).
  • the current collecting plate 21 is provided with a hole 21a through which fuel gas flows, and a hole 21b and hole 21c through which an oxidant flows.
  • the current collecting plate 21 is provided with a plurality of holes 21 d for guiding the oxidant to the cathode 53.
  • the cathode plate 22 is provided with a hole 22a through which the fuel gas flows, and a hole 22b and a hole 22c through which the oxidant flows.
  • the cathode plate 22 is provided with an oxidant flow path 22d along the X direction. Specifically, the oxidant flows on the lower surface side (Z2 direction side) of the flow path 22d.
  • the separator body 23 is provided with a hole 23a through which the fuel gas flows, and a hole 23b and a hole 23c through which the oxidant flows. Further, the surface of the separator body 23 is formed into a flat surface.
  • the anode plate 24 is provided with a hole 24a (and a hole 24d) through which fuel gas flows, and a hole 24b and a hole 24c through which oxidant flows.
  • the anode plate 24 is provided with a fuel gas flow path 24e along the X direction. The fuel gas flows through the upper surface side of the flow path 24e.
  • the current collecting plate 21, the cathode plate 22, the separator body 23, and the anode plate 24 are formed of conductive members.
  • the cell holder 25 is provided with a hole 25a through which fuel gas flows, and a hole 25b and hole 25c through which an oxidant flows. In addition, an opening 25d is provided at the center of the cell holder 25.
  • the insulating member 30 is provided with a hole 30e through which the fuel gas flows, and a hole 30b and a hole 30c through which the oxidant flows.
  • the insulating member 30 has a frame shape so as to surround the outside of the cell 50 (see FIG. 4).
  • An opening 30 d is provided at the center of the insulating member 30.
  • the insulating member 30 mixes the fuel gas supplied to the anode 51 through the hole 30e (opening 30d) and the oxidant supplied to the cathode 53 through the holes 30b and 30c. It is comprised so that this may be suppressed.
  • the insulating member 30 is configured to insulate between the cells 50 adjacent in the stacking direction.
  • the foamed nickel 40 is provided on the anode 51 side (Z2 direction side) of the cell 50.
  • the foamed nickel 40 has a substantially rectangular shape, and has substantially the same size (area) as an anode 51 and a solid electrolyte layer 52 described later of the cell 50.
  • the cell 50 includes an anode 51, a solid electrolyte layer 52, and a cathode 53.
  • the cathode 53 is formed on the surface on the Z1 direction side
  • the anode 51 is formed on the surface opposite to the surface on which the cathode 53 is formed (surface on the Z2 direction side).
  • the anode 51 is provided on substantially the entire surface of the solid electrolyte layer 52 on the Z2 direction side.
  • the cathode 53 is provided on a part of the surface of the solid electrolyte layer 52 on the Z1 direction side.
  • the cell retainer 60 is provided with a hole 60a through which the fuel gas flows, and a hole 60b and a hole 60c through which the oxidant flows.
  • an opening 60d is provided at the center of the cell presser 60.
  • the cell 50 is arrange
  • the cell retainer 60 is disposed so as to straddle the insulating member 30 and the solid electrolyte layer 52.
  • the cathode 53 is exposed from the opening 60 d of the cell presser 60.
  • the cathode 53 is electrically connected to the upper current collecting plate 21.
  • a separator 20a including a top plate but not including an anode plate is provided on the upper surface of the power generation unit 10 disposed at the uppermost position.
  • a separator 20b that includes a bottom plate but does not include a cathode plate is provided on the lower surface of the power generation unit 10 that is disposed at the lowermost position.
  • the fuel gas supplied to the anode 51 of the cell 50 flows from the hole 23 a on the X1 direction side of the separator body 23 to the upper surface side of the anode plate 24 through the hole 24 d of the anode plate 24. It flows into (Z1 direction side surface side).
  • the reacted fuel gas flows out through the hole 24a on the X2 direction side of the anode plate 24.
  • the oxidant (air) supplied to the cathode 53 of the cell 50 flows into the upper surface side (the lower surface side of the cathode plate 22) of the current collecting plate 21 from the hole 22 b on the X2 direction side of the cathode plate 22.
  • the oxidant after the reaction flows out through the hole 21c on the X1 direction side of the current collecting plate 21.
  • a cell stack 70 is constituted by a plurality of stacked power generation units 10.
  • a plurality of cell stacks 70 are stacked.
  • the elastic member 80 is arranged on one end side in the stacking direction of the cell stack 70 (the plurality of stacked power generation units 10) and presses the cell 50 toward the other end side in the stacking direction. Is provided.
  • the elastic member 80 is disposed between the stacked cell stacks 70 (the plurality of power generation units 10) so as to overlap the cells 50 of the power generation unit 10 in plan view.
  • the elastic member 80 has a substantially rectangular shape in plan view.
  • the elastic member 80 includes a ceramic fiber mat. The elastic member 80 presses the cell 50 when the fuel cell 100 is actually used after the cell stack 70 is completed, not when the fuel cell 100 (cell stack 70) described later is manufactured.
  • the intermediate member is disposed between the stacked cell stacks 70 (the plurality of power generation units 10) so as not to overlap the elastic member 80 on the outer peripheral side of the cell 50, and is an intermediate member that is harder than the elastic member 80.
  • a plate 81 is provided.
  • the intermediate plate 81 is made of metal harder than the elastic member 80 (for example, SUS: tainless steel).
  • the intermediate plate 81 has a frame shape, and the elastic member 80 is disposed in the opening 81 a of the frame-shaped intermediate plate 81.
  • an insulating intermediate insulating plate 82 is provided between the intermediate plate 81 and the cell stack 70 disposed below.
  • the intermediate insulating plate 82 is made of crystallized glass, for example. Crystallized glass is glass formed by reheating glass to precipitate crystals.
  • the intermediate insulating plate 82 has a frame shape, and the elastic member 80 is disposed in the opening 82 a of the frame-shaped intermediate insulating plate 82. That is, the opening 81a of the intermediate plate 81 and the opening 82a of the intermediate insulating plate 82 are provided so as to communicate with each other, and the elastic member 80 is disposed so as to straddle the opening 81a and the opening 82a. Yes.
  • the set of the elastic member 80, the intermediate plate 81, and the intermediate insulating plate 82 is disposed at a plurality of locations (between the cell stacks 70).
  • An end plate 83 is provided between the upper surface of the uppermost cell stack 70 and the set of the elastic member 80, the intermediate plate 81, and the intermediate insulating plate 82.
  • An insulating member 84 is provided on the upper surface of the set of the uppermost elastic member 80, the intermediate plate 81 and the intermediate insulating plate 82.
  • the insulating member 84 is made of mica, for example.
  • a pressing plate 90 is provided on the upper surface of the insulating member 84. Further, the pressing plate 90 is made of metal harder than the elastic member 80 (for example, SUS: Stainless steel).
  • a pressure member 91 for pressing the pressure plate 90 is provided on the upper surface of the pressure plate 90.
  • the pressurizing member 91 is composed of a plurality (five in this embodiment) of spring members 91a made of ceramic. The four corners of the substantially rectangular pressing plate 90 are pressed by the four spring members 91a, and the central portion of the approximately rectangular pressing plate 90 is pressed by the one spring member 91a.
  • the pressing plate 90 is provided with a recess 90a in which the spring member 91a is disposed.
  • a spring pressing plate 92 that presses the pressing member 91 (spring member 91a) is disposed above the pressing member 91 (Z1 direction side).
  • the spring pressing plate 92 is provided with a plurality of through holes 92a into which a plurality of rod-shaped members 93 are inserted.
  • the lower end of the rod-shaped member 93 is configured to be fixed to a rigid plate (not shown) or the like.
  • a plurality of rod-like members 93 are inserted into the through holes 92a of the spring pressing plate 92, the lower end is fixed, and the nut 94 is fastened to the upper end, whereby the spring pressing plate 92 is pressed downward.
  • the spring member 91 a is pressed, and the cell 50 is pressed via the pressing plate 90 and the elastic member 80.
  • an insulating member 95 made of, for example, crystallized glass is disposed below the cell stack 70 located at the lowest position.
  • the insulating member 95 is made of crystallized glass, for example.
  • the insulating member 30 includes ceramic particles 32 and amorphous glass 33. Specifically, the insulating member 30 includes 5 wt% or more and 30 wt% or less of ceramic particles 32.
  • the ceramic particles 32 are made of, for example, zirconia (zirconium dioxide: ZnO 2 ). In FIG. 5, the size of the ceramic particles 32 is emphasized and is larger than the actual size.
  • a cell stack 70 is configured by stacking a plurality of power generation units 10. As shown in FIG. 2, in the power generation unit 10, the separator 20, the insulating member 30, the foamed nickel 40, the cell 50, and the cell presser 60 are stacked in this order.
  • the insulating member 30 includes ceramic particles 32 and amorphous glass 33.
  • the insulating member 30 (insulating member 30a before the temperature rise) includes ceramic particles 32, glass 33, and a binder 34.
  • the particle size p of the ceramic particles 32 included in the insulating member 30a before the temperature rise is 10 ⁇ m or less.
  • the binder 34 is made of, for example, an acrylic copolymer.
  • the cell stack 70 (a plurality of stacked power generation units 10) is heated (heated) between time t0 and time t1.
  • the cell stack 70 is heated in an air atmosphere.
  • the cell stack 70 is heated in the air atmosphere from time t0 to time t4 described later.
  • the temperature prior to raising the temperature of the stacked power generation units 10 (cell stack 70) to a temperature T4 described later, the temperature is raised to a temperature T1 lower than the temperature T4, and the temperature T4 is increased.
  • the binder 34 in the insulating member 30a before the temperature rise is removed. Specifically, at time t1, the cell stack 70 is heated to the temperature T1. The temperature of the cell stack 70 is maintained at T1 between time t1 and time t2. Thereby, the binder 34 contained in the insulating member 30a is removed.
  • the temperature T4 is an example of the “first temperature” in the claims.
  • the temperature T1 is an example of the “second temperature” in the claims.
  • the binder 34 contained in the insulating member 30a before the temperature rise is removed by maintaining the temperature T1 lower than the temperature T2 at which the glass 33 softens. Specifically, the binder 34 is thermally decomposed and removed from the insulating member 30a. Further, the thermal decomposition start temperature or burnout start temperature of the binder 34 is lower than the temperature T2 at which the glass 33 is softened. Thereby, the glass 33 is not softened at the time t2.
  • the binder 34 is removed from the insulating member 30a before the temperature is raised to the temperature T4, so that the weight% of the ceramic particles 32 contained in the insulating member 30 after the step of removing the binder 34 is 5% by weight or more. 30% by weight or less. That is, the weight of the ceramic particles 32 with respect to the weight of the insulating member 30 after the binder 34 is removed (the weight of the ceramic particles 32 + the weight of the glass 33) is 5% or more and 30% or less.
  • a load F2 (to be described later) is used while increasing the temperature of the plurality of stacked power generation units 10 between the step of adjusting the thickness t of the insulating member 30 to be described later and the step of removing the binder 34. Is applied to the plurality of power generation units 10 adjacent to each other in the stacking direction. Thereby, contraction of the insulating member 30 is suppressed. Specifically, at time t2, the plurality of power generation units 10 are heated from the temperature T1. At time t2, a load F1 is applied to the plurality of power generation units 10. The state where the load F1 is applied is maintained from time t2 to time t5 described later.
  • the load F2 and the load F1 are examples of the “first load” and the “second load” in the claims, respectively.
  • the temperature of the plurality of power generation units 10 heated from time t2 reaches the temperature T2 at which the glass 33 softens at time t3.
  • the glass 33 contained in the insulating member 30 begins to soften at the time t3.
  • the glass 33 flows and the insulating member 30 is deformed. Therefore, in the present embodiment, the deformation of the insulating member 30 is suppressed by applying the load F1 to the plurality of power generation units 10 before the glass 33 included in the insulating member 30 is softened (time t2).
  • the plurality of power generation units 10 are heated to a temperature T3 that is higher than the temperature T1 and lower than a temperature T4 that will be described later.
  • reducing gas H 2 gas flow rate M1
  • H 2 gas flow rate M1 is placed under an atmosphere of.
  • the foamed nickel 40 is placed in an atmosphere of a reducing gas (H 2 gas), whereby the foamed nickel 40 in an oxidized state is reduced. And the hardness of the foaming nickel 40 becomes small.
  • the temperature T3 is an example of the “third temperature” in the claims.
  • the temperature of the power generation unit 10 (cell stack 70) reaches T3, and the state of temperature T3 is maintained until time t5.
  • the atmosphere is replaced with N 2 , and the power generation unit 10 is placed in an atmosphere of reducing gas (H 2 gas).
  • H 2 gas reducing gas
  • the foamed nickel 40 before being placed in the reducing gas (H 2 gas) atmosphere is oxidized, and the nickel in the oxidized state contained in the foamed nickel 40 by the reducing gas (H 2 gas). Is reduced to metallic nickel. Thereby, the hardness of the foamed nickel 40 becomes small.
  • the temperature of the plurality of stacked power generation units 10 is increased, and a load F2 is applied to the plurality of power generation units 10 adjacent to each other in the stacking direction so as to approach each other.
  • the thickness t is adjusted. Specifically, at time t5, the temperatures of the plurality of power generation units 10 are T3. At time t5, the flow rate of the reducing gas (H 2 gas) is decreased from M1 to M2. Then, a load F2 is applied to the plurality of power generation units 10 (cell stack 70) from time t5. Then, with the load F2 applied, the plurality of power generation units 10 are heated, and at time t6, the temperatures of the plurality of power generation units 10 become T4.
  • the temperature of the plurality of power generation units 10 is maintained at T4 with the load F2 applied until time t7. Since the temperature T4 is higher than the temperature T2 at which the glass 33 is softened, the glass 33 remains in a softened state from time t5, which is the time when the load F2 starts to be applied, to time t7. Thereby, the thickness t of the insulating member 30 can be adjusted.
  • the thickness t of the insulating member 30 is reduced from the thickness t1 in FIG. 7 to the thickness t2 in FIG.
  • the thickness of the foamed nickel 40 is also adjusted by the load F2. That is, the entire thickness of the plurality of power generation units 10 is adjusted by the load F2. That is, the thickness of each power generation unit 10 is adjusted.
  • the plurality of power generation units 10 are cooled. Specifically, the temperatures of the plurality of power generation units 10 are decreased stepwise from time t7 to time t8. Thereby, the several electric power generation unit 10 (cell stack 70) is completed.
  • the ceramic particles are provided so as to surround the outside of the cell 50 and suppress mixing of the fuel gas supplied to the anode 51 and the oxidant supplied to the cathode 53.
  • the insulating member 30 is configured to have the ceramic particles 32 and the amorphous glass 33, the insulating member 30 is cleaved unlike the case where the insulating member 30 is made of mica. There is no.
  • the insulating member 30 is passed through the insulating member 30 from the outside of the fuel cell 100. Air does not enter the fuel cell 100. As a result, it is possible to suppress the deterioration of the cell 50 due to air entering from the outside during shutdown.
  • the thickness t of the insulating member 30 is suppressed from being smaller than a predetermined thickness. Accordingly, it is possible to prevent the insulation from being unable to be ensured due to the decrease in the thickness t of the insulating member 30 and to secure the thickness so that the thickness of the power generation unit 10 is not too small. it can. Moreover, even when the glass 33 is softened by raising the temperature of the power generation unit 10, excessive flow of the glass 33 can be suppressed by the ceramic particles 32. In addition, since the insulating member 30 includes the amorphous glass 33, even when the insulating member 30 has cracks, the glass 33 is melted by raising the temperature of the power generation unit 10. Cracks can be repaired. As a result, cracks can be eliminated.
  • the temperature prior to raising the temperature of the plurality of stacked power generation units 10 to the temperature T4, the temperature is raised to the temperature T1 lower than the temperature T4, and the temperature is raised to the temperature T4.
  • a step of removing the binder 34 from the previous insulating member 30a is provided. Thereby, since the binder 34 is burnt down or thermally decomposed by raising the temperature of the stacked power generation units 10 to the temperature T1, the insulating member having the amorphous glass 33 and the ceramic particles 32 can be easily obtained. 30 can be formed.
  • the binder 34 contained in the insulating member 30a before the temperature rise is removed by maintaining the temperature T1 lower than the temperature T2 at which the glass 33 softens. Thereby, since the temperature T1 is lower than the temperature T2 at which the glass 33 is softened, the binder 34 can be removed before the glass 33 is softened.
  • the thermal decomposition start temperature or burnout start temperature of the binder 34 is lower than the temperature T2 at which the glass 33 softens. Thereby, the binder 34 can be easily removed before the glass 33 is softened.
  • the binder 34 is removed from the insulating member 30a before the temperature is raised to the temperature T4, so that the weight% of the ceramic particles 32 included in the insulating member 30 after the step of removing the binder 34 is reduced. 5 wt% or more and 30 wt% or less.
  • the weight percentage of the ceramic particles 32 is too small, the flow of the glass 33 becomes too large when the temperature of the power generation unit 10 is raised and the glass 33 is softened. That is, since the insulating member 30 cannot withstand the load and is crushed, the foamed nickel 40 disposed below the anode 51 of the cell 50 is also crushed excessively.
  • the weight percentage of the ceramic particles 32 is too large, even if the power generation unit 10 is heated and the glass 33 is softened, the flow of the glass 33 is small so that cracks occur and the thickness t of the insulating member 30 is adjusted. It becomes difficult to do. Therefore, as described above, by setting the weight% of the ceramic particles 32 included in the insulating member 30 to 5 wt% or more and 30 wt% or less, it is possible to suppress the flow of the glass 33 from being excessively increased. Excessive crushing of the foamed nickel 40 caused by the member 30 being crushed can be suppressed. Moreover, generation
  • the load is provided between the step of adjusting the thickness t of the insulating member 30 and the step of removing the binder 34 while raising the temperature of the plurality of stacked power generation units 10.
  • a step of suppressing contraction of the insulating member 30 by applying a load F1 smaller than F2 to a plurality of power generation units 10 adjacent to each other in the stacking direction in a direction adjacent to each other is provided.
  • the load F1 is applied to the plurality of power generation units 10 before the glass 33 included in the insulating member 30 is softened.
  • the load F1 is applied before the glass 33 softens, the deformation
  • the temperature is raised to a temperature T3 that is higher than the temperature T1 and lower than the temperature T4, and the foamed nickel 40 is placed in an atmosphere of reducing gas.
  • the step of reducing the hardness of the foamed nickel 40 by reducing the foamed nickel 40 in an oxidized state by arranging the foamed nickel 40 is provided.
  • the particle size p of the ceramic particles 32 contained in the insulating member 30 before the temperature rise is 10 ⁇ m or less. Therefore, it can be suppressed that the adjustment of the thickness t of the insulating member 30 is difficult due to the particle size p of the ceramic particles 32 being too large. That is, it is possible to prevent the thickness t from being reduced.
  • the power generation unit 10 includes the metallic foamed nickel 40 provided on the anode 51 side of the cell 50. Thereby, the thickness of the power generation unit 10 can be easily adjusted while ensuring conduction between the cells 50 by the metallic foamed nickel 40.
  • the elastic member 80 is disposed on one end side in the stacking direction of the plurality of stacked power generation units 10 and presses the cell 50 toward the other end side in the stacking direction. Is provided. Thereby, since the poor contact between the cell 50 included in each of the plurality of stacked power generation units 10 and the separator 20 (the member disposed between the cells 50 included in each adjacent power generation unit 10) is suppressed, An increase in the contact resistance between the cell 50 and the separator 20 can be suppressed.
  • the insulating member 30 has a frame shape so as to surround the outside of the cell 50. Thereby, the insulating member 30 can be easily disposed so as to surround the outside of the cell 50.
  • the fuel cell is a solid oxide fuel cell (SOFC)
  • SOFC solid oxide fuel cell
  • the fuel cell is a fuel cell other than a solid oxide fuel cell, such as a polymer electrolyte fuel cell (PEFC), a phosphoric acid fuel cell (PAFC), a molten carbonic acid fuel cell.
  • PEFC polymer electrolyte fuel cell
  • PAFC phosphoric acid fuel cell
  • MCFC Molten Carbonate Fuel Cell
  • the insulating member includes zirconia as the ceramic particles
  • the present invention is not limited to this.
  • the insulating member may contain substances other than zirconia such as alumina (aluminum oxide) as ceramic particles.
  • the thickness of the insulating member may be adjusted by applying a one-stage load while suppressing deformation of the insulating member.
  • the present invention is not limited to this.
  • a thickness adjusting member other than the foamed nickel may be used.
  • the elastic member is made of a ceramic fiber mat (sheet) made of alumina.
  • the present invention is not limited to this.
  • the elastic member may be constituted by a member other than a ceramic fiber mat (sheet) made of alumina.
  • the cell is pressed by the spring member via the elastic member, but the present invention is not limited to this.
  • the cell may be pressed via an elastic member by a member other than a spring member such as a cushion material or a mat.
  • the fuel cell (power generation unit) is a counter flow fuel cell in which the fuel gas and the air flow so as to face each other.
  • the present invention is not limited to this.
  • the present invention can be applied to a cross-flow fuel cell in which fuel gas and air flow so as to intersect each other.

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Abstract

This method for manufacturing a fuel cell (100) is provided with a step in which a plurality of power generation units (10) are heated to a first temperature (T4), and a first load (F2) is applied to adjacent pairs among the plurality of power generation units (10) in mutually approaching directions, whereby the thickness (t) of an insulating member (30) is adjusted.

Description

燃料電池の製造方法および燃料電池Fuel cell manufacturing method and fuel cell
　この発明は、燃料電池の製造方法および燃料電池に関する。 The present invention relates to a fuel cell manufacturing method and a fuel cell.
　従来、燃料電池が知られている。国際公開第２０１１／１４８７６９号には、一対のインターコネクタと、一対のインターコネクタの間に設けられる、セル本体と、セル本体の外縁部の上面に接合して、空気流路と燃料流路とを遮断するセパレータとを備える燃料電池が開示されている。また、セパレータの空気極側と燃料極側とには、それぞれ、板形状のガスシール部が設けられている。また、ガスシール部は、たとえば、マイカ（雲母）により構成されている。 Conventionally, fuel cells are known. In International Publication No. 2011/148769, a pair of interconnectors, a cell body provided between the pair of interconnectors, and an air flow path and a fuel flow path are joined to the upper surface of the outer edge of the cell body. A fuel cell comprising a separator that shuts off the battery is disclosed. In addition, plate-shaped gas seal portions are provided on the air electrode side and the fuel electrode side of the separator, respectively. Moreover, the gas seal part is comprised with the mica (mica), for example.
　また、特開２０１３－２０８８６号公報に記載の燃料電池にも、一対のインターコネクタと、一対のインターコネクタの間に設けられる、シール部材および電解質電極接合体とを備える燃料電池が開示されている。また、シール部材は、たとえば、マイカにより構成されている。 Also, a fuel cell described in Japanese Patent Application Laid-Open No. 2013-20886 also discloses a fuel cell including a pair of interconnectors and a seal member and an electrolyte electrode assembly provided between the pair of interconnectors. . Moreover, the seal member is made of mica, for example.
国際公開第２０１１／１４８７６９号International Publication No. 2011/148769 特開２０１３－２０８８６号公報JP 2013-20886 A
　ここで、国際公開第２０１１／１４８７６９号および特開２０１３－２０８８６号公報に記載のような従来の燃料電池において、燃料電池がシャットダウンされた際、燃料電池の温度が低下する。このため、燃料電池内の空気の体積が小さくなる。そして、ガスシール部（シール部材）をマイカにより構成した場合、マイカはケイ素塩が積層された層状構造を有するため、劈開しやすい。このため、燃料電池内の空気の体積が小さくなり、燃料電池内の気圧が小さくなることに起因して、燃料電池の外部から薄いマイカの層の間の隙間を介して、空気が燃料電池内に侵入するという不都合がある。このため、シャットダウン時、たとえば４００度以上の高温状態で空気がスタック内に侵入することによりセルが酸化して劣化するという問題点がある。 Here, in the conventional fuel cell as described in International Publication No. 2011/148769 and Japanese Patent Laid-Open No. 2013-20886, when the fuel cell is shut down, the temperature of the fuel cell decreases. For this reason, the volume of the air in a fuel cell becomes small. When the gas seal portion (seal member) is made of mica, the mica has a layered structure in which silicon salts are laminated, and thus is easily cleaved. For this reason, the volume of air in the fuel cell is reduced, and the air pressure in the fuel cell is reduced, so that the air passes through the gap between the thin mica layers from the outside of the fuel cell. There is an inconvenience of entering. For this reason, at the time of shutdown, there exists a problem that a cell oxidizes and deteriorates, when air penetrate | invades into a stack, for example in a high temperature state 400 degreeC or more.
　この発明は、上記のような課題を解決するためになされたものであり、この発明の１つの目的は、シャットダウン時に外部から侵入する空気に起因するセルの劣化を抑制することが可能な燃料電池の製造方法および燃料電池を提供することである。 The present invention has been made to solve the above-described problems, and one object of the present invention is a fuel cell capable of suppressing cell deterioration caused by air entering from the outside during shutdown. And a fuel cell.
　上記目的を達成するために、この発明の第１の局面による燃料電池の製造方法は、一方の表面にアノードが形成され他方の表面にカソードが形成されたセルと、セルの外側を取り囲むように設けられ、アノードに供給される燃料ガスとカソードに供給される酸化剤とが混合するのを抑制する、セラミック粒子と非晶質であるガラスとを有する絶縁部材とを含む発電ユニットを、複数積層する工程と、積層された複数の発電ユニットを第１の温度に昇温するとともに、積層方向に隣接する複数の発電ユニットに、互いに近接する方向に第１の荷重を加えることにより、絶縁部材の厚みを調整する工程と、を備える。 To achieve the above object, a method of manufacturing a fuel cell according to a first aspect of the present invention includes a cell having an anode formed on one surface and a cathode formed on the other surface, and surrounding the outside of the cell. A plurality of power generation units, each of which is provided and includes an insulating member having ceramic particles and amorphous glass, which suppresses mixing of fuel gas supplied to the anode and oxidant supplied to the cathode. And heating the plurality of stacked power generation units to a first temperature and applying a first load in a direction adjacent to each other to the plurality of power generation units adjacent to each other in the stacking direction. And a step of adjusting the thickness.
　この発明の第１の局面による燃料電池の製造方法では、上記のように、セルの外側を取り囲むように設けられ、アノードに供給される燃料ガスと、カソードに供給される酸化剤とが混合するのを抑制する、セラミック粒子と非晶質であるガラスとを有する絶縁部材とを含む発電ユニットを、複数積層する工程を備える。これにより、絶縁部材がセラミック粒子と非晶質であるガラスとを有するように構成されているので、絶縁部材がマイカから構成されている場合と異なり、絶縁部材が劈開することがない。その結果、燃料電池のシャットダウン時に、燃料電池内の温度が低下することにより、燃料電池内の空気の体積が小さくなった場合でも、燃料電池の外部から絶縁部材を介して、空気が燃料電池内に侵入することはない。その結果、シャットダウン時に外部から侵入する空気に起因するセルの劣化を抑制することができる。 In the fuel cell manufacturing method according to the first aspect of the present invention, as described above, the fuel gas is provided so as to surround the outside of the cell, and the fuel gas supplied to the anode and the oxidant supplied to the cathode are mixed. And a step of laminating a plurality of power generation units including an insulating member having ceramic particles and amorphous glass. Thereby, since the insulating member is configured to have ceramic particles and amorphous glass, the insulating member is not cleaved unlike the case where the insulating member is made of mica. As a result, even when the volume of the air in the fuel cell is reduced due to a decrease in the temperature in the fuel cell at the time of shutting down the fuel cell, the air passes through the insulating member from the outside of the fuel cell. Never invade. As a result, it is possible to suppress cell deterioration caused by air entering from the outside during shutdown.
　また、絶縁部材がセラミック粒子を有しているので、絶縁部材の厚みが、所定の厚みよりも小さくなることが抑制される。これにより、絶縁部材の厚みが小さくなることに起因して絶縁性が確保できなくなるのを抑制することができるとともに、発電ユニットの厚みが小さくなり過ぎないように厚みを確保することができる。また、発電ユニットを昇温させることにより、ガラスが軟化した場合でも、ガラスの過度な流動をセラミック粒子により抑制することができる。また、絶縁部材が非晶質であるガラスを有しているので、絶縁部材にクラックが生じている場合でも、発電ユニットを昇温することにより、ガラスが融解することによって、クラックを修復することができる。その結果、クラックをなくすことができる。 Further, since the insulating member has ceramic particles, the thickness of the insulating member is suppressed from becoming smaller than a predetermined thickness. Accordingly, it is possible to prevent the insulation from being unable to be ensured due to the reduction in the thickness of the insulating member, and it is possible to ensure the thickness so that the thickness of the power generation unit does not become too small. Moreover, even when the glass is softened by raising the temperature of the power generation unit, excessive flow of the glass can be suppressed by the ceramic particles. Moreover, since the insulating member has an amorphous glass, even when the insulating member has a crack, the crack is repaired by melting the glass by raising the temperature of the power generation unit. Can do. As a result, cracks can be eliminated.
　上記第１の局面による燃料電池の製造方法において、好ましくは、積層された複数の発電ユニットを第１の温度に昇温するのに先立って、第１の温度よりも低い第２の温度に昇温するとともに、第１の温度に昇温前の絶縁部材からバインダを取り除く工程をさらに備える。このように構成すれば、積層された複数の発電ユニットを第２の温度に昇温することで、バインダが焼失あるいは熱分解するので、容易に、非晶質であるガラスとセラミック粒子とを有する絶縁部材を形成することができる。 In the fuel cell manufacturing method according to the first aspect, preferably, the temperature of the plurality of stacked power generation units is raised to a second temperature lower than the first temperature prior to raising the temperature to the first temperature. The method further includes the step of removing the binder from the insulating member before the temperature is raised to the first temperature. If comprised in this way, since it heats up or heats the laminated | stacked several electric power generation unit to 2nd temperature, a binder will burn out or thermally decompose, Therefore It has an amorphous glass and ceramic particle | grain easily An insulating member can be formed.
　この場合、好ましくは、バインダを取り除く工程は、ガラスが軟化する温度よりも低い第２の温度を維持することにより、昇温前の絶縁部材に含まれるバインダを取り除く工程を含む。このように構成すれば、第２の温度が、ガラスが軟化する温度よりも低いので、ガラスが軟化する前にバインダを取り除くことができる。 In this case, preferably, the step of removing the binder includes a step of removing the binder contained in the insulating member before the temperature rise by maintaining a second temperature lower than the temperature at which the glass softens. If comprised in this way, since 2nd temperature is lower than the temperature which glass softens, a binder can be removed before glass softens.
　上記バインダを取り除く工程を備える燃料電池の製造方法において、好ましくは、バインダの熱分解開始温度または焼失開始温度は、ガラスが軟化する温度よりも低い。このように構成すれば、容易に、ガラスが軟化する前にバインダを取り除くことができる。 In the fuel cell manufacturing method including the step of removing the binder, preferably, the thermal decomposition start temperature or the burnout start temperature of the binder is lower than the temperature at which the glass softens. If comprised in this way, a binder can be easily removed before glass softens.
　上記バインダを取り除く工程を備える燃料電池の製造方法において、好ましくは、バインダを取り除く工程は、第１の温度に昇温前の絶縁部材からバインダを取り除くことにより、バインダを取り除く工程後の絶縁部材に含まれるセラミック粒子の重量％を、５重量％以上３０重量％以下にする。ここで、セラミック粒子の重量％が少な過ぎると、発電ユニットを昇温させてガラスが軟化した場合に、ガラスの流動が大きくなり過ぎる。すなわち、絶縁部材が荷重に耐えることができずに絶縁部材が潰れてしまうので、セルのアノードの下方に配置される厚み調整部材も過度に潰れてしまう。また、セラミック粒子の重量％が多過ぎると、発電ユニットを昇温させてガラスを軟化させても、ガラスの流動が少ないので、クラックが生じるとともに、絶縁部材の厚みを調整しにくくなる。そこで、上記のように、絶縁部材に含まれるセラミック粒子の重量％を、５重量％以上３０重量％以下にすることにより、ガラスの過度な流動が抑制されるので、絶縁部材が潰れることに起因する厚み調整部材の過度の潰れを抑制することができる。また、ガラスの流動が少な過ぎることに起因する、クラックの発生と、絶縁部材の厚みの調整が困難になることとを抑制することができる。 Preferably, in the method of manufacturing a fuel cell including the step of removing the binder, the step of removing the binder is performed on the insulating member after the step of removing the binder by removing the binder from the insulating member before raising the temperature to the first temperature. The weight percent of the ceramic particles contained is 5 wt% or more and 30 wt% or less. Here, when the weight percentage of the ceramic particles is too small, the flow of the glass becomes too large when the power generation unit is heated to soften the glass. That is, since the insulating member cannot withstand the load and the insulating member is crushed, the thickness adjusting member disposed below the anode of the cell is also crushed excessively. On the other hand, if the weight percentage of the ceramic particles is too large, even if the power generation unit is heated to soften the glass, the glass does not flow so much that cracks occur and it is difficult to adjust the thickness of the insulating member. Therefore, as described above, by setting the weight percent of the ceramic particles contained in the insulating member to 5 wt% or more and 30 wt% or less, excessive flow of the glass is suppressed, and therefore the insulating member is crushed. Excessive crushing of the thickness adjusting member to be performed can be suppressed. Moreover, generation | occurrence | production of a crack resulting from there being too little flow of glass, and the adjustment of the thickness of an insulating member can be suppressed.
　上記バインダを取り除く工程を備える燃料電池の製造方法において、好ましくは、絶縁部材の厚みを調整する工程とバインダを取り除く工程との間に設けられ、積層された複数の発電ユニットを昇温させながら、第１の荷重よりも小さい第２の荷重を、積層方向に隣接する複数の発電ユニットに、互いに近接する方向に加えることにより、絶縁部材の収縮を抑制する工程をさらに備える。このように構成すれば、絶縁部材の両側から第２の荷重が加えられるので、発電ユニットを昇温させることによるガラスの軟化に起因する、絶縁部材の変形を効果的に抑制することができる。 In the method of manufacturing a fuel cell including the step of removing the binder, preferably provided between the step of adjusting the thickness of the insulating member and the step of removing the binder, while heating the plurality of stacked power generation units, The method further includes a step of suppressing contraction of the insulating member by applying a second load smaller than the first load to a plurality of power generation units adjacent to each other in the stacking direction in a direction adjacent to each other. If comprised in this way, since a 2nd load is applied from the both sides of an insulating member, the deformation | transformation of an insulating member resulting from the softening of the glass by heating up a power generation unit can be suppressed effectively.
　この場合、好ましくは、絶縁部材の収縮を抑制する工程は、絶縁部材に含まれるガラスが軟化する前に、第２の荷重を複数の発電ユニットに加える工程を含む。このように構成すれば、ガラスが軟化する前に第２の荷重が加えられるので、発電ユニットを昇温させることによるガラスの軟化に起因する、絶縁部材の変形を確実に抑制することができる。 In this case, preferably, the step of suppressing the shrinkage of the insulating member includes a step of applying a second load to the plurality of power generation units before the glass contained in the insulating member softens. If comprised in this way, since a 2nd load is applied before glass softens, the deformation | transformation of an insulating member resulting from softening of glass by heating up an electric power generation unit can be suppressed reliably.
　上記バインダを取り除く工程を備える燃料電池の製造方法において、好ましくは、発電ユニットは、セルのアノード側に設けられる金属製の厚み調整部材をさらに含み、バインダを取り除く工程の後、第２の温度よりも高くかつ第１の温度よりも低い第３の温度に昇温するとともに、還元性ガスの雰囲気下に厚み調整部材を配置することにより、酸化した状態の厚み調整部材を還元することによって、厚み調整部材の硬さを小さくする工程をさらに備える。このように構成すれば、厚み調整部材の硬さが小さくなるので、第１の荷重を加えることにより、絶縁部材の厚みを調整する際に、厚み調整部材の厚みも調整することができる。すなわち、厚み調整部材を含む発電ユニットの厚みを調整することができる。 In the method of manufacturing a fuel cell including the step of removing the binder, preferably, the power generation unit further includes a metal thickness adjusting member provided on the anode side of the cell, and after the step of removing the binder, The thickness of the oxidized thickness adjusting member is reduced by placing the thickness adjusting member under an atmosphere of reducing gas while raising the temperature to a third temperature that is higher than the first temperature and lower than the first temperature. The method further includes a step of reducing the hardness of the adjustment member. If comprised in this way, since the hardness of a thickness adjustment member will become small, when adjusting the thickness of an insulating member by applying a 1st load, the thickness of a thickness adjustment member can also be adjusted. That is, the thickness of the power generation unit including the thickness adjusting member can be adjusted.
　上記第１の局面による燃料電池の製造方法において、好ましくは、昇温前の絶縁部材に含まれるセラミック粒子の粒径は、１０μｍ以下である。このように構成すれば、セラミック粒子の粒径が大き過ぎることに起因して、絶縁部材の厚みの調整が困難になるのを抑制することができる。すなわち、厚みを小さくすることができなくなるのを抑制することができる。 In the fuel cell manufacturing method according to the first aspect, preferably, the particle size of the ceramic particles contained in the insulating member before the temperature rise is 10 μm or less. If comprised in this way, it can suppress that it becomes difficult to adjust the thickness of an insulating member resulting from the particle size of a ceramic particle being too large. That is, it becomes possible to prevent the thickness from being reduced.
　この発明の第２の局面による燃料電池は、積層された複数の発電ユニットを備え、発電ユニットは、一方の表面にアノードが形成され、他方の表面にカソードが形成されたセルと、セルの外側を取り囲むように設けられ、アノードに供給される燃料ガスと、カソードに供給される酸化剤とが混合するのを抑制する、セラミック粒子と非晶質であるガラスとを有する絶縁部材とを含む。 A fuel cell according to a second aspect of the present invention includes a plurality of stacked power generation units, and the power generation unit includes a cell having an anode formed on one surface and a cathode formed on the other surface, and an outer side of the cell. And an insulating member having ceramic particles and amorphous glass that suppresses mixing of the fuel gas supplied to the anode and the oxidant supplied to the cathode.
　この発明の第２の局面による燃料電池では、上記のように、発電ユニットは、セルの外側を取り囲むように設けられ、アノードに供給される燃料ガスと、カソードに供給される酸化剤とが混合するのを抑制する、セラミック粒子と非晶質であるガラスとを有する絶縁部材とを含む。これにより、絶縁部材がセラミック粒子と非晶質であるガラスとを有するように構成されているので、絶縁部材がマイカから構成されている場合と異なり、絶縁部材が劈開することがない。その結果、燃料電池のシャットダウン時に、燃料電池内の温度が低下することにより、燃料電池内の空気の体積が小さくなった場合でも、燃料電池の外部から絶縁部材を介して、空気が燃料電池内に侵入することはない。その結果、シャットダウン時に外部から侵入する空気に起因するセルの劣化を抑制することが可能な燃料電池を提供することができる。 In the fuel cell according to the second aspect of the present invention, as described above, the power generation unit is provided so as to surround the outside of the cell, and the fuel gas supplied to the anode and the oxidant supplied to the cathode are mixed. And an insulating member having ceramic particles and amorphous glass. Thereby, since the insulating member is configured to have ceramic particles and amorphous glass, the insulating member is not cleaved unlike the case where the insulating member is made of mica. As a result, even when the volume of the air in the fuel cell is reduced due to a decrease in the temperature in the fuel cell at the time of shutting down the fuel cell, the air passes through the insulating member from the outside of the fuel cell. Never invade. As a result, it is possible to provide a fuel cell capable of suppressing cell deterioration caused by air entering from the outside during shutdown.
　また、絶縁部材がセラミック粒子を有しているので、発電ユニットの厚みの確保、ガラスの過度な流動の抑制、および、クラックの修復を図ることができる。 Further, since the insulating member has ceramic particles, it is possible to secure the thickness of the power generation unit, suppress excessive flow of glass, and repair cracks.
　上記第２の局面による燃料電池において、好ましくは、絶縁部材は、５重量％以上３０重量％以下のセラミック粒子を含む。このように構成すれば、ガラスの過度な流動が抑制されるので、絶縁部材が潰れることに起因する厚み調整部材の潰れを抑制することができる。また、ガラスの流動が少な過ぎることに起因する、クラックの発生と、絶縁部材の厚みの調整が困難になることとを抑制することができる。 In the fuel cell according to the second aspect, the insulating member preferably contains 5% by weight or more and 30% by weight or less of ceramic particles. If comprised in this way, since the excessive flow of glass is suppressed, the collapse of the thickness adjustment member resulting from a collapse of an insulating member can be suppressed. Moreover, generation | occurrence | production of a crack resulting from there being too little flow of glass, and the adjustment of the thickness of an insulating member can be suppressed.
　上記第２の局面による燃料電池において、好ましくは、発電ユニットは、セルのアノード側に設けられる金属製の厚み調整部材をさらに含む。このように構成すれば、容易に、セル間の導通を金属製の厚み調整部材により確保しながら、発電ユニットの厚みを調整することができる。 In the fuel cell according to the second aspect, the power generation unit preferably further includes a metal thickness adjusting member provided on the anode side of the cell. If comprised in this way, the thickness of an electric power generation unit can be adjusted easily, ensuring the conduction | electrical_connection between cells by metal thickness adjustment members.
　上記第２の局面による燃料電池において、好ましくは、積層された複数の発電ユニットの積層方向の一方の端部側に配置され、セルを積層方向の他方の端部側に向けて押圧する弾性部材をさらに備える。このように構成すれば、積層された複数の発電ユニットにそれぞれ含まれるセルとセパレータ（隣接する発電ユニットにそれぞれ含まれるセルの間に配置される部材）との接触不良が抑制されるので、セルとセパレータとの接触抵抗が大きくなるのを抑制することができる。 In the fuel cell according to the second aspect, preferably, the elastic member is disposed on one end side in the stacking direction of the plurality of stacked power generation units and presses the cell toward the other end side in the stacking direction. Is further provided. If comprised in this way, since the contact failure with the cell each contained in the laminated | stacked several electric power generation unit and a separator (The member arrange | positioned between each cell contained in an adjacent electric power generation unit) is suppressed, a cell And the contact resistance between the separator and the separator can be prevented from increasing.
　上記第２の局面による燃料電池において、好ましくは、絶縁部材は、セルの外側を取り囲むように枠形状を有する。このように構成すれば、容易に、セルの外側を取り囲むように絶縁部材を配置することができる。 In the fuel cell according to the second aspect, the insulating member preferably has a frame shape so as to surround the outside of the cell. If comprised in this way, an insulating member can be easily arrange | positioned so that the outer side of a cell may be surrounded.
　本発明によれば、上記のように、燃料電池のシャットダウン時に外部から侵入する空気に起因するセルの劣化を抑制することができる。 According to the present invention, as described above, it is possible to suppress cell deterioration caused by air entering from the outside when the fuel cell is shut down.
本発明の一実施形態による燃料電池の分解斜視図である。1 is an exploded perspective view of a fuel cell according to an embodiment of the present invention. 本発明の一実施形態による発電ユニットの分解斜視図である。It is a disassembled perspective view of the electric power generation unit by one Embodiment of this invention. 本発明の一実施形態によるセパレータの分解斜視図である。It is a disassembled perspective view of the separator by one Embodiment of this invention. 本発明の一実施形態による燃料電池の模式的な断面図である。It is typical sectional drawing of the fuel cell by one Embodiment of this invention. 本発明の一実施形態による絶縁部材の模式的な断面図である。It is a typical sectional view of an insulating member by one embodiment of the present invention. 本発明の一実施形態による昇温前の絶縁部材の模式的な断面図である。It is typical sectional drawing of the insulating member before temperature rising by one Embodiment of this invention. 本発明の一実施形態による燃料電池（セルスタック）の製造方法を説明するための図である。It is a figure for demonstrating the manufacturing method of the fuel cell (cell stack) by one Embodiment of this invention.
　以下、本発明の実施形態を図面に基づいて説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
　［本実施形態］
　（燃料電池の構成）
　図１～図５を参照して、本実施形態による燃料電池１００の構成について説明する。なお、燃料電池１００は、固体酸化物形燃料電池（ＳＯＦＣ）である。また、燃料電池１００は、発電ユニット１０を複数積層することにより構成されている。なお、発電ユニット１０は、燃料ガスと酸化剤（空気）とが対向するように流れる（カウンタフロー）ように構成されている。 [This embodiment]
(Configuration of fuel cell)
The configuration of the fuel cell 100 according to the present embodiment will be described with reference to FIGS. The fuel cell 100 is a solid oxide fuel cell (SOFC). The fuel cell 100 is configured by stacking a plurality of power generation units 10. The power generation unit 10 is configured to flow so that the fuel gas and the oxidant (air) face each other (counter flow).
　図２に示すように、発電ユニット１０では、下方側（Ｚ２方向側）から、セパレータ２０と、絶縁部材３０と、金属多孔体である発泡ニッケル４０と、セル５０と、セル押さえ６０とが、この順で積層されている。なお、発泡ニッケル４０は、特許請求の範囲の「厚み調整部材」の一例である。 As shown in FIG. 2, in the power generation unit 10, from the lower side (Z2 direction side), the separator 20, the insulating member 30, the foamed nickel 40 that is a metal porous body, the cell 50, and the cell presser 60 are They are stacked in this order. The nickel foam 40 is an example of the “thickness adjusting member” in the claims.
　図３に示すように、セパレータ２０では、下方側（Ｚ２方向側）から、集電プレート２１と、カソードプレート２２と、セパレータ本体２３と、アノードプレート２４と、セルホルダ２５とが、この順で積層されている。 As shown in FIG. 3, in the separator 20, the current collecting plate 21, the cathode plate 22, the separator body 23, the anode plate 24, and the cell holder 25 are stacked in this order from the lower side (Z2 direction side). Has been.
　集電プレート２１は、セル５０のカソード５３に接触する（図４参照）ように構成されている。また、集電プレート２１には、燃料ガスが流通する孔部２１ａと、酸化剤が流通する孔部２１ｂおよび孔部２１ｃとが設けられている。また、集電プレート２１には、酸化剤をカソード５３に導くための複数の孔部２１ｄが設けられている。 The current collecting plate 21 is configured to be in contact with the cathode 53 of the cell 50 (see FIG. 4). The current collecting plate 21 is provided with a hole 21a through which fuel gas flows, and a hole 21b and hole 21c through which an oxidant flows. The current collecting plate 21 is provided with a plurality of holes 21 d for guiding the oxidant to the cathode 53.
　カソードプレート２２には、燃料ガスが流通する孔部２２ａと、酸化剤が流通する孔部２２ｂおよび孔部２２ｃとが設けられている。また、カソードプレート２２には、Ｘ方向に沿って、酸化剤の流路２２ｄが設けられている。具体的には、酸化剤は、流路２２ｄの下面側（Ｚ２方向側）を流通する。 The cathode plate 22 is provided with a hole 22a through which the fuel gas flows, and a hole 22b and a hole 22c through which the oxidant flows. The cathode plate 22 is provided with an oxidant flow path 22d along the X direction. Specifically, the oxidant flows on the lower surface side (Z2 direction side) of the flow path 22d.
　また、セパレータ本体２３には、燃料ガスが流通する孔部２３ａと、酸化剤が流通する孔部２３ｂおよび孔部２３ｃとが設けられている。また、セパレータ本体２３の表面は、平坦面状に形成されている。 Further, the separator body 23 is provided with a hole 23a through which the fuel gas flows, and a hole 23b and a hole 23c through which the oxidant flows. Further, the surface of the separator body 23 is formed into a flat surface.
　また、アノードプレート２４には、燃料ガスが流通する孔部２４ａ（および孔部２４ｄ）と、酸化剤が流通する孔部２４ｂおよび孔部２４ｃとが設けられている。また、アノードプレート２４には、Ｘ方向に沿って、燃料ガスの流路２４ｅが設けられている。燃料ガスは、流路２４ｅの上面側を流通する。なお、集電プレート２１、カソードプレート２２、セパレータ本体２３およびアノードプレート２４は、導電性の部材により形成されている。これにより、セパレータ２０の上面側に配置されるセル５０と、下面側に配置されるセル５０とが導通する。すなわち、セパレータ２０の上面側に配置されるセル５０と、下面側に配置されるセル５０とが電気的に接続される。 Further, the anode plate 24 is provided with a hole 24a (and a hole 24d) through which fuel gas flows, and a hole 24b and a hole 24c through which oxidant flows. The anode plate 24 is provided with a fuel gas flow path 24e along the X direction. The fuel gas flows through the upper surface side of the flow path 24e. The current collecting plate 21, the cathode plate 22, the separator body 23, and the anode plate 24 are formed of conductive members. Thereby, the cell 50 arrange | positioned at the upper surface side of the separator 20 and the cell 50 arrange | positioned at the lower surface side conduct | electrically_connect. That is, the cell 50 disposed on the upper surface side of the separator 20 and the cell 50 disposed on the lower surface side are electrically connected.
　また、セルホルダ２５には、燃料ガスが流通する孔部２５ａと、酸化剤が流通する孔部２５ｂおよび孔部２５ｃとが設けられている。また、セルホルダ２５の中央部には、開口部２５ｄが設けられている。 The cell holder 25 is provided with a hole 25a through which fuel gas flows, and a hole 25b and hole 25c through which an oxidant flows. In addition, an opening 25d is provided at the center of the cell holder 25.
　また、絶縁部材３０には、燃料ガスが流通する孔部３０ｅと、酸化剤が流通する孔部３０ｂおよび孔部３０ｃとが設けられている。また、本実施形態では、絶縁部材３０は、セル５０の外側を取り囲むように（図４参照）、枠形状を有する。そして、絶縁部材３０の中央部には、開口部３０ｄが設けられている。絶縁部材３０は、孔部３０ｅ（開口部３０ｄ）を流通してアノード５１に供給される燃料ガスと、孔部３０ｂおよび孔部３０ｃを流通してカソード５３に供給される酸化剤とが混合するのを抑制するように構成されている。また、絶縁部材３０は、積層方向に隣接するセル５０間を絶縁するように構成されている。 Further, the insulating member 30 is provided with a hole 30e through which the fuel gas flows, and a hole 30b and a hole 30c through which the oxidant flows. In the present embodiment, the insulating member 30 has a frame shape so as to surround the outside of the cell 50 (see FIG. 4). An opening 30 d is provided at the center of the insulating member 30. The insulating member 30 mixes the fuel gas supplied to the anode 51 through the hole 30e (opening 30d) and the oxidant supplied to the cathode 53 through the holes 30b and 30c. It is comprised so that this may be suppressed. The insulating member 30 is configured to insulate between the cells 50 adjacent in the stacking direction.
　また、図４に示すように、本実施形態では、発泡ニッケル４０は、セル５０のアノード５１側（Ｚ２方向側）に設けられている。また、発泡ニッケル４０は、略矩形形状を有し、セル５０の後述するアノード５１および固体電界質層５２と略同じ大きさ（面積）を有する。 Further, as shown in FIG. 4, in the present embodiment, the foamed nickel 40 is provided on the anode 51 side (Z2 direction side) of the cell 50. In addition, the foamed nickel 40 has a substantially rectangular shape, and has substantially the same size (area) as an anode 51 and a solid electrolyte layer 52 described later of the cell 50.
　図４に示すように、セル５０は、アノード５１、固体電界質層５２、カソード５３を含む。なお、セル５０は、Ｚ１方向側の面にカソード５３が形成され、カソード５３が形成される面とは反対側の面（Ｚ２方向側の面）にアノード５１が形成されている。また、アノード５１は、固体電界質層５２のＺ２方向側表面の略全面上に設けられている。カソード５３は、固体電界質層５２のＺ１方向側の表面の一部上に設けられている。 As shown in FIG. 4, the cell 50 includes an anode 51, a solid electrolyte layer 52, and a cathode 53. In the cell 50, the cathode 53 is formed on the surface on the Z1 direction side, and the anode 51 is formed on the surface opposite to the surface on which the cathode 53 is formed (surface on the Z2 direction side). The anode 51 is provided on substantially the entire surface of the solid electrolyte layer 52 on the Z2 direction side. The cathode 53 is provided on a part of the surface of the solid electrolyte layer 52 on the Z1 direction side.
　また、図３に示すように、セル押さえ６０には、燃料ガスが流通する孔部６０ａと、酸化剤が流通する孔部６０ｂおよび孔部６０ｃとが設けられている。また、セル押さえ６０の中央部には、開口部６０ｄが設けられている。 As shown in FIG. 3, the cell retainer 60 is provided with a hole 60a through which the fuel gas flows, and a hole 60b and a hole 60c through which the oxidant flows. In addition, an opening 60d is provided at the center of the cell presser 60.
　そして、図４に示すように、セルホルダ２５の開口部２５ｄ、および、絶縁部材３０の開口部３０ｄ内にセル５０が配置されている。また、セル押さえ６０は、絶縁部材３０と固体電界質層５２とに跨るように配置されている。これにより、カソード５３は、セル押さえ６０の開口部６０ｄから露出している。そして、カソード５３は、上方側の集電プレート２１に電気的に接続されている。 And as shown in FIG. 4, the cell 50 is arrange | positioned in the opening part 25d of the cell holder 25, and the opening part 30d of the insulating member 30. As shown in FIG. The cell retainer 60 is disposed so as to straddle the insulating member 30 and the solid electrolyte layer 52. As a result, the cathode 53 is exposed from the opening 60 d of the cell presser 60. The cathode 53 is electrically connected to the upper current collecting plate 21.
　また、図２に示すように、最も上方に配置される発電ユニット１０の上面上には、トッププレートを含む一方アノードプレートは含まないセパレータ２０ａが設けられている。また、最も下方に配置される発電ユニット１０の下面上には、ボトムプレートを含む一方カソードプレートは含まないセパレータ２０ｂが設けられている。 Further, as shown in FIG. 2, a separator 20a including a top plate but not including an anode plate is provided on the upper surface of the power generation unit 10 disposed at the uppermost position. A separator 20b that includes a bottom plate but does not include a cathode plate is provided on the lower surface of the power generation unit 10 that is disposed at the lowermost position.
　図３に示すように、セル５０のアノード５１に供給される燃料ガスは、セパレータ本体２３のＸ１方向側の孔部２３ａから、アノードプレート２４の孔部２４ｄを介して、アノードプレート２４の上面側（Ｚ１方向側面側）に流入する。また、反応後の燃料ガスは、アノードプレート２４のＸ２方向側の孔部２４ａを介して流出する。また、セル５０のカソード５３に供給される酸化剤（空気）は、カソードプレート２２のＸ２方向側の孔部２２ｂから、集電プレート２１の上面側（カソードプレート２２の下面側）に流入する。また、反応後の酸化剤は、集電プレート２１のＸ１方向側の孔部２１ｃを介して流出する。 As shown in FIG. 3, the fuel gas supplied to the anode 51 of the cell 50 flows from the hole 23 a on the X1 direction side of the separator body 23 to the upper surface side of the anode plate 24 through the hole 24 d of the anode plate 24. It flows into (Z1 direction side surface side). The reacted fuel gas flows out through the hole 24a on the X2 direction side of the anode plate 24. Further, the oxidant (air) supplied to the cathode 53 of the cell 50 flows into the upper surface side (the lower surface side of the cathode plate 22) of the current collecting plate 21 from the hole 22 b on the X2 direction side of the cathode plate 22. Further, the oxidant after the reaction flows out through the hole 21c on the X1 direction side of the current collecting plate 21.
　また、図１に示すように、積層された複数の発電ユニット１０により、セルスタック７０が構成されている。また、燃料電池１００では、セルスタック７０が、複数積層されている。そして、本実施形態では、セルスタック７０（積層された複数の発電ユニット１０）の積層方向の一方の端部側に配置され、セル５０を積層方向の他方の端部側に押圧する弾性部材８０が設けられている。具体的には、弾性部材８０は、平面視において、発電ユニット１０のセル５０に重なるように、積層されるセルスタック７０（複数の発電ユニット１０）の間に配置されている。また、弾性部材８０は、平面視において、略矩形形状を有する。また、弾性部材８０は、セラミックファイバーマットを含む。なお、弾性部材８０は、後述する燃料電池１００（セルスタック７０）の製造時ではなく、セルスタック７０が完成した後、燃料電池１００が実際に使用される際に、セル５０を押圧する。 Further, as shown in FIG. 1, a cell stack 70 is constituted by a plurality of stacked power generation units 10. In the fuel cell 100, a plurality of cell stacks 70 are stacked. In this embodiment, the elastic member 80 is arranged on one end side in the stacking direction of the cell stack 70 (the plurality of stacked power generation units 10) and presses the cell 50 toward the other end side in the stacking direction. Is provided. Specifically, the elastic member 80 is disposed between the stacked cell stacks 70 (the plurality of power generation units 10) so as to overlap the cells 50 of the power generation unit 10 in plan view. The elastic member 80 has a substantially rectangular shape in plan view. The elastic member 80 includes a ceramic fiber mat. The elastic member 80 presses the cell 50 when the fuel cell 100 is actually used after the cell stack 70 is completed, not when the fuel cell 100 (cell stack 70) described later is manufactured.
　また、平面視において、セル５０の外周側に弾性部材８０と重ならないように、積層されるセルスタック７０（複数の発電ユニット１０）の間に配置され、弾性部材８０よりも硬い部材からなる中間プレート８１が設けられている。また、中間プレート８１は、弾性部材８０よりも硬い金属製（たとえば、ＳＵＳ：Ｓｔａｉｎｌｅｓｓ　ｓｔｅｅｌ）である。中間プレート８１は、額縁形状を有しており、弾性部材８０は、額縁形状の中間プレート８１の開口部８１ａ内に配置されている。 Further, in a plan view, the intermediate member is disposed between the stacked cell stacks 70 (the plurality of power generation units 10) so as not to overlap the elastic member 80 on the outer peripheral side of the cell 50, and is an intermediate member that is harder than the elastic member 80. A plate 81 is provided. The intermediate plate 81 is made of metal harder than the elastic member 80 (for example, SUS: tainless steel). The intermediate plate 81 has a frame shape, and the elastic member 80 is disposed in the opening 81 a of the frame-shaped intermediate plate 81.
　また、中間プレート８１と、下方に配置されるセルスタック７０との間には、絶縁性の中間絶縁プレート８２が設けられている。中間絶縁プレート８２は、たとえば、結晶化ガラスからなる。なお、結晶化ガラスとは、ガラスを再加熱して、結晶を析出させることにより形成されたガラスである。中間絶縁プレート８２は、額縁形状を有しており、弾性部材８０は、額縁形状の中間絶縁プレート８２の開口部８２ａ内に配置されている。すなわち、中間プレート８１の開口部８１ａと、中間絶縁プレート８２の開口部８２ａとは連通するように設けられており、弾性部材８０は、開口部８１ａと開口部８２ａとに跨るように配置されている。 Further, an insulating intermediate insulating plate 82 is provided between the intermediate plate 81 and the cell stack 70 disposed below. The intermediate insulating plate 82 is made of crystallized glass, for example. Crystallized glass is glass formed by reheating glass to precipitate crystals. The intermediate insulating plate 82 has a frame shape, and the elastic member 80 is disposed in the opening 82 a of the frame-shaped intermediate insulating plate 82. That is, the opening 81a of the intermediate plate 81 and the opening 82a of the intermediate insulating plate 82 are provided so as to communicate with each other, and the elastic member 80 is disposed so as to straddle the opening 81a and the opening 82a. Yes.
　また、弾性部材８０、中間プレート８１および中間絶縁プレート８２の組は、複数の箇所（セルスタック７０の間）に配置されている。また、最上段のセルスタック７０の上面上と、弾性部材８０、中間プレート８１および中間絶縁プレート８２の組との間には、エンドプレート８３が設けられている。また、最上段の弾性部材８０、中間プレート８１および中間絶縁プレート８２の組の上面上に、絶縁部材８４が設けられている。絶縁部材８４は、たとえば、マイカにより構成されている。 Further, the set of the elastic member 80, the intermediate plate 81, and the intermediate insulating plate 82 is disposed at a plurality of locations (between the cell stacks 70). An end plate 83 is provided between the upper surface of the uppermost cell stack 70 and the set of the elastic member 80, the intermediate plate 81, and the intermediate insulating plate 82. An insulating member 84 is provided on the upper surface of the set of the uppermost elastic member 80, the intermediate plate 81 and the intermediate insulating plate 82. The insulating member 84 is made of mica, for example.
　また、絶縁部材８４の上面上に押圧プレート９０が設けられている。また、押圧プレート９０は、弾性部材８０よりも硬い金属製（たとえば、ＳＵＳ：Ｓｔａｉｎｌｅｓｓ　ｓｔｅｅｌ）である。 Further, a pressing plate 90 is provided on the upper surface of the insulating member 84. Further, the pressing plate 90 is made of metal harder than the elastic member 80 (for example, SUS: Stainless steel).
　また、押圧プレート９０の上面上に、押圧プレート９０を加圧する加圧部材９１が設けられている。具体的には、加圧部材９１は、セラミックから形成されている複数（本実施形態では５個）のばね部材９１ａからなる。そして、４個のばね部材９１ａにより、略矩形形状の押圧プレート９０の４隅が加圧され、１個のばね部材９１ａにより、略矩形形状の押圧プレート９０の中央部が加圧されている。また、押圧プレート９０には、ばね部材９１ａが配置される凹部９０ａが設けられている。 Further, a pressure member 91 for pressing the pressure plate 90 is provided on the upper surface of the pressure plate 90. Specifically, the pressurizing member 91 is composed of a plurality (five in this embodiment) of spring members 91a made of ceramic. The four corners of the substantially rectangular pressing plate 90 are pressed by the four spring members 91a, and the central portion of the approximately rectangular pressing plate 90 is pressed by the one spring member 91a. The pressing plate 90 is provided with a recess 90a in which the spring member 91a is disposed.
　また、加圧部材９１の上方（Ｚ１方向側）には、加圧部材９１（ばね部材９１ａ）を押圧するばね押圧プレート９２が配置されている。ばね押圧プレート９２には、複数の棒状部材９３が挿入される複数の貫通孔９２ａが設けられている。棒状部材９３の下方端は、図示しない剛体プレートなどに固定されるように構成されている。そして、複数の棒状部材９３が、ばね押圧プレート９２の貫通孔９２ａに挿入され、下方端が固定されるとともに、上方端にナット９４が締結されることにより、ばね押圧プレート９２が下方に押圧される。これにより、ばね部材９１ａが押圧されて、押圧プレート９０および弾性部材８０を介して、セル５０が押圧される。 Further, a spring pressing plate 92 that presses the pressing member 91 (spring member 91a) is disposed above the pressing member 91 (Z1 direction side). The spring pressing plate 92 is provided with a plurality of through holes 92a into which a plurality of rod-shaped members 93 are inserted. The lower end of the rod-shaped member 93 is configured to be fixed to a rigid plate (not shown) or the like. A plurality of rod-like members 93 are inserted into the through holes 92a of the spring pressing plate 92, the lower end is fixed, and the nut 94 is fastened to the upper end, whereby the spring pressing plate 92 is pressed downward. The As a result, the spring member 91 a is pressed, and the cell 50 is pressed via the pressing plate 90 and the elastic member 80.
　また、最も下方に位置するセルスタック７０の下方には、たとえば、結晶化ガラスからなる絶縁部材９５が配置されている。絶縁部材９５は、たとえば結晶化ガラスから構成されている。 Further, an insulating member 95 made of, for example, crystallized glass is disposed below the cell stack 70 located at the lowest position. The insulating member 95 is made of crystallized glass, for example.
　（絶縁部材の詳細な構造）
　次に、絶縁部材３０の詳細な構造について説明する。 (Detailed structure of insulation member)
Next, the detailed structure of the insulating member 30 will be described.
　本実施形態では、図５に示すように、絶縁部材３０は、セラミック粒子３２と非晶質であるガラス３３とを有する。具体的には、絶縁部材３０は、５重量％以上３０重量％以下のセラミック粒子３２を含んでいる。また、セラミック粒子３２は、たとえば、ジルコニア（二酸化ジルコニウム：ＺｎＯ２）からなる。なお、図５では、セラミック粒子３２の大きさが強調されて、実際よりも大きく記載されている。 In the present embodiment, as shown in FIG. 5, the insulating member 30 includes ceramic particles 32 and amorphous glass 33. Specifically, the insulating member 30 includes 5 wt% or more and 30 wt% or less of ceramic particles 32. The ceramic particles 32 are made of, for example, zirconia (zirconium dioxide: ZnO 2 ). In FIG. 5, the size of the ceramic particles 32 is emphasized and is larger than the actual size.
　（燃料電池の製造方法）
　次に、図１、図２および、図５～図７を参照して、燃料電池１００（セルスタック７０）の製造方法について説明する。なお、図７では、セラミック粒子３２およびバインダ３４の大きさが強調されて、実際よりも大きく記載されている。 (Fuel cell manufacturing method)
Next, a method for manufacturing the fuel cell 100 (cell stack 70) will be described with reference to FIGS. 1, 2, and 5 to 7. FIG. In FIG. 7, the sizes of the ceramic particles 32 and the binder 34 are emphasized and shown larger than the actual size.
　まず、図１に示すように、発電ユニット１０が、複数積層されることにより、セルスタック７０が構成される。図２に示すように、発電ユニット１０は、セパレータ２０と、絶縁部材３０と、発泡ニッケル４０と、セル５０と、セル押さえ６０とが、この順で積層されている。また、絶縁部材３０は、セラミック粒子３２と非晶質であるガラス３３とを有する。 First, as shown in FIG. 1, a cell stack 70 is configured by stacking a plurality of power generation units 10. As shown in FIG. 2, in the power generation unit 10, the separator 20, the insulating member 30, the foamed nickel 40, the cell 50, and the cell presser 60 are stacked in this order. The insulating member 30 includes ceramic particles 32 and amorphous glass 33.
　具体的には、図６に示すように、絶縁部材３０（昇温前の絶縁部材３０ａ）には、セラミック粒子３２、ガラス３３およびバインダ３４が含まれている。ここで、本実施形態では、昇温前の絶縁部材３０ａに含まれるセラミック粒子３２の粒径ｐは、１０μｍ以下である。また、バインダ３４は、たとえば、アクリル共重合体からなる。 Specifically, as shown in FIG. 6, the insulating member 30 (insulating member 30a before the temperature rise) includes ceramic particles 32, glass 33, and a binder 34. Here, in the present embodiment, the particle size p of the ceramic particles 32 included in the insulating member 30a before the temperature rise is 10 μm or less. The binder 34 is made of, for example, an acrylic copolymer.
　次に、図７に示すように、時刻ｔ０～時刻ｔ１の間において、セルスタック７０（複数積層された発電ユニット１０）が昇温（加熱）される。セルスタック７０は、空気雰囲気下において昇温される。なお、時刻ｔ０から、後述する時刻ｔ４まで、空気雰囲気下においてセルスタック７０が昇温される。 Next, as shown in FIG. 7, the cell stack 70 (a plurality of stacked power generation units 10) is heated (heated) between time t0 and time t1. The cell stack 70 is heated in an air atmosphere. The cell stack 70 is heated in the air atmosphere from time t0 to time t4 described later.
　そして、本実施形態では、積層された複数の発電ユニット１０（セルスタック７０）を後述する温度Ｔ４に昇温するのに先立って、温度Ｔ４よりも低い温度Ｔ１に昇温するとともに、温度Ｔ４に昇温前の絶縁部材３０ａのうちのバインダ３４を取り除く。具体的には、時刻ｔ１において、セルスタック７０は、温度Ｔ１に昇温される。そして、時刻ｔ１～時刻ｔ２の間において、セルスタック７０の温度は、Ｔ１に維持される。これにより、絶縁部材３０ａに含まれるバインダ３４が取り除かれる。なお、温度Ｔ４は、特許請求の範囲の「第１の温度」の一例である。また、温度Ｔ１は、特許請求の範囲の「第２の温度」の一例である。 In the present embodiment, prior to raising the temperature of the stacked power generation units 10 (cell stack 70) to a temperature T4 described later, the temperature is raised to a temperature T1 lower than the temperature T4, and the temperature T4 is increased. The binder 34 in the insulating member 30a before the temperature rise is removed. Specifically, at time t1, the cell stack 70 is heated to the temperature T1. The temperature of the cell stack 70 is maintained at T1 between time t1 and time t2. Thereby, the binder 34 contained in the insulating member 30a is removed. The temperature T4 is an example of the “first temperature” in the claims. The temperature T1 is an example of the “second temperature” in the claims.
　また、本実施形態では、ガラス３３が軟化する温度Ｔ２よりも低い温度Ｔ１を維持することにより、昇温前の絶縁部材３０ａに含まれるバインダ３４が取り除かれる。具体的には、バインダ３４が熱分解されることにより、絶縁部材３０ａから取り除かれる。また、バインダ３４の熱分解開始温度または焼失開始温度温は、ガラス３３が軟化する温度Ｔ２よりも低い。これにより、時刻ｔ２では、ガラス３３は軟化していない。 In this embodiment, the binder 34 contained in the insulating member 30a before the temperature rise is removed by maintaining the temperature T1 lower than the temperature T2 at which the glass 33 softens. Specifically, the binder 34 is thermally decomposed and removed from the insulating member 30a. Further, the thermal decomposition start temperature or burnout start temperature of the binder 34 is lower than the temperature T2 at which the glass 33 is softened. Thereby, the glass 33 is not softened at the time t2.
　また、本実施形態では、温度Ｔ４に昇温前の絶縁部材３０ａからバインダ３４を取り除くことにより、バインダ３４を取り除く工程後の絶縁部材３０に含まれるセラミック粒子３２の重量％を、５重量％以上３０重量％以下にする。すなわち、バインダ３４が取り除かれた後の絶縁部材３０の重量（セラミック粒子３２の重量＋ガラス３３の重量）に対するセラミック粒子３２の重量が、５％以上３０％以下となる。 In the present embodiment, the binder 34 is removed from the insulating member 30a before the temperature is raised to the temperature T4, so that the weight% of the ceramic particles 32 contained in the insulating member 30 after the step of removing the binder 34 is 5% by weight or more. 30% by weight or less. That is, the weight of the ceramic particles 32 with respect to the weight of the insulating member 30 after the binder 34 is removed (the weight of the ceramic particles 32 + the weight of the glass 33) is 5% or more and 30% or less.
　次に、本実施形態では、後述する絶縁部材３０の厚みｔを調整する工程とバインダ３４を取り除く工程との間に、積層された複数の発電ユニット１０を昇温させながら、後述する荷重Ｆ２よりも小さい荷重Ｆ１を、積層方向に隣接する複数の発電ユニット１０に、互いに近接する方向に加える。これにより、絶縁部材３０の収縮が抑制される。具体的には、時刻ｔ２において、複数の発電ユニット１０が温度Ｔ１より昇温される。そして、時刻ｔ２において、複数の発電ユニット１０に、荷重Ｆ１が加えられる。なお、荷重Ｆ１が加えられた状態は、時刻ｔ２から後述する時刻ｔ５まで維持される。なお、荷重Ｆ２および荷重Ｆ１は、それぞれ、特許請求の範囲の「第１の荷重」および「第２の荷重」の一例である。 Next, in the present embodiment, a load F2 (to be described later) is used while increasing the temperature of the plurality of stacked power generation units 10 between the step of adjusting the thickness t of the insulating member 30 to be described later and the step of removing the binder 34. Is applied to the plurality of power generation units 10 adjacent to each other in the stacking direction. Thereby, contraction of the insulating member 30 is suppressed. Specifically, at time t2, the plurality of power generation units 10 are heated from the temperature T1. At time t2, a load F1 is applied to the plurality of power generation units 10. The state where the load F1 is applied is maintained from time t2 to time t5 described later. The load F2 and the load F1 are examples of the “first load” and the “second load” in the claims, respectively.
　時刻ｔ２から昇温された複数の発電ユニット１０の温度は、時刻ｔ３において、ガラス３３が軟化する温度Ｔ２に達する。これにより、時刻ｔ３において、絶縁部材３０に含まれるガラス３３が軟化し始める。ここで、ガラス３３が軟化することにより、ガラス３３が流動して、絶縁部材３０が変形する。そこで、本実施形態では、絶縁部材３０に含まれるガラス３３が軟化する前（時刻ｔ２）に、荷重Ｆ１を複数の発電ユニット１０に加えることにより、絶縁部材３０の変形が抑制される。 The temperature of the plurality of power generation units 10 heated from time t2 reaches the temperature T2 at which the glass 33 softens at time t3. Thereby, the glass 33 contained in the insulating member 30 begins to soften at the time t3. Here, when the glass 33 is softened, the glass 33 flows and the insulating member 30 is deformed. Therefore, in the present embodiment, the deformation of the insulating member 30 is suppressed by applying the load F1 to the plurality of power generation units 10 before the glass 33 included in the insulating member 30 is softened (time t2).
　次に、本実施形態では、バインダ３４を取り除く工程の後、複数の発電ユニット１０（セルスタック７０）が、温度Ｔ１よりも高くかつ後述する温度Ｔ４よりも低い温度Ｔ３に昇温されるとともに、還元性ガス（Ｈ２ガス、流量Ｍ１）の雰囲気下に配置される。これにより、発泡ニッケル４０が還元性ガス（Ｈ２ガス）の雰囲気下に配置されることにより、酸化した状態の発泡ニッケル４０が還元される。そして、発泡ニッケル４０の硬さを小さくなる。なお、温度Ｔ３は、特許請求の範囲の「第３の温度」の一例である。 Next, in the present embodiment, after the step of removing the binder 34, the plurality of power generation units 10 (cell stacks 70) are heated to a temperature T3 that is higher than the temperature T1 and lower than a temperature T4 that will be described later. reducing gas (H 2 gas flow rate M1) is placed under an atmosphere of. Thus, the foamed nickel 40 is placed in an atmosphere of a reducing gas (H 2 gas), whereby the foamed nickel 40 in an oxidized state is reduced. And the hardness of the foaming nickel 40 becomes small. The temperature T3 is an example of the “third temperature” in the claims.
　具体的には、時刻ｔ４において、発電ユニット１０（セルスタック７０）の温度がＴ３となり、時刻ｔ５まで、温度Ｔ３の状態が維持される。そして、時刻ｔ３において、Ｎ２で雰囲気を置換するとともに、発電ユニット１０が還元性ガス（Ｈ２ガス）の雰囲気下に配置される。ここで、還元性ガス（Ｈ２ガス）の雰囲気下に配置される前の発泡ニッケル４０は酸化しており、還元性ガス（Ｈ２ガス）により、発泡ニッケル４０に含まれる酸化した状態のニッケルが、金属のニッケルに還元される。これにより、発泡ニッケル４０の硬さが小さくなる。 Specifically, at time t4, the temperature of the power generation unit 10 (cell stack 70) reaches T3, and the state of temperature T3 is maintained until time t5. At time t3, the atmosphere is replaced with N 2 , and the power generation unit 10 is placed in an atmosphere of reducing gas (H 2 gas). Here, the foamed nickel 40 before being placed in the reducing gas (H 2 gas) atmosphere is oxidized, and the nickel in the oxidized state contained in the foamed nickel 40 by the reducing gas (H 2 gas). Is reduced to metallic nickel. Thereby, the hardness of the foamed nickel 40 becomes small.
　次に、本実施形態では、積層された複数の発電ユニット１０を昇温するとともに、積層方向に隣接する複数の発電ユニット１０に、互いに近接する方向に荷重Ｆ２を加えることにより、絶縁部材３０の厚みｔを調整する。具体的には、時刻ｔ５では、複数の発電ユニット１０の温度は、Ｔ３である。また、時刻ｔ５において、還元性ガス（Ｈ２ガス）の流量がＭ１からＭ２に減少される。そして、時刻ｔ５から、複数の発電ユニット１０（セルスタック７０）に、荷重Ｆ２が加えられる。そして、荷重Ｆ２が加えられた状態で、複数の発電ユニット１０が昇温され、時刻ｔ６において、複数の発電ユニット１０の温度が、Ｔ４となる。その後、時刻ｔ７まで、荷重Ｆ２が加えられた状態で、複数の発電ユニット１０の温度がＴ４に維持される。温度Ｔ４は、ガラス３３が軟化する温度Ｔ２よりも大きいため、荷重Ｆ２が加えられ始めた時刻である時刻ｔ５から、時刻ｔ７までは、ガラス３３は軟化したままの状態である。これにより、絶縁部材３０の厚みｔが調整可能になる。 Next, in the present embodiment, the temperature of the plurality of stacked power generation units 10 is increased, and a load F2 is applied to the plurality of power generation units 10 adjacent to each other in the stacking direction so as to approach each other. The thickness t is adjusted. Specifically, at time t5, the temperatures of the plurality of power generation units 10 are T3. At time t5, the flow rate of the reducing gas (H 2 gas) is decreased from M1 to M2. Then, a load F2 is applied to the plurality of power generation units 10 (cell stack 70) from time t5. Then, with the load F2 applied, the plurality of power generation units 10 are heated, and at time t6, the temperatures of the plurality of power generation units 10 become T4. Thereafter, the temperature of the plurality of power generation units 10 is maintained at T4 with the load F2 applied until time t7. Since the temperature T4 is higher than the temperature T2 at which the glass 33 is softened, the glass 33 remains in a softened state from time t5, which is the time when the load F2 starts to be applied, to time t7. Thereby, the thickness t of the insulating member 30 can be adjusted.
　具体的には、絶縁部材３０の厚みｔが、図７の厚みｔ１の状態から、図５の厚みｔ２の状態に小さくされる。なお、発泡ニッケル４０が還元されることにより、硬さが小さくされているため、荷重Ｆ２により、発泡ニッケル４０の厚みも調整される。すなわち、荷重Ｆ２により、複数の発電ユニット１０の全体の厚みが調整される。つまり、各々の発電ユニット１０の厚みが調整される。 Specifically, the thickness t of the insulating member 30 is reduced from the thickness t1 in FIG. 7 to the thickness t2 in FIG. In addition, since the hardness is reduced by reducing the foamed nickel 40, the thickness of the foamed nickel 40 is also adjusted by the load F2. That is, the entire thickness of the plurality of power generation units 10 is adjusted by the load F2. That is, the thickness of each power generation unit 10 is adjusted.
　そして、時刻ｔ７以降、複数の発電ユニット１０が降温される。具体的には、複数の発電ユニット１０の温度は、時刻ｔ７から時刻ｔ８の間で、段階的に降温される。これにより、複数の発電ユニット１０（セルスタック７０）が完成する。 And after time t7, the plurality of power generation units 10 are cooled. Specifically, the temperatures of the plurality of power generation units 10 are decreased stepwise from time t7 to time t8. Thereby, the several electric power generation unit 10 (cell stack 70) is completed.
　（本実施形態の効果）
　本実施形態では、以下のような効果を得ることができる。 (Effect of this embodiment)
In the present embodiment, the following effects can be obtained.
　本実施形態では、上記のように、セル５０の外側を取り囲むように設けられ、アノード５１に供給される燃料ガスと、カソード５３に供給される酸化剤とが混合するのを抑制する、セラミック粒子３２と非晶質であるガラス３３とを有する絶縁部材３０とを含む発電ユニット１０を、複数積層する工程を備える。これにより、絶縁部材３０がセラミック粒子３２と非晶質であるガラス３３とを有するように構成されているので、絶縁部材３０がマイカから構成されている場合と異なり、絶縁部材３０が劈開することがない。その結果、燃料電池１００のシャットダウン時に、燃料電池１００内の温度が低下することにより、燃料電池１００内の空気の体積が小さくなった場合でも、燃料電池１００の外部から絶縁部材３０を介して、空気が燃料電池１００内に侵入することはない。その結果、シャットダウン時に外部から侵入する空気に起因するセル５０の劣化を抑制することができる。 In the present embodiment, as described above, the ceramic particles are provided so as to surround the outside of the cell 50 and suppress mixing of the fuel gas supplied to the anode 51 and the oxidant supplied to the cathode 53. A step of laminating a plurality of power generation units 10 each including the insulating member 30 having 32 and amorphous glass 33. Thereby, since the insulating member 30 is configured to have the ceramic particles 32 and the amorphous glass 33, the insulating member 30 is cleaved unlike the case where the insulating member 30 is made of mica. There is no. As a result, even when the volume of air in the fuel cell 100 is reduced due to a decrease in the temperature in the fuel cell 100 when the fuel cell 100 is shut down, the insulating member 30 is passed through the insulating member 30 from the outside of the fuel cell 100. Air does not enter the fuel cell 100. As a result, it is possible to suppress the deterioration of the cell 50 due to air entering from the outside during shutdown.
　また、絶縁部材３０がセラミック粒子３２を有しているので、絶縁部材３０の厚みｔが、所定の厚みよりも小さくなることが抑制される。これにより、絶縁部材３０の厚みｔが小さくなることに起因して絶縁性が確保できなくなるのを抑制することができるとともに、発電ユニット１０の厚みが小さくなり過ぎないように厚みを確保することができる。また、発電ユニット１０を昇温させることにより、ガラス３３が軟化した場合でも、ガラス３３の過度な流動をセラミック粒子３２により抑制することができる。また、絶縁部材３０が非晶質であるガラス３３を有しているので、絶縁部材３０にクラックが生じている場合でも、発電ユニット１０を昇温することにより、ガラス３３が融解することによって、クラックを修復することができる。その結果、クラックをなくすことができる。 Further, since the insulating member 30 has the ceramic particles 32, the thickness t of the insulating member 30 is suppressed from being smaller than a predetermined thickness. Accordingly, it is possible to prevent the insulation from being unable to be ensured due to the decrease in the thickness t of the insulating member 30 and to secure the thickness so that the thickness of the power generation unit 10 is not too small. it can. Moreover, even when the glass 33 is softened by raising the temperature of the power generation unit 10, excessive flow of the glass 33 can be suppressed by the ceramic particles 32. In addition, since the insulating member 30 includes the amorphous glass 33, even when the insulating member 30 has cracks, the glass 33 is melted by raising the temperature of the power generation unit 10. Cracks can be repaired. As a result, cracks can be eliminated.
　また、本実施形態では、上記のように、積層された複数の発電ユニット１０を温度Ｔ４に昇温するのに先立って、温度Ｔ４よりも低い温度Ｔ１に昇温するとともに、温度Ｔ４に昇温前の絶縁部材３０ａのうちのバインダ３４を取り除く工程を備える。これにより、積層された複数の発電ユニット１０を温度Ｔ１に昇温することで、バインダ３４が焼失または熱分解するので、容易に、非晶質であるガラス３３とセラミック粒子３２とを有する絶縁部材３０を形成することができる。 In the present embodiment, as described above, prior to raising the temperature of the plurality of stacked power generation units 10 to the temperature T4, the temperature is raised to the temperature T1 lower than the temperature T4, and the temperature is raised to the temperature T4. A step of removing the binder 34 from the previous insulating member 30a is provided. Thereby, since the binder 34 is burnt down or thermally decomposed by raising the temperature of the stacked power generation units 10 to the temperature T1, the insulating member having the amorphous glass 33 and the ceramic particles 32 can be easily obtained. 30 can be formed.
　また、本実施形態では、上記のように、ガラス３３が軟化する温度Ｔ２よりも低い温度Ｔ１を維持することにより、昇温前の絶縁部材３０ａに含まれるバインダ３４を取り除く。これにより、温度Ｔ１が、ガラス３３が軟化する温度Ｔ２よりも低いので、ガラス３３が軟化する前にバインダ３４を取り除くことができる。 In the present embodiment, as described above, the binder 34 contained in the insulating member 30a before the temperature rise is removed by maintaining the temperature T1 lower than the temperature T2 at which the glass 33 softens. Thereby, since the temperature T1 is lower than the temperature T2 at which the glass 33 is softened, the binder 34 can be removed before the glass 33 is softened.
　また、本実施形態では、上記のように、バインダ３４の熱分解開始温度または焼失開始温度は、ガラス３３が軟化する温度Ｔ２よりも低い。これにより、容易に、ガラス３３が軟化する前にバインダ３４を取り除くことができる。 In the present embodiment, as described above, the thermal decomposition start temperature or burnout start temperature of the binder 34 is lower than the temperature T2 at which the glass 33 softens. Thereby, the binder 34 can be easily removed before the glass 33 is softened.
　また、本実施形態では、上記のように、温度Ｔ４に昇温前の絶縁部材３０ａからバインダ３４を取り除くことにより、バインダ３４を取り除く工程後の絶縁部材３０に含まれるセラミック粒子３２の重量％を、５重量％以上３０重量％以下にする。ここで、セラミック粒子３２の重量％が少な過ぎると、発電ユニット１０を昇温させてガラス３３が軟化した場合に、ガラス３３の流動が大きくなり過ぎる。すなわち、絶縁部材３０が荷重に耐えることができずに潰れてしまうので、セル５０のアノード５１の下方に配置される発泡ニッケル４０も過度に潰れてしまう。また、セラミック粒子３２の重量％が多過ぎると、発電ユニット１０を昇温させてガラス３３を軟化させても、ガラス３３の流動が少ないので、クラックが生じるとともに、絶縁部材３０の厚みｔを調整しにくくなる。そこで、上記のように、絶縁部材３０に含まれるセラミック粒子３２の重量％を、５重量％以上３０重量％以下にすることにより、ガラス３３の流動が大きくなり過ぎることが抑制されるので、絶縁部材３０が潰れることに起因する発泡ニッケル４０の過度の潰れを抑制することができる。また、ガラス３３の流動が少な過ぎることに起因する、クラックの発生と、絶縁部材３０の厚みｔの調整が困難になることとを抑制することができる。 In the present embodiment, as described above, the binder 34 is removed from the insulating member 30a before the temperature is raised to the temperature T4, so that the weight% of the ceramic particles 32 included in the insulating member 30 after the step of removing the binder 34 is reduced. 5 wt% or more and 30 wt% or less. Here, if the weight percentage of the ceramic particles 32 is too small, the flow of the glass 33 becomes too large when the temperature of the power generation unit 10 is raised and the glass 33 is softened. That is, since the insulating member 30 cannot withstand the load and is crushed, the foamed nickel 40 disposed below the anode 51 of the cell 50 is also crushed excessively. On the other hand, when the weight percentage of the ceramic particles 32 is too large, even if the power generation unit 10 is heated and the glass 33 is softened, the flow of the glass 33 is small so that cracks occur and the thickness t of the insulating member 30 is adjusted. It becomes difficult to do. Therefore, as described above, by setting the weight% of the ceramic particles 32 included in the insulating member 30 to 5 wt% or more and 30 wt% or less, it is possible to suppress the flow of the glass 33 from being excessively increased. Excessive crushing of the foamed nickel 40 caused by the member 30 being crushed can be suppressed. Moreover, generation | occurrence | production of the crack resulting from there being too little flow of the glass 33, and the adjustment of the thickness t of the insulating member 30 can be suppressed.
　また、本実施形態では、上記のように、絶縁部材３０の厚みｔを調整する工程とバインダ３４を取り除く工程との間に設けられ、積層された複数の発電ユニット１０を昇温させながら、荷重Ｆ２よりも小さい荷重Ｆ１を、積層方向に隣接する複数の発電ユニット１０に、互いに近接する方向に加えることにより、絶縁部材３０の収縮を抑制する工程を備える。これにより、絶縁部材３０の両側から荷重Ｆ１が加えられるので、発電ユニット１０を昇温させることによるガラス３３の軟化に起因する、絶縁部材３０の変形を効果的に抑制することができる。 Further, in the present embodiment, as described above, the load is provided between the step of adjusting the thickness t of the insulating member 30 and the step of removing the binder 34 while raising the temperature of the plurality of stacked power generation units 10. A step of suppressing contraction of the insulating member 30 by applying a load F1 smaller than F2 to a plurality of power generation units 10 adjacent to each other in the stacking direction in a direction adjacent to each other is provided. Thereby, since the load F1 is applied from both sides of the insulating member 30, deformation of the insulating member 30 due to softening of the glass 33 caused by raising the temperature of the power generation unit 10 can be effectively suppressed.
　また、本実施形態では、上記のように、絶縁部材３０に含まれるガラス３３が軟化する前に、荷重Ｆ１を複数の発電ユニット１０に加える。これにより、ガラス３３が軟化する前に荷重Ｆ１が加えられるので、発電ユニット１０を昇温させることによるガラス３３の軟化に起因する、絶縁部材３０の変形を確実に抑制することができる。 In the present embodiment, as described above, the load F1 is applied to the plurality of power generation units 10 before the glass 33 included in the insulating member 30 is softened. Thereby, since the load F1 is applied before the glass 33 softens, the deformation | transformation of the insulating member 30 resulting from the softening of the glass 33 by heating up the electric power generation unit 10 can be suppressed reliably.
　また、本実施形態では、上記のように、バインダ３４を取り除く工程の後、温度Ｔ１よりも高くかつ温度Ｔ４よりも低い温度Ｔ３に昇温するとともに、還元性ガスの雰囲気下に発泡ニッケル４０を配置することにより、酸化した状態の発泡ニッケル４０を還元することによって、発泡ニッケル４０の硬さを小さくする工程を備える。これにより、発泡ニッケル４０の硬さが小さくなるので、荷重Ｆ２を加えることにより、絶縁部材３０の厚みｔを調整する際に、発泡ニッケル４０の厚みも調整することができる。すなわち、発泡ニッケル４０を含む発電ユニット１０の厚みを調整することができる。 In the present embodiment, as described above, after the step of removing the binder 34, the temperature is raised to a temperature T3 that is higher than the temperature T1 and lower than the temperature T4, and the foamed nickel 40 is placed in an atmosphere of reducing gas. The step of reducing the hardness of the foamed nickel 40 by reducing the foamed nickel 40 in an oxidized state by arranging the foamed nickel 40 is provided. Thereby, since the hardness of the foamed nickel 40 becomes small, the thickness of the foamed nickel 40 can be adjusted when the thickness t of the insulating member 30 is adjusted by applying the load F2. That is, the thickness of the power generation unit 10 including the foamed nickel 40 can be adjusted.
　また、本実施形態では、上記のように、昇温前の絶縁部材３０に含まれるセラミック粒子３２の粒径ｐは、１０μｍ以下である。これにより、セラミック粒子３２の粒径ｐが大き過ぎることに起因して、絶縁部材３０の厚みｔの調整が困難になるのを抑制することができる。すなわち、厚みｔを小さくすることができなくなるのを抑制することができる。 In the present embodiment, as described above, the particle size p of the ceramic particles 32 contained in the insulating member 30 before the temperature rise is 10 μm or less. Thereby, it can be suppressed that the adjustment of the thickness t of the insulating member 30 is difficult due to the particle size p of the ceramic particles 32 being too large. That is, it is possible to prevent the thickness t from being reduced.
　また、本実施形態では、上記のように、発電ユニット１０は、セル５０のアノード５１側に設けられる金属製の発泡ニッケル４０を含む。これにより、容易に、セル５０間の導通を金属製の発泡ニッケル４０により確保しながら、発電ユニット１０の厚みを調整することができる。 In the present embodiment, as described above, the power generation unit 10 includes the metallic foamed nickel 40 provided on the anode 51 side of the cell 50. Thereby, the thickness of the power generation unit 10 can be easily adjusted while ensuring conduction between the cells 50 by the metallic foamed nickel 40.
　また、本実施形態では、上記のように、積層された複数の発電ユニット１０の積層方向の一方の端部側に配置され、セル５０を積層方向の他方の端部側に押圧する弾性部材８０を備える。これにより、積層された複数の発電ユニット１０にそれぞれ含まれるセル５０とセパレータ２０（隣接する発電ユニット１０にそれぞれ含まれるセル５０の間に配置される部材）との接触不良が抑制されるので、セル５０とセパレータ２０との接触抵抗が大きくなるのを抑制することができる。 In the present embodiment, as described above, the elastic member 80 is disposed on one end side in the stacking direction of the plurality of stacked power generation units 10 and presses the cell 50 toward the other end side in the stacking direction. Is provided. Thereby, since the poor contact between the cell 50 included in each of the plurality of stacked power generation units 10 and the separator 20 (the member disposed between the cells 50 included in each adjacent power generation unit 10) is suppressed, An increase in the contact resistance between the cell 50 and the separator 20 can be suppressed.
　また、本実施形態では、上記のように、絶縁部材３０は、セル５０の外側を取り囲むように枠形状を有する。これにより、容易に、セル５０の外側を取り囲むように絶縁部材３０を配置することができる。 In this embodiment, as described above, the insulating member 30 has a frame shape so as to surround the outside of the cell 50. Thereby, the insulating member 30 can be easily disposed so as to surround the outside of the cell 50.
　［変形例］
　なお、今回開示された実施形態および実施例は、すべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は、上記した実施形態および実施例の説明ではなく特許請求の範囲によって示され、さらに特許請求の範囲と均等の意味および範囲内でのすべての変更（変形例）が含まれる。 [Modification]
The embodiments and examples disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is shown not by the above description of the embodiments and examples but by the scope of claims for patent, and includes all modifications (modifications) within the meaning and scope equivalent to the scope of claims for patent.
　たとえば、上記実施形態では、燃料電池が、固体酸化物形燃料電池（ＳＯＦＣ）である例を示したが、本発明はこれに限られない。たとえば、燃料電池が、固体酸化物形燃料電池以外の燃料電池である、固体高分子形燃料電池（ＰＥＦＣ：Ｐｏｌｙｍｅｒ　Ｅｌｅｃｔｒｏｌｙｔｅ　Ｆｕｅｌ　Ｃｅｌｌ）、りん酸形燃料電池（ＰＡＦＣ：Ｐｈｏｓｐｈｏｒｉｃ　Ａｃｉｄ　Ｆｕｅｌ　Ｃｅｌｌ）、溶融炭酸塩形燃料電池（ＭＣＦＣ：Ｍｏｌｔｅｎ　Ｃａｒｂｏｎａｔｅ　Ｆｕｅｌ　Ｃｅｌｌ）などでもよい。 For example, in the above embodiment, an example in which the fuel cell is a solid oxide fuel cell (SOFC) is shown, but the present invention is not limited to this. For example, the fuel cell is a fuel cell other than a solid oxide fuel cell, such as a polymer electrolyte fuel cell (PEFC), a phosphoric acid fuel cell (PAFC), a molten carbonic acid fuel cell. A salt fuel cell (MCFC: Molten Carbonate Fuel Cell) may be used.
　また、上記実施形態では、絶縁部材に、セラミック粒子としてジルコニアが含まれる例を示したが、本発明はこれに限られない。たとえば、絶縁部材に、セラミック粒子として、たとえば、アルミナ（酸化アルミニウム）などのジルコニア以外の物質が含まれていてもよい。 In the above embodiment, the example in which the insulating member includes zirconia as the ceramic particles is shown, but the present invention is not limited to this. For example, the insulating member may contain substances other than zirconia such as alumina (aluminum oxide) as ceramic particles.
　また、上記実施形態では、酸化した状態の発泡ニッケルを還元することによって、発泡ニッケルの硬さを小さくする工程が行われる例を示したが、本発明はこれに限られない。たとえば、発泡ニッケルの硬さを小さくする必要がなければ、この工程を行わなくてもよい。 In the above embodiment, an example is shown in which the step of reducing the hardness of the foamed nickel by reducing the oxidized nickel foam is performed, but the present invention is not limited to this. For example, if it is not necessary to reduce the hardness of the nickel foam, this step may not be performed.
　また、上記実施形態では、セルスタックに２段階の荷重（荷重Ｆ１および荷重Ｆ２）が加えられる例を示したが、本発明はこれに限られない。たとえば、１段階の荷重を加えることにより、絶縁部材の変形を抑制しながら、絶縁部材の厚みを調整してもよい。 In the above embodiment, an example in which two-stage loads (load F1 and load F2) are applied to the cell stack has been shown, but the present invention is not limited to this. For example, the thickness of the insulating member may be adjusted by applying a one-stage load while suppressing deformation of the insulating member.
　また、上記実施形態では、厚み調整部材として、発泡ニッケルを用いる例を示したが、本発明はこれに限られない。本発明では、発泡ニッケル以外の厚み調整部材を用いてもよい。 In the above embodiment, the example in which the foamed nickel is used as the thickness adjusting member is shown, but the present invention is not limited to this. In the present invention, a thickness adjusting member other than the foamed nickel may be used.
　また、上記実施形態では、弾性部材が、アルミナからなるセラミックファイバーマット（シート）から構成されている例を示したが、本発明はこれに限られない。たとえば、アルミナからなるセラミックファイバーマット（シート）以外の部材により弾性部材を構成してもよい。 In the above embodiment, the elastic member is made of a ceramic fiber mat (sheet) made of alumina. However, the present invention is not limited to this. For example, the elastic member may be constituted by a member other than a ceramic fiber mat (sheet) made of alumina.
　また、上記実施形態では、ばね部材により、弾性部材を介してセルを押圧する例を示したが、本発明はこれに限られない。たとえば、クッション材、マットなどのばね部材以外の部材により、弾性部材を介してセルを押圧してもよい。 In the above embodiment, an example is shown in which the cell is pressed by the spring member via the elastic member, but the present invention is not limited to this. For example, the cell may be pressed via an elastic member by a member other than a spring member such as a cushion material or a mat.
　また、上記実施形態では、燃料電池（発電ユニット）が、燃料ガスと空気とが対向するように流れるカウンタフローの燃料電池である例を示したが、本発明はこれに限られない。たとえば、燃料ガスと空気とが交差するように流れるクロスフローの燃料電池にも、本発明を適用することが可能である。 In the above embodiment, the fuel cell (power generation unit) is a counter flow fuel cell in which the fuel gas and the air flow so as to face each other. However, the present invention is not limited to this. For example, the present invention can be applied to a cross-flow fuel cell in which fuel gas and air flow so as to intersect each other.
　１０　発電ユニット
　３０　絶縁部材
　３２　ガラス
　３３　セラミック粒子
　３４　バインダ
　４０　発泡ニッケル（厚み調整部材）
　５０　セル
　５１　アノード
　５３　カソード
　８０　弾性部材
　１００　燃料電池
　Ｆ１　荷重（第２の荷重）
　Ｆ２　荷重（第１の荷重）
　ｔ　厚み
　Ｔ１　温度（第２の温度）
　Ｔ３　温度（第３の温度）
　Ｔ４　温度（第１の温度） DESCRIPTION OF SYMBOLS 10 Power generation unit 30 Insulating member 32 Glass 33 Ceramic particle 34 Binder 40 Foam nickel (thickness adjustment member)
50 cells 51 anode 53 cathode 80 elastic member 100 fuel cell F1 load (second load)
F2 load (first load)
t thickness T1 temperature (second temperature)
T3 temperature (third temperature)
T4 temperature (first temperature)

Claims (14)

  1. 　一方の表面にアノードが形成され他方の表面にカソードが形成されたセルと、前記セルの外側を取り囲むように設けられ、前記アノードに供給される燃料ガスと前記カソードに供給される酸化剤とが混合するのを抑制する、セラミック粒子と非晶質であるガラスとを有する絶縁部材とを含む発電ユニットを、複数積層する工程と、
    　積層された前記複数の発電ユニットを第１の温度に昇温するとともに、積層方向に隣接する前記複数の発電ユニットに、互いに近接する方向に第１の荷重を加えることにより、前記絶縁部材の厚みを調整する工程と、を備える、燃料電池の製造方法。     A cell having an anode formed on one surface and a cathode formed on the other surface, and a fuel gas provided to surround the outside of the cell and supplied to the anode and an oxidant supplied to the cathode A step of laminating a plurality of power generation units each including an insulating member having ceramic particles and amorphous glass that suppresses mixing; and
    The temperature of the plurality of power generation units stacked is increased to a first temperature, and the first load is applied to the plurality of power generation units adjacent to each other in the stacking direction so as to approach each other. And a step of adjusting the fuel cell manufacturing method.
  2. 　積層された前記複数の発電ユニットを前記第１の温度に昇温するのに先立って、前記第１の温度よりも低い第２の温度に昇温するとともに、前記第１の温度に昇温前の前記絶縁部材からバインダを取り除く工程をさらに備える、請求項１に記載の燃料電池の製造方法。 Prior to raising the temperature of the plurality of stacked power generation units to the first temperature, the temperature is raised to a second temperature lower than the first temperature, and before raising the temperature to the first temperature. The method of manufacturing a fuel cell according to claim 1, further comprising a step of removing a binder from the insulating member.
  3. 　前記バインダを取り除く工程は、前記ガラスが軟化する温度よりも低い前記第２の温度を維持することにより、昇温前の前記絶縁部材に含まれる前記バインダを取り除く工程を含む、請求項２に記載の燃料電池の製造方法。 The step of removing the binder includes the step of removing the binder contained in the insulating member before the temperature rise by maintaining the second temperature lower than a temperature at which the glass softens. Fuel cell manufacturing method.
  4. 　前記バインダの熱分解開始温度または焼失開始温度は、前記ガラスが軟化する温度よりも低い、請求項２に記載の燃料電池の製造方法。 The fuel cell manufacturing method according to claim 2, wherein a thermal decomposition start temperature or a burnout start temperature of the binder is lower than a temperature at which the glass softens.
  5. 　前記バインダを取り除く工程は、前記第１の温度に昇温前の前記絶縁部材から前記バインダを取り除くことにより、前記バインダを取り除く工程後の前記絶縁部材に含まれる前記セラミック粒子の重量％を、５重量％以上３０重量％以下にする、請求項２に記載の燃料電池の製造方法。 The step of removing the binder comprises removing 5% of the ceramic particles contained in the insulating member after the step of removing the binder by removing the binder from the insulating member before raising the temperature to the first temperature. The method for producing a fuel cell according to claim 2, wherein the fuel cell content is not less than 30% by weight and not more than 30% by weight.
  6. 　前記絶縁部材の厚みを調整する工程と前記バインダを取り除く工程との間に設けられ、積層された前記複数の発電ユニットを昇温させながら、前記第１の荷重よりも小さい第２の荷重を、積層方向に隣接する前記複数の発電ユニットに、互いに近接する方向に加えることにより、前記絶縁部材の収縮を抑制する工程をさらに備える、請求項２に記載の燃料電池の製造方法。 A second load smaller than the first load is provided between the step of adjusting the thickness of the insulating member and the step of removing the binder while raising the temperature of the stacked power generation units. The method for manufacturing a fuel cell according to claim 2, further comprising a step of suppressing contraction of the insulating member by adding the plurality of power generation units adjacent to each other in a stacking direction in a direction close to each other.
  7. 　前記絶縁部材の収縮を抑制する工程は、前記絶縁部材に含まれる前記ガラスが軟化する前に、前記第２の荷重を前記複数の発電ユニットに加える工程を含む、請求項６に記載の燃料電池の製造方法。 The fuel cell according to claim 6, wherein the step of suppressing contraction of the insulating member includes a step of applying the second load to the plurality of power generation units before the glass included in the insulating member is softened. Manufacturing method.
  8. 　前記発電ユニットは、前記セルの前記アノード側に設けられる金属製の厚み調整部材をさらに含み、
    　前記バインダを取り除く工程の後、前記第２の温度よりも高くかつ前記第１の温度よりも低い第３の温度に昇温するとともに、還元性ガスの雰囲気下に前記厚み調整部材を配置することにより、酸化した状態の前記厚み調整部材を還元することによって、前記厚み調整部材の硬さを小さくする工程をさらに備える、請求項２に記載の燃料電池の製造方法。     The power generation unit further includes a metal thickness adjusting member provided on the anode side of the cell,
    After the step of removing the binder, the temperature is raised to a third temperature that is higher than the second temperature and lower than the first temperature, and the thickness adjusting member is disposed in a reducing gas atmosphere. The method of manufacturing a fuel cell according to claim 2, further comprising reducing the hardness of the thickness adjusting member by reducing the thickness adjusting member in an oxidized state.
  9. 　昇温前の前記絶縁部材に含まれる前記セラミック粒子の粒径は、１０μｍ以下である、請求項１に記載の燃料電池の製造方法。 2. The method of manufacturing a fuel cell according to claim 1, wherein a particle size of the ceramic particles contained in the insulating member before the temperature rise is 10 μm or less.
  10. 　積層された複数の発電ユニットを備え、
    　前記発電ユニットは、
    　一方の表面にアノードが形成され、他方の表面にカソードが形成されたセルと、
    　前記セルの外側を取り囲むように設けられ、前記アノードに供給される燃料ガスと、前記カソードに供給される酸化剤とが混合するのを抑制する、セラミック粒子と非晶質であるガラスとを有する絶縁部材とを含む、燃料電池。     It has a plurality of power generation units stacked,
    The power generation unit is
    A cell having an anode formed on one surface and a cathode formed on the other surface;
    The ceramic particles and the amorphous glass are provided so as to surround the outside of the cell and suppress mixing of the fuel gas supplied to the anode and the oxidant supplied to the cathode. A fuel cell comprising an insulating member.
  11. 　前記絶縁部材は、５重量％以上３０重量％以下の前記セラミック粒子を含む、請求項１０に記載の燃料電池。 11. The fuel cell according to claim 10, wherein the insulating member includes 5 wt% or more and 30 wt% or less of the ceramic particles.
  12. 　前記発電ユニットは、前記セルの前記アノード側に設けられる金属製の厚み調整部材をさらに含む、請求項１０に記載の燃料電池。 The fuel cell according to claim 10, wherein the power generation unit further includes a metal thickness adjusting member provided on the anode side of the cell.
  13. 　積層された前記複数の発電ユニットの積層方向の一方の端部側に配置され、前記セルを前記積層方向の他方の端部側に向けて押圧する弾性部材をさらに備える、請求項１０に記載の燃料電池。 The elastic member that is disposed on one end side in the stacking direction of the plurality of stacked power generation units and that presses the cell toward the other end side in the stacking direction. Fuel cell.
  14. 　前記絶縁部材は、前記セルの外側を取り囲むように枠形状を有する、請求項１０に記載の燃料電池。 The fuel cell according to claim 10, wherein the insulating member has a frame shape so as to surround the outside of the cell.
PCT/JP2017/016466 2016-05-06 2017-04-26 Method for manufacturing fuel cell, and fuel cell WO2017191787A1 (en)

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