JP7366090B2 - Method of manufacturing the composite - Google Patents

Description

The technology disclosed herein relates to a method for manufacturing a composite.

A fuel cell including a solid electrolyte layer (hereinafter referred to as "SOFC") is known as one type of fuel cell that generates power using an electrochemical reaction between hydrogen and oxygen. A fuel cell single cell (hereinafter simply referred to as a "single cell"), which is the smallest structural unit of SOFC, faces an electrolyte layer in a predetermined direction (hereinafter referred to as "first direction") with the electrolyte layer in between. It includes an air electrode and a fuel electrode.

The SOFC manufacturing method includes a step of forming a printed pattern that will become an air electrode or a fuel electrode (hereinafter referred to as an "electrode layer") by, for example, screen printing an electrolyte layer. In this process, the so-called saddle phenomenon, in which the peripheral edge of the printed pattern swells, may occur. When the printed pattern in which the saddle phenomenon has occurred is fired, an electrode layer having convex portions on the periphery that are higher than the center portion is formed. When a fuel cell stack is constructed using a plurality of single cells each having an electrode layer having such a convex portion, stress may be excessively concentrated due to the convex portion of the electrode layer being pressed against another member (for example, a current collecting member). However, as a result, there is a risk that, for example, a single cell or the like may be damaged.

Therefore, a technique is conventionally known in which a printed pattern is formed by screen printing and fired, and then the surface of the printed pattern is ground by laser processing to remove the convex portions (for example, see Patent Document 1).

Japanese Patent Application Publication No. 2015-84281

With the conventional technology of cutting convex parts by laser processing, for example, the manufacturing time of the SOFC becomes longer due to the time required for laser processing, and the quality of the single cell deteriorates due to adhesion of grinding debris generated during laser processing. Therefore, there is room for further improvement, such as the development of an alternative technology to this conventional technique or a technique that can be used in combination with this conventional technique.

These issues are also common to single electrolytic cells, which are the constituent units of solid oxide electrolytic cells (hereinafter referred to as "SOEC"), which generate hydrogen using the electrolysis reaction of water. This is a challenge. Note that, in this specification, a single fuel cell cell and a single electrolytic cell are collectively referred to as an electrochemical reaction single cell. In addition, such problems are common not only when forming a printed pattern that becomes an electrode layer, but also when forming a printed pattern that becomes a component of a composite that includes at least an electrochemical reaction single cell. be.

This specification discloses a technique that can solve at least part of the above-mentioned problems.

The technology disclosed in this specification can be realized, for example, as the following form.

(1) The method for manufacturing a composite disclosed herein includes at least an electrochemical reaction single cell including a solid electrolyte layer, and an air electrode and a fuel electrode facing each other with the solid electrolyte layer in between. In the method for manufacturing a composite, the step of preparing a base member having a flat surface at least in part; The step of setting the printing area in a deformed position higher than the central position of the printing area, and performing screen printing on the printing area of the base member in the deformed position, allows the composite material to be applied to the printing area of the base member. forming a predetermined printing pattern forming a part of the printing pattern.

In the present method for manufacturing a composite, the base member is brought into a deformed position in which the peripheral edge of the print area on the base member is higher than the center of the print area. Then, screen printing is performed on the printing area on the base member in the deformed position, and a predetermined printing pattern is formed on the printing area on the base member. As a result, a so-called saddle phenomenon may occur at the periphery of the printed pattern. However, when the base member on which the printed pattern is formed returns from the deformed position to the pre-deformed position, the height of the peripheral edge of the printed pattern decreases accordingly. Therefore, according to the present method for manufacturing a composite, it is possible to manufacture a composite in which the influence of the swelling of the peripheral edge of the printed pattern caused by the saddle phenomenon is suppressed.

(2) In the above method for manufacturing a composite, the base member is arranged on a flat arrangement surface, and a spacer is sandwiched between the base member and the arrangement surface, so that the deformed posture is achieved. It is also possible to have a configuration in which According to the method for manufacturing the present composite body, the base member can be brought into a deformed position by a relatively simple method of using a spacer.

(3) In the method for manufacturing a composite, at least a portion of the spacer overlaps with the peripheral edge of the printing area of the base member, and the width of the spacer in the horizontal direction is 4 mm when viewed in the vertical direction. The thickness may be 10 mm or less, and the vertical thickness of the spacer may be 0.05 mm or more and 0.1 mm or less. According to the method for manufacturing the present composite, the printing area on the base member in the deformed position can be made into a relatively gently curved surface. Therefore, the load applied to the base member in the deformed state is reduced, and for example, damage to the base member can be suppressed.

(4) In the method for manufacturing the composite, an auxiliary member having a receiving surface that makes surface contact with the screen printing plate used in the screen printing is arranged on the outer peripheral side of the base member in the deformed posture, The screen printing may be performed on the printing area on the base member. In the manufacturing method of this composite, in screen printing, the receiving surface of the auxiliary member disposed on the outer peripheral side of the base member in a deformed posture comes into surface contact with the screen printing plate, so that the pressing force from the screen printing plate is applied to the screen printing plate. distributed on the receiving surface. Thereby, according to the method for manufacturing the present composite, it is possible to prevent the pressing force from the screen printing plate from concentrating on the base member in the deformed position and damaging it.

(5) The method for manufacturing a composite body includes the step of firing the base member on which the printed pattern is formed, and after the firing, the base member has returned to its pre-deformation position. The height difference between the central portion and the peripheral portion may be within ±5 μm. According to the manufacturing method of the present composite, the saddle phenomenon is less likely to occur than when the difference in height between the central part and the peripheral part of the printed pattern is not within ±5 μm when the underlying member has returned to its pre-deformation position after firing. The influence of the resulting swelling of the peripheral edge of the printed pattern is more effectively suppressed.

Note that the technology disclosed in this specification can be realized in various forms, for example, an electrochemical reaction single cell (a fuel cell single cell or an electrolytic single cell), an electric cell having an electrochemical reaction single cell, etc. It can be realized in the form of an electrochemical reaction cell stack (fuel cell stack or electrolytic cell stack) including a plurality of chemical reaction units, a method for manufacturing them, and the like.

A perspective view showing the external configuration of a fuel cell stack 100 in an embodiment. An explanatory diagram showing the XZ cross-sectional configuration of the fuel cell stack 100 at the II-II position in FIG. An explanatory diagram showing the YZ cross-sectional configuration of the fuel cell stack 100 at the position III-III in FIG. An explanatory diagram showing the XZ cross-sectional configuration of two power generation units 102 adjacent to each other at the same position as the cross section shown in FIG. An explanatory diagram showing a YZ cross-sectional configuration of two mutually adjacent power generation units 102 at the same position as the cross section shown in FIG. 3 An explanatory diagram showing a support member 200, a spacer 300, and an auxiliary member 400 used in screen printing in this embodiment Explanatory diagram showing a process for forming a print pattern 114P on a half cell 110P Schematic diagram for explaining the difference in the magnitude of the load on the half cell 110P depending on the presence or absence of the auxiliary member 400 Explanatory diagram showing performance evaluation results

A. Embodiment:
A-1. composition:
(Configuration of fuel cell stack 100)
FIG. 1 is a perspective view showing an external configuration of a fuel cell stack 100 in this embodiment, and FIG. 2 is an explanatory diagram showing an XZ cross-sectional configuration of the fuel cell stack 100 at a position II-II in FIG. FIG. 3 is an explanatory diagram showing a YZ cross-sectional configuration of the fuel cell stack 100 at the position III-III in FIG. Each figure shows mutually orthogonal XYZ axes for specifying directions. In this specification, for convenience, the positive Z-axis direction will be referred to as the upward direction, and the negative Z-axis direction will be referred to as the downward direction, but the fuel cell stack 100 is actually oriented in a different direction. may be installed. The same applies to FIG. 4 and subsequent figures. Note that the vertical direction is an example of a first direction in the claims.

The fuel cell stack 100 includes a plurality (seven in this embodiment) of power generation units 102 and a pair of end plates 104 and 106. The seven power generation units 102 are arranged in a predetermined arrangement direction (vertical direction in this embodiment). A pair of end plates 104 and 106 are arranged so as to sandwich an assembly composed of seven power generation units 102 from above and below.

A plurality of holes (eight in this embodiment) that penetrate in the vertical direction are formed in the peripheral edge of each layer (power generation unit 102, end plates 104, 106) that constitutes the fuel cell stack 100 around the Z-axis direction. The corresponding holes formed in each layer communicate with each other in the vertical direction to form a communication hole 108 extending in the vertical direction from one end plate 104 to the other end plate 106. In the following description, the holes formed in each layer of the fuel cell stack 100 to constitute the communication holes 108 may also be referred to as the communication holes 108.

A bolt 22 extending in the vertical direction is inserted into each communication hole 108, and the fuel cell stack 100 is fastened by the bolt 22 and nuts 24 fitted on both sides of the bolt 22. As shown in FIGS. 2 and 3, between the nut 24 fitted on one side (upper side) of the bolt 22 and the upper surface of the end plate 104 that constitutes the upper end of the fuel cell stack 100, An insulating sheet 26 is interposed between the nut 24 fitted on the other side (lower side) of the nut 22 and the lower surface of the end plate 106 that constitutes the lower end of the fuel cell stack 100. However, at a location where a gas passage member 27 (described later) is provided, an insulating sheet is placed between the nut 24 and the surface of the end plate 106, and on the upper and lower sides of the gas passage member 27 and the gas passage member 27, respectively. 26 is interposed. The insulating sheet 26 is made of, for example, a mica sheet, a ceramic fiber sheet, a ceramic powder sheet, a glass sheet, a glass-ceramic composite, or the like.

The outer diameter of the shaft portion of each bolt 22 is smaller than the inner diameter of each communication hole 108. Therefore, a space is ensured between the outer circumferential surface of the shaft portion of each bolt 22 and the inner circumferential surface of each communication hole 108. As shown in FIGS. 1 and 2, near the midpoint of one side (the side in the positive X-axis direction of the two sides parallel to the Y-axis) on the outer periphery of the fuel cell stack 100 around the Z-axis direction. The space formed by the located bolt 22 (bolt 22A) and the communication hole 108 into which the bolt 22A is inserted is a space into which oxidizing gas OG is introduced from outside the fuel cell stack 100, and the oxidizing gas OG is It functions as an oxidizing gas introduction manifold 161 that is a gas flow path for supplying the power generation unit 102, and inside the side opposite to this side (the side on the negative side of the X-axis of the two sides parallel to the Y-axis). The space formed by the bolt 22 (bolt 22B) located near the point and the communication hole 108 through which the bolt 22B is inserted contains oxidant off-gas OOG, which is gas discharged from the air chamber 166 of each power generation unit 102. It functions as an oxidizing gas exhaust manifold 162 that exhausts the oxidant gas to the outside of the fuel cell stack 100. Note that in this embodiment, air, for example, is used as the oxidant gas OG.

Further, as shown in FIGS. 1 and 3, the midpoint of one side (the side in the positive Y-axis direction of the two sides parallel to the X-axis) on the outer periphery of the fuel cell stack 100 around the Z-axis direction The space formed by the bolt 22 (bolt 22D) located nearby and the communication hole 108 into which the bolt 22D is inserted allows fuel gas FG to be introduced from outside the fuel cell stack 100, and the fuel gas FG to be passed through the space. A bolt that functions as a fuel gas introduction manifold 171 for supplying to the power generation unit 102 and is located near the midpoint of the side opposite to this side (the side on the negative side of the Y-axis of the two sides parallel to the X-axis) 22 (bolts 22E) and the communication holes 108 into which the bolts 22E are inserted, the space is configured to transport fuel off-gas FOG, which is gas discharged from the fuel chamber 176 of each power generation unit 102, to the outside of the fuel cell stack 100. It functions as a fuel gas exhaust manifold 172 that discharges fuel gas to. In this embodiment, a hydrogen-rich gas obtained by reforming city gas, for example, is used as the fuel gas FG.

The fuel cell stack 100 is provided with four gas passage members 27. Each gas passage member 27 has a hollow cylindrical main body 28 and a hollow cylindrical branch 29 branching from a side surface of the main body 28 . The hole in the branch portion 29 communicates with the hole in the main body portion 28 . A gas pipe (not shown) is connected to the branch portion 29 of each gas passage member 27. Further, as shown in FIG. 2, the hole in the main body 28 of the gas passage member 27 located at the position of the bolt 22A forming the oxidant gas introduction manifold 161 communicates with the oxidant gas introduction manifold 161, A hole in the main body portion 28 of the gas passage member 27 located at the position of the bolt 22B forming the oxidant gas discharge manifold 162 communicates with the oxidant gas discharge manifold 162. Further, as shown in FIG. 3, the holes in the main body 28 of the gas passage member 27 disposed at the positions of the bolts 22D forming the fuel gas introduction manifold 171 communicate with the fuel gas introduction manifold 171, and A hole in the main body portion 28 of the gas passage member 27 located at the position of the bolt 22E forming the exhaust manifold 172 communicates with the fuel gas exhaust manifold 172.

(Configuration of end plates 104, 106)
The pair of end plates 104 and 106 are flat conductive members that are approximately rectangular when viewed in the Z-axis direction, and are made of stainless steel, for example. One end plate 104 is arranged above the uppermost power generation unit 102, and the other end plate 106 is arranged below the lowermost power generation unit 102. A plurality of power generation units 102 are held in a pressed state by a pair of end plates 104 and 106. The upper end plate 104 functions as a positive output terminal of the fuel cell stack 100, and the lower end plate 106 functions as a negative output terminal of the fuel cell stack 100.

(Configuration of power generation unit 102)
FIG. 4 is an explanatory diagram showing the XZ cross-sectional structure of two power generation units 102 adjacent to each other at the same position as the cross section shown in FIG. 2, and FIG. FIG. 2 is an explanatory diagram showing a YZ cross-sectional configuration of two power generation units 102. FIG.

As shown in FIGS. 4 and 5, the power generation unit 102 includes a single cell 110, a separator 120, an air electrode side frame 130, an air electrode side current collector 134, a fuel electrode side frame 140, and a fuel electrode side frame 130. It includes a current collector 144 and a pair of interconnectors 150 forming the uppermost layer and the lowermost layer of the power generation unit 102. Holes corresponding to the communication holes 108 into which the bolts 22 described above are inserted are formed in the peripheral edges of the separator 120, the air electrode side frame 130, the fuel electrode side frame 140, and the interconnector 150 around the Z-axis direction.

The interconnector 150 is a substantially rectangular flat plate-shaped conductive member when viewed in the Z-axis direction, and is made of a material containing Cr, such as ferritic stainless steel. The interconnector 150 ensures electrical continuity between the power generation units 102 and prevents reaction gases from mixing between the power generation units 102 . In addition, in this embodiment, when two power generation units 102 are arranged adjacently, one interconnector 150 is shared by the two adjacent power generation units 102. That is, the upper interconnector 150 in a certain power generation unit 102 is the same member as the lower interconnector 150 in another power generation unit 102 adjacent to the upper side of the power generation unit 102. Furthermore, since the fuel cell stack 100 includes a pair of end plates 104 and 106, the uppermost power generation unit 102 in the fuel cell stack 100 does not include the upper interconnector 150, and the lowermost power generation unit 102 does not include the upper interconnector 150. The power generation unit 102 does not include a lower interconnector 150 (see FIGS. 2 and 3).

The single cell 110 includes an electrolyte layer 112, an air electrode (cathode) 114 disposed above the electrolyte layer 112, a fuel electrode (anode) 116 disposed below the electrolyte layer 112, and an electrolyte layer 112. An intermediate layer 180 is provided between the layer 112 and the air electrode 114. Note that the single cell 110 of this embodiment is a fuel electrode supported type single cell in which the other layers (electrolyte layer 112, air electrode 114, intermediate layer 180) that constitute the single cell 110 are supported by the fuel electrode 116.

The electrolyte layer 112 is a substantially rectangular flat plate-shaped member when viewed in the Z-axis direction, and is a dense layer (low porosity). The electrolyte layer 112 includes a solid oxide (eg, YSZ (yttria-stabilized zirconia), ScSZ (scandia-stabilized zirconia), CSZ (calcia-stabilized zirconia)). In this way, the single cell 110 of this embodiment is a solid oxide fuel cell (SOFC) that uses a solid oxide as an electrolyte.

The air electrode 114 is a substantially rectangular plate-shaped member smaller than the electrolyte layer 112 when viewed in the Z-axis direction, and is a porous layer with a higher porosity than the electrolyte layer 112. The air electrode 114 is made of a perovskite oxide represented by ABO ₃ (for example, lanthanum strontium cobalt iron oxide (LSCF), lanthanum strontium iron oxide (LSF), lanthanum strontium cobalt oxide (LSC), lanthanum strontium manganese oxide). (LSM), lanthanum nickel iron oxide (LNF), etc.).

The fuel electrode 116 is a substantially rectangular flat member having substantially the same size as the electrolyte layer 112 when viewed in the Z-axis direction, and is a porous layer having a higher porosity than the electrolyte layer 112 . Although not shown, in this embodiment, the fuel electrode 116 includes a substrate layer that constitutes the lower surface of the fuel electrode 116 and a functional layer located between the substrate layer and the electrolyte layer 112. The functional layer of the fuel electrode 116 is a layer that mainly functions to generate electrons and water vapor by reacting oxygen ions supplied from the electrolyte layer 112 with hydrogen, etc. contained in the fuel gas FG. It contains Ni, which is a conductive material, and an oxygen ion conductive oxide (for example, YSZ). Further, the substrate layer of the fuel electrode 116 is a layer that mainly functions to support the functional layer, the electrolyte layer 112, and the air electrode 114, and is made of Ni, which is an electron conductive substance, and an oxygen ion conductive oxide ( For example, YSZ).

The intermediate layer (reaction prevention layer) 180 is a flat plate-shaped member that is approximately rectangular when viewed in the Z-axis direction. The intermediate layer 180 is formed of a solid oxide having ion conductivity, such as SDC (samarium doped ceria), GDC (gadolinium doped ceria), LDC (lanthanum doped ceria), and YDC (yttrium doped ceria).

The separator 120 is a frame-shaped member in which a substantially rectangular hole 121 that penetrates vertically is formed near the center, and is made of metal, for example. The surrounding portion of the hole 121 in the separator 120 faces the peripheral edge of the surface of the electrolyte layer 112 on the air electrode 114 side. The separator 120 is bonded to the electrolyte layer 112 (single cell 110) by a bonding portion 124 formed of a brazing material (for example, Ag brazing) disposed at opposing portions. The separator 120 separates an air chamber 166 facing the air electrode 114 and a fuel chamber 176 facing the fuel electrode 116, thereby preventing gas from leaking from one electrode side to the other electrode side at the periphery of the single cell 110. suppressed.

The air electrode side frame 130 is a frame-like member in which a substantially rectangular hole 131 is formed near the center and penetrates in the vertical direction, and is made of an insulator such as mica, for example. The hole 131 of the air electrode side frame 130 constitutes an air chamber 166 facing the air electrode 114. The air electrode side frame 130 is in contact with the peripheral edge of the surface of the separator 120 on the side opposite to the side facing the electrolyte layer 112 and the peripheral edge of the surface of the interconnector 150 on the side opposite to the air electrode 114. . Further, the pair of interconnectors 150 included in the power generation unit 102 are electrically insulated by the air electrode side frame 130. The air electrode side frame 130 also includes an oxidizing gas supply communication hole 132 that communicates between the oxidizing gas introduction manifold 161 and the air chamber 166, and an oxidizing gas supply communication hole 132 that communicates between the air chamber 166 and the oxidizing gas discharge manifold 162. A discharge communication hole 133 is formed.

The fuel electrode side frame 140 is a frame-shaped member in which a substantially rectangular hole 141 that vertically penetrates is formed near the center, and is made of metal, for example. The hole 141 of the fuel electrode side frame 140 constitutes a fuel chamber 176 facing the fuel electrode 116. The fuel electrode side frame 140 is in contact with the peripheral edge of the surface of the separator 120 facing the electrolyte layer 112 and the peripheral edge of the surface of the interconnector 150 facing the fuel electrode 116 . The fuel electrode side frame 140 also includes a fuel gas supply communication hole 142 that communicates between the fuel gas introduction manifold 171 and the fuel chamber 176, and a fuel gas discharge communication hole 143 that communicates between the fuel chamber 176 and the fuel gas discharge manifold 172. is formed.

The fuel electrode side current collector 144 is arranged within the fuel chamber 176. The fuel electrode side current collector 144 includes an interconnector facing part 146, an electrode facing part 145, and a connecting part 147 connecting the electrode facing part 145 and the interconnector facing part 146, and is made of, for example, nickel or nickel alloy. , stainless steel, etc. The electrode facing portion 145 is in contact with the surface of the fuel electrode 116 on the side opposite to the side facing the electrolyte layer 112, and the interconnector facing portion 146 is in contact with the surface of the interconnector 150 on the side opposite to the fuel electrode 116. are in contact. However, as described above, since the lowest power generation unit 102 in the fuel cell stack 100 does not include the lower interconnector 150, the interconnector facing portion 146 in the power generation unit 102 is located on the lower end plate. 106 is in contact. Since the fuel electrode side current collector 144 has such a configuration, it electrically connects the fuel electrode 116 and the interconnector 150 (or the end plate 106). Note that a spacer 149 made of mica, for example, is arranged between the electrode facing part 145 and the interconnector facing part 146. Therefore, the fuel electrode side current collector 144 follows the deformation of the power generation unit 102 due to temperature cycles and reaction gas pressure fluctuations, and connects the fuel electrode 116 and the interconnector 150 (or end plate 106) via the fuel electrode side current collector 144. Good electrical connection is maintained.

The air electrode side current collector 134 is arranged within the air chamber 166. The air electrode side current collector 134 is composed of a plurality of substantially square columnar current collector elements 135, and is made of a material containing Cr, such as ferritic stainless steel. The air electrode side current collector 134 is in contact with the surface of the air electrode 114 on the side opposite to the side facing the electrolyte layer 112 and the surface of the interconnector 150 on the side opposite to the air electrode 114. However, as described above, since the uppermost power generation unit 102 in the fuel cell stack 100 does not include the upper interconnector 150, the air electrode side current collector 134 in the power generation unit 102 is connected to the upper end plate. 104 is in contact. Since the air electrode side current collector 134 has such a configuration, it electrically connects the air electrode 114 and the interconnector 150 (or the end plate 104). A conductive bonding layer may be interposed between the air electrode 114 and the air electrode side current collector 134 to bond them together. Note that the air electrode side current collector 134 and the interconnector 150 may be configured as an integral member.

A-2. Operation of fuel cell stack 100:
As shown in FIGS. 2 and 4, the oxidizing gas OG is supplied through a gas pipe (not shown) connected to the branch part 29 of the gas passage member 27 provided at the position of the oxidizing gas introduction manifold 161. Then, the oxidizing gas OG is supplied to the oxidizing gas introduction manifold 161 through the branch portion 29 of the gas passage member 27 and the hole of the main body 28, and is supplied to the oxidizing gas introduction manifold 161 from the oxidizing gas introduction manifold 161 to the oxidizing gas OG of each power generation unit 102. The agent gas is supplied to the air chamber 166 via the agent gas supply communication hole 132. Further, as shown in FIGS. 3 and 5, fuel gas FG is supplied via a gas pipe (not shown) connected to a branch part 29 of the gas passage member 27 provided at the position of the fuel gas introduction manifold 171. Then, the fuel gas FG is supplied to the fuel gas introduction manifold 171 via the branch part 29 of the gas passage member 27 and the hole of the main body part 28, and is connected to the fuel gas supply communication of each power generation unit 102 from the fuel gas introduction manifold 171. The fuel chamber 176 is supplied through the hole 142 .

When the oxidant gas OG is supplied to the air chamber 166 of each power generation unit 102 and the fuel gas FG is supplied to the fuel chamber 176, power generation is performed in the single cell 110 by an electrochemical reaction between the oxidant gas OG and the fuel gas FG. be exposed. This power generation reaction is an exothermic reaction. In each power generation unit 102, the air electrode 114 of the single cell 110 is electrically connected to one interconnector 150 via the air electrode side current collector 134, and the fuel electrode 116 is electrically connected via the fuel electrode side current collector 144. It is electrically connected to the other interconnector 150. Further, the plurality of power generation units 102 included in the fuel cell stack 100 are electrically connected in series. Therefore, the electrical energy generated in each power generation unit 102 is extracted from the end plates 104 and 106 that function as output terminals of the fuel cell stack 100. Note that SOFC generates power at a relatively high temperature (for example, 700°C to 1000°C), so after startup, the fuel cell stack 100 is not connected to the heater ( (not shown).

As shown in FIGS. 2 and 4, the oxidant off-gas OOG discharged from the air chamber 166 of each power generation unit 102 is discharged to the oxidant gas discharge manifold 162 through the oxidant gas discharge communication hole 133, and further oxidized. The fuel cell stack 100 is passed through the main body portion 28 of the gas passage member 27 provided at the position of the agent gas discharge manifold 162 and the hole in the branch portion 29, and through a gas pipe (not shown) connected to the branch portion 29. is discharged to the outside. Further, the fuel off-gas FOG discharged from the fuel chamber 176 of each power generation unit 102 is discharged to the fuel gas discharge manifold 172 via the fuel gas discharge communication hole 143, as shown in FIGS. Externally through the main body 28 and branch section 29 of the gas passage member 27 provided at the exhaust manifold 172, and through a gas pipe (not shown) connected to the branch section 29, be discharged.

A-3. Method for manufacturing fuel cell stack 100:
The method for manufacturing the fuel cell stack 100 of this embodiment is, for example, as follows.

(Formation of laminate of electrolyte layer 112 and fuel electrode 116)
A butyral resin, a plasticizer dioctyl phthalate (DOP), a dispersant, and a mixed solvent of toluene and ethanol are added to the YSZ powder and mixed in a ball mill to prepare a slurry. The obtained slurry is made into a thin film by a doctor blade method to obtain a green sheet for an electrolyte layer having a predetermined thickness (for example, about 6 μm). In addition, organic beads as a pore-forming material, butyral resin, DOP as a plasticizer, a dispersant, and a mixed solvent of toluene and ethanol were added to the mixed powder of NiO powder and YSZ powder. Mix in a ball mill to prepare a slurry. The obtained slurry is made into a thin film by a doctor blade method to obtain a green sheet for a fuel electrode substrate layer having a predetermined thickness (for example, about 400 μm). In addition, butyral resin, DOP as a plasticizer, a dispersant, and a mixed solvent of toluene and ethanol were added to the mixed powder of NiO powder and YSZ powder, and the mixture was mixed in a ball mill to form a slurry. Prepare. The obtained slurry is made into a thin film by a doctor blade method to obtain a green sheet for a fuel electrode functional layer having a predetermined thickness (for example, about 11 μm). By pasting and press-bonding each green sheet, a molded body in which a fuel electrode substrate layer green sheet, a fuel electrode functional layer green sheet, and an electrolyte layer green sheet are laminated in this order is obtained.

Next, the molded body is degreased at a predetermined temperature (for example, about 280° C.), and then fired at a predetermined temperature (for example, about 1350° C.) for a predetermined time (for example, about 1 hour). As a result, a laminate of the electrolyte layer 112 and the fuel electrode 116 is obtained.

(Formation of intermediate layer 180)
Polyvinyl alcohol as an organic binder and butyl carbitol as an organic solvent are added and mixed to the GDC powder, and the viscosity is adjusted to prepare a paste for the intermediate layer. The obtained intermediate layer paste is applied to the surface of the electrolyte layer 112 in the above-described laminate by, for example, screen printing, and baked at a predetermined temperature (for example, 1200° C.). As a result, the intermediate layer 180 is formed, and a laminate of the intermediate layer 180, the electrolyte layer 112, and the fuel electrode 116 is obtained. Hereinafter, this stacked body will be referred to as a "half cell 110P." The half cell 110P is an example of a "base member" in the claims, and the above-mentioned "formation of a laminate of the electrolyte layer 112 and the fuel electrode 116" and "formation of the intermediate layer 180" are "formation of the intermediate layer 180" in the claims. This is an example of the step of preparing a base member.

(Formation of air electrode 114)
A mixed powder of a perovskite oxide (for example, LSCF) powder and a sulfate (for example, SrSO ₄ ) powder is prepared, and polyvinyl alcohol as an organic binder and butyl carbitol as an organic solvent are added to the mixed powder. A paste for the air electrode is prepared by adding and mixing and adjusting the viscosity. The obtained air electrode paste is applied to the surface of the intermediate layer 180 in the half cell 110P by screen printing to form a printed pattern 114P.

Hereinafter, the process for forming the print pattern 114P on the half cell 110P will be described in detail. FIG. 6 is an explanatory diagram showing the support member 200, spacer 300, and auxiliary member 400 used in screen printing in this embodiment. FIG. 6(B) shows the top configuration of the support member 200, and FIG. 6(A) shows the XZ cross-sectional configuration of the support member 200 at the AA position in FIG. 6(B). ing.

First, as shown in FIG. 6, the support member 200 includes a peripheral wall portion 210 and an arrangement portion 220. The placement section 220 is a rectangular flat plate-like portion, and has a flat placement surface 222 . The peripheral wall part 210 is a rectangular frame-shaped part arranged so as to surround the periphery of the arrangement part 220. The upper end of the peripheral wall portion 210 protrudes above the placement surface 222 of the placement portion 220. In addition, in this embodiment, the outer circumferential surface of the arrangement part 220 is arranged so as to contact the inner circumferential surface 212 of the peripheral wall part 210.

A spacer 300 is arranged on the arrangement surface 222 of the arrangement section 220. The spacer 300 has a rectangular frame shape when viewed in the vertical direction (see FIG. 6(B)). The outer size of the spacer 300 is such that it can be accommodated within the peripheral wall portion 210 of the support member 200. The vertical thickness D1 of the spacer 300 is smaller than the horizontal width D2 of the spacer 300. That is, the spacer 300 has a flat shape that is thin in the vertical direction (see FIG. 6(A)). In this embodiment, the outer peripheral surface of the spacer 300 is arranged so as to contact the inner peripheral surface 212 of the peripheral wall portion 210 of the support member 200. Note that the spacer 300 is preferably arranged at a position closer to the peripheral edge of the arrangement surface 222 when viewed in the vertical direction. Further, when viewed in the vertical direction, the width D2 of the spacer 300 is preferably 1/2 or less of the shortest distance from the center of the placement surface 222 to the peripheral edge of the placement surface 222, and is 1/4 or less of the shortest distance. The distance is preferably 1/8 or less of the shortest distance.

An auxiliary member 400 is arranged on the upper surface 214 of the peripheral wall part 210 of the arrangement part 220. The shape of the auxiliary member 400 when viewed in the vertical direction is a rectangular frame shape (see FIG. 6(B)). The size of the inner circumferential side of the auxiliary member 400 is larger than the inner circumferential edge of the upper surface 214 of the peripheral wall section 210 and smaller than the outer circumferential edge of the upper surface 214 of the peripheral wall section 210. The vertical thickness D3 of the auxiliary member 400 is smaller than the horizontal width D4 of the auxiliary member 400. That is, the auxiliary member 400 has a flat shape that is thin in the vertical direction (see FIG. 6(A)).

FIG. 7 is an explanatory diagram showing a process for forming a print pattern 114P on a half cell 110P. FIG. 7A shows the half cell 110P supported by the support member 200, the screen printing plate 230, and the squeegee 240. The screen printing plate 230 has a plate frame 232 and a screen mesh 234. The plate frame 232 is a frame-shaped body having an opening, and a screen mesh 234 is stretched so as to close the opening.

First, as shown in FIG. 7(A), the half cell 110P is placed on the placement surface 222 of the support member 200. Here, as described above, since the spacer 300 is arranged on the arrangement surface 222 of the support member 200, the spacer 300 is interposed between the peripheral portion of the half cell 110P and the arrangement surface 222. As a result, the half cell 110P assumes a deformed posture. The deformed posture is such that the position H2 of the peripheral edge of the print area E on the upper surface of the half cell 110P is higher than the position H1 of the center of the print area E. The printing area E is an area where the air electrode paste is printed by screen printing (an area where the printing pattern 114P is formed). In this embodiment, the center part of the half cell 110P contacts the arrangement surface 222, and the peripheral part of the half cell 110P is curved so as to be pushed upward by the spacer 300. As a result, the half cell 110P takes the deformed posture described above. There is. The peripheral edge of the half cell 110P in the deformed posture is inclined downward toward the center of the half cell 110P.

In this embodiment, at least a portion of the spacer 300 overlaps the peripheral edge of the print area E of the half cell 110P when viewed in the vertical direction. The horizontal width D2 of the spacer 300 is 4 mm or more and 10 mm or less, and the vertical thickness D1 of the spacer 300 is 0.05 mm or more and 0.1 mm or less.

In this embodiment, the protruding length of the peripheral wall portion 210 with respect to the arrangement surface 222 of the support member 200 (the depth of the recess of the support member 200) is shorter than the thickness of the half cell 110P. Therefore, the position H2 of the peripheral edge of the half cell 110P in the deformed posture is above the upper surface of the peripheral wall 210 of the support member 200. The auxiliary member 400 is used to fill the height gap between the peripheral edge of the half cell 110P in the deformed posture and the top surface of the peripheral wall 210.

The auxiliary member 400 is arranged around the half cell 110P in the deformed posture when viewed in the vertical direction. The height of the receiving surface 410, which is the upper surface of the auxiliary member 400, is approximately the same as the position H2 of the peripheral edge of the half cell 110P in the deformed posture. During screen printing, the receiving surface 410 of the auxiliary member 400 comes into surface contact with the screen printing plate 230 (print frame 232). The screen printing plate 230 is placed on the upper surface of the auxiliary member 400 so that the entire auxiliary member 400 overlaps the plate frame 232 of the screen printing plate 230 when viewed in the vertical direction, and the air electrode paste is applied to the screen using the squeegee 240. The screen mesh 234 of the printing plate 230 is filled. As a result, the air electrode paste is transferred to the print area E of the half cell 110P in the deformed posture, and as a result, a print pattern 114P is formed in the print area E.

Next, when the screen printing plate 230 is separated from the printed pattern 114P, a saddle phenomenon occurs. In the saddle phenomenon, when the screen printing plate 230 is separated from the print pattern 114P, the air electrode paste that was in contact with the inner peripheral surface forming the opening in the plate frame 232 expands, and the peripheral edge of the print pattern 114P bulges. It is a phenomenon. As shown in FIG. 7(B), due to the occurrence of the saddle phenomenon, a convex portion 115P that protrudes upward is formed at the peripheral edge of the printed pattern 114P, and the position H4 of the convex portion 115P is located at the center of the printed pattern 114P. It becomes higher than position H3. Furthermore, a downwardly recessed portion 117P is formed between the convex portion 115P and the central portion.

However, as shown in FIG. 7C, when the half cell 110P on which the printed pattern 114P is formed is returned from the deformed position to the undeformed position before deformation (the position in which the half cell 110P is flat), Accordingly, the position of the convex portion 115P on the peripheral edge of the print pattern becomes lower. In FIG. 7C, the position of the convex portion 115P on the periphery of the print pattern is approximately the same as the position H3 at the center of the print pattern 114P. Next, the half cell 110P on which the printed pattern 114P is formed is dried in a non-deformed state and fired at a predetermined temperature (for example, about 1100° C.). As a result, the air electrode 114 is formed, and the single cell 110 including the fuel electrode 116, the electrolyte layer 112, the intermediate layer 180, and the air electrode 114 is manufactured. In this single cell 110, the peripheral edge of the air electrode 114 is suppressed from rising significantly relative to the center. After firing, it is preferable that the height difference between the central part and the peripheral part of the air electrode 114 in a state where the half cell 110P has returned to its pre-deformation posture is within ±5 μm.

After producing a plurality of unit cells 110 according to the method described above, an assembly process (for example, a process of attaching other members such as a separator 120 to each unit cell 110, a process of stacking a plurality of unit cells 110, and a process of fastening with bolts 22) process, etc.). Through the above steps, manufacturing of the fuel cell stack 100 is completed.

A-4. Effects of this embodiment:
As described above, in this embodiment, the half cell 110P is put into a deformed posture in which the position H2 of the peripheral edge of the print area E in the half cell 110P is higher than the position H1 of the center of the print area E (see FIG. )reference). Then, screen printing is performed on the printing area E in the half cell 110P in the deformed posture, and a predetermined printing pattern 114P is formed on the printing area E in the half cell 110P. As a result, a so-called saddle phenomenon may occur at the periphery of the printed pattern 114P (see FIG. 7(B)). However, when the half cell 110P on which the printed pattern 114P is formed returns from the deformed posture to the pre-deformed posture, the height of the peripheral edge of the printed pattern 114P decreases accordingly (see FIG. 7C). Therefore, according to the manufacturing method of this embodiment, it is possible to manufacture the single cell 110 (fuel cell stack 100) in which the influence of the swelling of the peripheral edge of the printed pattern 114P caused by the saddle phenomenon is suppressed.

Further, in this embodiment, the peripheral edge of the printing area E of the half cell 110P in the deformed posture is inclined downward toward the center of the printing area E. Therefore, in screen printing, the amount of paste applied to the periphery of the printing area E is smaller than the amount of paste applied to the center of the printing area E. Therefore, before the screen printing plate 230 is pulled up, the thickness of the peripheral portion of the printed pattern 114P is thinner than the thickness of the central portion of the printed pattern 114P. As a result, when the screen printing plate 230 is pulled up from the printed pattern 114P, although the periphery of the printed pattern 114P swells due to the saddle phenomenon, the half cells 110P in the deformed posture return to the pre-deformed posture, so that the printed pattern 114P It is possible to suppress the swelling of the peripheral portion relative to the central portion.

In this embodiment, the half cell 110P is placed on the flat placement surface 222, and the spacer 300 is sandwiched between the half cell 110P and the placement surface 222, so that the half cell 110P is brought into a deformed posture (see FIG. 7(A). )reference). As a result, the printed pattern 114P can be brought into a deformed position using the relatively simple method of using the spacer 300.

In this embodiment, at least a portion of the spacer 300 overlaps the peripheral edge of the print area E of the half cell 110P when viewed in the vertical direction (see FIGS. 7A and 7B). The horizontal width D2 of the spacer 300 is 4 mm or more and 10 mm or less, and the thickness D1 of the spacer 300 is 0.05 mm or more and 0.1 mm or less. Thereby, the printing area E in the half cell 110P in the deformed posture can be made into a relatively gently curved surface. Therefore, the load applied to the half cell 110P in the deformed posture is reduced, and for example, damage to the half cell 110P can be suppressed. In particular, it is more effective when the thickness relationship of each layer of the half cell 110P satisfies the following conditions.
The thickness of the electrolyte layer 112 (fired body) is 5 μm or more and 10 μm or less.
The thickness of the functional layer (fired body) of the fuel electrode 116 is 10 μm or more and 20 μm or less.
The thickness of the substrate layer (fired body) of the fuel electrode 116 is 300 μm or more and 800 μm or less.
The thickness of the intermediate layer 180 (fired body) is 1 μm or more and 9 μm or less.

In this embodiment, the printing area E in the half cell 110P is arranged with the auxiliary member 400 having the receiving surface 410 in surface contact with the screen printing plate 230 used in screen printing on the outer peripheral side of the half cell 110P in the deformed posture. Screen printing is performed on the image (see FIG. 7(A)). Here, FIG. 8 is a schematic diagram for explaining the difference in the magnitude of the load on the half cell 110P depending on the presence or absence of the auxiliary member 400. Note that in FIG. 8, the screen mesh 234 is omitted.

FIG. 8A shows the load state on the half cell 110P when the auxiliary member 400 is not used. In this state, only the half cell 110P in the deformed posture contacts the screen printing plate 230 (plate frame 232). Therefore, the pressing force F from the screen printing plate 230 pressed against the squeegee 240 is concentrated on the peripheral edge of the half cell 110P, and there is a possibility that the half cell 110P may be damaged. On the other hand, FIG. 8(B) shows the load state on the half cell 110P when the auxiliary member 400 is used. In this state, in addition to the half cell 110P in the deformed posture, the auxiliary member 400 is in surface contact with the screen printing plate 230. Therefore, the pressing force F from the screen printing plate 230 is dispersed, and the force f applied to the peripheral edge of the half cell 110P is reduced. Thereby, it is possible to prevent the pressing force F from the screen printing board 230 from concentrating on the half cell 110P in the deformed posture and damaging it. Furthermore, the force applied from the screen printing plate 230 to the air electrode paste filled on the half cell 110P is reduced, so that the peripheral edge of the half cell 110P may be damaged due to excessive force being applied to the air electrode paste. It is possible to suppress a large increase.

In this embodiment, after firing, it is preferable that the difference in height between the central part and the peripheral part of the printed pattern 114P (air electrode 114) in a state where the half cell 110P has returned to its pre-deformation posture is within ±5 μm. As a result, compared to the case where the difference in height between the central part and the peripheral part of the printed pattern 114P that has returned to its pre-deformation position is not within ±5 μm, the influence of the swelling of the peripheral part of the printed pattern due to the saddle phenomenon is reduced. , more effectively suppressed.

A-5. Performance evaluation:
Performance evaluation performed using samples of a plurality of single cells 110 will be described below. FIG. 9 is an explanatory diagram showing the performance evaluation results. As shown in FIG. 9, each of the samples S1 to S12 has differences in whether or not a spacer 300 is used, the size of the spacer 300, and whether or not an auxiliary member 400 is used in the process of forming the above-described printed pattern 114P in a half cell 110P. are different from each other. The saddle height at the air electrode 114 was measured for the single cell 110 manufactured under each condition. The saddle height is the value obtained by subtracting the "thickness of the unit cell 110 at the center of the air electrode 114" from the "thickness of the unit cell 110 at the peripheral edge of the air electrode 114." The larger the value of the saddle height, the larger the swell of the peripheral edge of the air electrode 114 relative to the center. The thickness of each portion of the single cell 110 was measured at 0.1 mm intervals using a known thickness measuring device equipped with a laser displacement meter.

Specifically, in the sample S1, the spacer 300 is not used, and the half cell 110P is arranged on the arrangement surface 222 of the support member 200 in an undeformed posture. As a result, the saddle height of sample S1 was 22 μm, which was the largest value.

In samples S2 to S6, a spacer 300 having a width D2 of 2 mm or more and 12 mm or less and a thickness D1 of 0.03 mm or more and 0.15 mm or less was used, and the auxiliary member 400 was used except for sample S6. As a result, the saddle heights of samples S2 to S6 were -9 μm or more and 14 μm or less, which were reduced compared to sample S1. These results show that by using the spacer 300, the saddle height can be reduced. In sample S4, although the saddle height was reduced compared to sample S1, the slope of the surface at the peripheral edge of the air electrode 114 was steeper, and the air electrode side current collector 134 was lower than that of samples S7 to S12. A decrease in connectivity was confirmed.

In samples S7 to S12, a spacer 300 with a width D2 of 4 mm or more and 10 mm or less and a thickness D1 of 0.05 mm or more and 0.1 mm or less was used, and an auxiliary member 400 was used. As a result, the saddle heights of samples S7 to S12 were −5 μm or more and 5 μm or less, which were reduced compared to sample S1. Furthermore, in samples S7 to S11, a spacer 300 with a width D2 of 4 mm or more and 6 mm or less and a thickness D1 of 0.05 mm or more and 0.08 mm or less was used, and an auxiliary member 400 was used. As a result, the saddle heights of samples S7 to S11 were −1 μm or more and 5 μm or less, which were further reduced compared to samples S2 to S6.

Further, samples S6 and S11 differ only in the presence or absence of the auxiliary member 400. From the evaluation results of these samples S6 and S11, it can be seen that by using the auxiliary member 400, the saddle height can be more effectively reduced.

Further, samples S8 to S11 have different saddle heights even though the manufacturing conditions regarding the spacer 300 and the auxiliary member 400 are the same. The reason for this is that the viscosity of the air electrode paste used for screen printing is different for samples S8 to S11. Specifically, for samples S1 to S8 and S12, the viscosity of the air electrode paste is the same, and for sample S9, the viscosity of the air electrode paste is higher than that of samples S1 to S8 and S12. For samples S10 and S11, the viscosity of the air electrode paste is lower than that for samples S1 to S8 and S12. The higher the viscosity of the air electrode paste, the lower the saddle height tends to be. However, according to the present evaluation results, it can be seen that even if the viscosity of the air electrode paste changes, the saddle height can be sufficiently suppressed by setting the dimensions of the spacer 300 within the range of the present invention.

B. Variant:
The technology disclosed in this specification is not limited to the above-described embodiments, and can be modified into various forms without departing from the gist thereof. For example, the following modifications are also possible.

The configurations of the single cell 110 or the fuel cell stack 100 in the above embodiments are merely examples, and can be modified in various ways. For example, in the embodiment described above, the single cell 110 includes the intermediate layer 180, but the single cell 110 may not include the intermediate layer 180.

In the embodiment described above, the number of single cells 110 included in the fuel cell stack 100 is merely an example, and the number of single cells 110 is determined as appropriate depending on the output voltage etc. required of the fuel cell stack 100.

Further, in the above embodiment, the space between the outer peripheral surface of the shaft of each bolt 22 and the inner peripheral surface of each communication hole 108 is used as each manifold, but instead of this, the shaft of each bolt 22 is used as a manifold. An axial hole may be formed in the section and the hole may be used as each manifold. Moreover, each manifold may be provided separately from each communication hole 108 into which each bolt 22 is inserted.

Further, the materials constituting each member in the above embodiment are merely examples, and each member may be composed of other materials.

Furthermore, although the above embodiments are directed to the flat unit cell 110, the technology disclosed in this specification is similarly applicable to other unit cells other than the flat unit cell.

Further, in the above embodiment, the target is a SOFC that generates power using an electrochemical reaction between hydrogen contained in the fuel gas and oxygen contained in the oxidant gas, but the technology disclosed in this specification It can be similarly applied to electrolytic single cells, which are the constituent units of solid oxide electrolytic cells (SOEC) that generate hydrogen using the electrolysis reaction of water, and electrolytic cell stacks that include multiple electrolytic single cells. be. Note that the configuration of the electrolytic cell stack is not described in detail here because it is publicly known as described in, for example, Japanese Patent Application Laid-open No. 2016-81813, but it is generally similar to the fuel cell stack 100 in the embodiment described above. It is the composition. That is, the fuel cell stack 100 in the embodiment described above may be read as an electrolytic cell stack, the power generation unit 102 may be read as an electrolytic cell unit, and the single cell 110 may be read as an electrolytic single cell. However, during operation of the electrolytic cell stack, a voltage is applied between the two electrodes such that the air electrode 114 is positive (anode) and the fuel electrode 116 is negative (cathode), and a voltage is applied through the communication hole 108. Water vapor is supplied as a raw material gas. As a result, an electrolytic reaction of water occurs in each electrolytic cell unit, hydrogen gas is generated in the fuel chamber 176, and hydrogen is extracted to the outside of the electrolytic cell stack through the communication hole 108. Also in the manufacturing method of an electrolytic unit cell and an electrolytic cell stack having such a configuration, it is possible to manufacture a composite body in which the influence of swelling of the peripheral edge of the printed pattern caused by the saddle phenomenon is suppressed.

The method for manufacturing the fuel cell stack 100 in the above embodiment is just an example, and various modifications are possible. For example, in the above embodiment, the "composite" is the single cell 110, but it may also include the current collector element 135 and the interconnector 150 in addition to the single cell 110.

In the embodiment described above, the "underlying member" was the half cell 110P, and the "part of the composite" was the air electrode 114. However, the "underlying member" is not limited to a flat plate, and may be any component that has at least a partially flat surface. The "part of the composite" may be any part that is screen printed on the base member. For example, the "base member" may be a laminate of the electrolyte layer 112 and the fuel electrode 116, and the "part of the composite" may be the intermediate layer 180. Further, the "underlying member" may be the single cell 110, and the "part of the composite" may be the air electrode side current collector 134, or the joint portion that joins the single cell 110 and the air electrode side current collector 134. . Further, the "underlying member" may be a conductive support, and the "part of the composite" may be an electrolyte layer. Further, "a part of the composite" does not need to be a component of the composite, and may be, for example, a carrier film or the like. Further, the base member is not limited to one after firing, but may be one before firing (for example, secondary firing).

In the embodiment described above, the support member 200 may be configured without the peripheral wall portion 210. The spacer 300 is not limited to a flat shape, but may have a rectangular cross section. Further, in the above embodiment, the spacer 300 has a frame shape disposed over the entire circumference of the half cell 110P, but it may also have a circular frame shape, or a spacer disposed partially in the circumferential direction of the half cell 110P (e.g. It may be constructed from a plurality of parts) or a bottomed member having a recess that opens upward. Further, the outer peripheral surface of the spacer 300 may be arranged so as to be spaced apart from the inner peripheral surface 212 of the peripheral wall portion 210 of the support member 200. In short, the spacer should just have a configuration that causes the base member placed on the flat placement surface to be in the above-described deformed position. Alternatively, a recess may be formed in the placement surface 222 of the support member 200 without using the spacer 300, and by placing the half cell 110P in this recess, the half cell 110P may be placed in a deformed posture.

In the above embodiment, the auxiliary member 400 is not limited to a flat shape, but may have a rectangular cross section. Further, in the embodiment described above, when the half cell 110P is in a deformed posture, the spacer 300 may be disposed outside the periphery of the print area E of the half cell 110P when viewed in the vertical direction.

22: Bolt 24: Nut 26: Insulating sheet 27: Gas passage member 28: Main body 29: Branch 100: Fuel cell stack 102: Power generation unit 104, 106: End plate 108: Communication hole 110: Single cell 110P: Half cell 112 : Electrolyte layer 114: Air electrode 114P: Print pattern 115P: Convex portion 116: Fuel electrode 117P: Recessed portion 120: Separator 124: Joint portion 130: Air electrode side frame 132: Oxidizing gas supply communication hole 133: Oxidizing gas discharge Communication hole 134: Air electrode side current collector 135: Current collector element 140: Fuel electrode side frame 142: Fuel gas supply communication hole 143: Fuel gas discharge communication hole 144: Fuel electrode side current collector 145: Electrode opposing part 146 : Interconnector opposing part 147: Connection part 150: Interconnector 161: Oxidizing gas introduction manifold 162: Oxidizing gas exhaust manifold 166: Air chamber 171: Fuel gas introduction manifold 172: Fuel gas exhaust manifold 176: Fuel chamber 180: Intermediate Layer 200: Support member 210: Peripheral wall portion 212: Inner peripheral surface 214: Upper surface 220: Arrangement portion 222: Arrangement surface 230: Screen printing board 232: Plate frame 234: Screen mesh 240: Squeegee 300: Spacer 400: Auxiliary member 410: Receiving surface E: Printing area FG: Fuel gas FOG: Fuel off-gas OG: Oxidizing gas OOG: Oxidizing off-gas

Claims (5)

In a method for producing a composite including at least an electrochemical reaction unit cell comprising a solid electrolyte layer, and an air electrode and a fuel electrode facing each other with the solid electrolyte layer in between,
preparing a base member having at least a partially flat surface;
placing the base member in a deformed position in which the peripheral edge of the predetermined printing area on the flat surface of the base member is higher than the center of the printing area;
forming a predetermined printing pattern constituting a part of the composite in the printing area of the base member by performing screen printing on the print area of the base member in the deformed posture;
firing the base member with the printed pattern formed thereon in a state where it has returned to its pre-deformation position;
A method for producing a composite, comprising: In the method for producing a composite according to claim 1,
Production of a composite body, characterized in that the base member is placed on a flat placement surface, and a spacer is sandwiched between the base member and the placement surface to take the deformed posture. Method. In the method for producing a composite according to claim 2,
When viewed in a vertical direction, at least a portion of the spacer overlaps the peripheral edge of the printing area of the base member,
A method for manufacturing a composite body, characterized in that the width of the spacer in the horizontal direction is 4 mm or more and 10 mm or less, and the thickness of the spacer in the vertical direction is 0.05 mm or more and 0.1 mm or less. In the method for producing a composite according to any one of claims 1 to 3,
With an auxiliary member having a receiving surface in surface contact with the screen printing plate used in the screen printing being placed on the outer peripheral side of the base member in the deformed posture, the printing area of the base member is A method for producing a composite, characterized by carrying out screen printing. In the method for producing a composite according to any one of claims 1 to 4,
After firing the base member on which the printed pattern is formed, the height difference between the central part and the peripheral part of the printed pattern in a state where the base member has returned to its pre-deformation posture is within ±5 μm. A method for producing a composite body characterized by:

Images