JP4453455B2 - Fuel cell - Google Patents

Description

  The present invention relates to a hydrogen separation membrane fuel cell.

  In recent years, fuel cells that generate electricity by reacting hydrogen and oxygen have attracted attention as power generation means. As such a fuel cell, there is a fuel cell provided with a proton conductive electrolyte layer. For example, Patent Document 1 discloses a hydrogen separation membrane fuel cell including a hydrogen separation membrane that can selectively supply hydrogen to a proton conduction type electrolyte layer (electrolyte membrane). In such a fuel cell, the proton-conducting electrolyte layer is formed in close contact with a hydrogen-permeable metal layer that functions as a hydrogen separation membrane.

JP-A-5-299105

  A hydrogen permeable metal expands as it permeates hydrogen. The expansion ratio due to heat differs between the electrolyte layer and the hydrogen permeable metal. Therefore, in the hydrogen separation membrane fuel cell, the electrolyte layer and the hydrogen permeable metal warp due to such a difference in expansion ratio, the electrolyte layer cracks, and a part of the electrolyte layer is a hydrogen separation membrane. There was a possibility of peeling off from above.

  When the electrolyte layer is peeled off together with the electrode layer formed on the electrolyte layer, the hydrogen separation membrane is exposed to the oxygen channel on the oxygen electrode side. As a result, hydrogen that has passed through the hydrogen separation membrane directly reacts with oxygen that passes through the oxygen channel, and power generation does not occur. Moreover, there is a possibility that conductive material dust adheres and the hydrogen separation membrane on the hydrogen electrode side and the oxygen electrode are short-circuited.

  The present invention has been made in order to solve at least a part of the above-described problems, and an object of the present invention is to provide a technology that makes it difficult for an electrolyte layer to be peeled off from other components even when environmental changes occur in a fuel cell. And

  In order to achieve the above object, according to the present invention, the fuel cell has the following configuration as one aspect. This fuel cell is supplied with fuel gas from a fuel gas flow path through which a fuel gas containing hydrogen passes, and supplies an oxidizing gas from a hydrogen electrode that selectively permeates hydrogen and an oxidizing gas flow path through which an oxidizing gas containing oxygen passes. Is located between the oxygen electrode, the hydrogen electrode and the oxygen electrode, directly or indirectly joined to the hydrogen electrode and the oxygen electrode, and reduces the amount of deformation due to the external force of the electrolyte layer through which hydrogen ions are transmitted. A rigidity improving member.

  In such an aspect, since the deformation of the electrolyte layer is reduced by the rigidity improving member, the electrolyte layer is not easily broken even if force is applied to the electrolyte layer. Therefore, the electrolyte layer is difficult to peel off from other constituent members.

  In addition, it is preferable that a rigidity improvement member is located between an oxygen electrode and an electrolyte layer, and is provided so that a part of electrolyte layer may be coat | covered directly or indirectly. If it is set as such an aspect, peeling of an electrolyte layer can be prevented by a rigidity improvement member, without interrupting | blocking permeation | transmission of the hydrogen ion which goes to a oxygen electrode from a hydrogen electrode.

  Moreover, it can also be set as the aspect by which the rigidity improvement member was provided in the grid | lattice shape between the oxygen electrode and the electrolyte layer. If it is set as such an aspect, the deformation amount of an electrolyte layer can be reduced efficiently with a rigidity improvement member with a small volume.

  The rigidity improving member is located between the oxidant gas flow path and the oxygen electrode, and is provided so as to indirectly cover a part of the electrolyte layer and to expose at least a part of the oxygen electrode to the oxidant gas flow path. It can also be set as an embodiment. If it is set as such an aspect, peeling of an electrolyte layer can be prevented by a rigidity improvement member, without interrupting contact with the oxygen electrode of oxidizing gas.

  In addition, the rigidity improving member may be a layer that is located between the oxidizing gas flow path and the oxygen electrode and has a void that communicates with each other. Even in such an embodiment, it is possible to prevent the electrolyte layer from peeling off by the rigidity improving member without blocking the contact of the oxidizing gas with the oxygen electrode.

  The rigidity improving member can also be a glass fiber present in the electrolyte layer. Even in such an embodiment, the amount of deformation of the electrolyte layer can be reduced to prevent the electrolyte layer from peeling off.

  In addition, the electrolyte layer may include a plurality of hydrogen ion permeable members that are arranged in a plane perpendicular to the direction from the oxygen electrode to the hydrogen electrode and each transmit hydrogen ions. In such an aspect, it is preferable that at least a part of the rigidity improving member is integrally provided between the hydrogen electrode and the oxygen electrode and between the plurality of hydrogen ion permeable members. In such an aspect, while the ion permeability is ensured by the plurality of hydrogen ion permeable members, it is possible to suppress the situation where the force applied to the electrolyte layer is concentrated on one place of the electrolyte layer and the electrolyte layer is destroyed. it can.

  It is also possible to adopt a mode in which another part of the rigidity improving member covers a part of the hydrogen ion permeable member on the oxygen electrode side with respect to the electrolyte layer. In such an embodiment, the electrolyte layer is partially covered and held by the rigidity improving member. For this reason, even if the electrolyte layer is cracked, the electrolyte layer is difficult to peel off.

  The present invention can be realized in various forms, for example, in the form of a fuel cell, a method for manufacturing a fuel cell, a method for forming an electrolyte layer for a fuel cell or a laminated structure, and the like. it can.

A. First embodiment:
FIG. 1 is a cross-sectional view showing a laminated structure 100a (unit cell) used in the fuel cell of the first embodiment. The laminated structure 100 a includes an oxygen flow path member 20 having an oxygen gas flow path 22 and a hydrogen flow path member 30 having a fuel gas flow path 32. Between the oxygen flow path member 20 and the hydrogen flow path member 30, a hydrogen separation membrane 120, an electrolyte layer 110, an oxygen electrode 130, and a beam portion 140 are formed in this order from the hydrogen flow path member 30 side toward the oxygen flow path member 20. Has been. The hydrogen separation membrane 120, the electrolyte layer 110, the oxygen electrode 130, and the beam portion 140 are collectively referred to as a laminated structure 100a. The cross-sectional shape of this laminated structure 100a in a plane perpendicular to the direction from the hydrogen flow path member 30 side to the oxygen flow path member 20 is a rectangle. The laminated structure 100a is sandwiched between the oxygen flow path member 20 also serving as a separator and the hydrogen flow path member 30, and constitutes one cell of the fuel cell as a whole.

  The oxygen channel member 20 is formed of stainless steel (SUS). The oxygen channel member 20 has a groove portion 21, and the groove portion 21 constitutes an oxygen gas channel 22. The beam portion 140 is formed in a lattice shape on the oxygen electrode 130. A portion 131 on the surface of the oxygen electrode 130 where the beam portion 140 is not formed is exposed to the oxygen gas flow path 22. For this reason, the oxygen-containing gas flowing through the oxygen gas flow path 22 comes into contact with the surface of the electrolyte layer 110. In the first embodiment, the oxygen-containing gas is air.

  The hydrogen flow path member 30 is also formed of stainless steel (SUS). The hydrogen flow path member 30 has a groove 31, and the groove 31 forms a fuel gas flow path 32. The hydrogen-containing gas flowing through the fuel gas channel 32 contacts the hydrogen separation membrane 120 of the laminated structure 100a. In the present specification, this hydrogen-containing gas is also referred to as “fuel gas”. Hydrogen in the fuel gas passes through the laminated structure 100a from the hydrogen separation membrane 120 side toward the oxygen electrode 130 side, and reacts with oxygen in the oxygen-containing gas on the oxygen electrode 130 side. The oxygen flow path member 20 and the hydrogen flow path member 30 may be formed of a material other than stainless steel, and any oxygen flow member 20 and hydrogen flow path member 30 can have confidentiality. Can be made of material.

  The hydrogen separation membrane 120 is made of palladium (Pd) with a thickness of about 40 μm. The hydrogen separation membrane 120 selectively permeates hydrogen in the hydrogen-containing gas. This hydrogen separation membrane 120 also functions as a hydrogen electrode. During operation of the fuel cell, electrons move from the hydrogen electrode (hydrogen separation membrane 120) to the oxygen electrode 130 through an electric circuit (not shown). In addition to the palladium, the hydrogen separation membrane 120 may be formed of a noble metal such as a palladium alloy, or a VA group element such as vanadium (V), niobium (Nb), or tantalum (Ta).

Whether or not a certain material “permeates hydrogen” or “permeates hydrogen” depends on whether the material has a thickness of 1.0 μm and a hydrogen permeability coefficient of 1.0 × at 700 ° C. It can be determined by whether or not it is larger than 10 ⁻¹⁰ (mol / m · s · Pa ^1/2 ). In addition, when the material of the antioxidant part 122 is formed with a thickness of 1.0 μm, the hydrogen permeation coefficient is less than 1.0 × 10 ⁻⁹ (mol / m · s · Pa ^1/2 ) at 700 ° C. It is more preferable to make the material larger. The same applies to materials that “permeate hydrogen” or “permeate hydrogen”, which are used in the following sections of the fuel cell.

The electrolyte layer 110 is formed between the oxygen electrode 130 and the hydrogen separation membrane 120, and is joined to the oxygen electrode 130 and the hydrogen separation membrane 120. The thickness of the electrolyte layer 110 can be 0.1 to 1.0 μm. The electrolyte layer 110 is formed of a BaCeO ₃ -based ceramic that is a perovskite proton conductor compound. The perovskite proton conductor compound has proton conductivity in a state where oxygen atoms are introduced into the deficiency of interstitial oxygen.

The electrolyte layer 110 is made of SrCeO ₃ , SrZrO ₃ , CaZrO ₃ , or pyrochlore proton conductor compounds such as Gd ₂ Ti ₂ O ₇ , La ₂ Zr ₂ O ₇ , etc. It can also be formed. That is, the electrolyte layer 110 can be formed of a solid oxide having proton conductivity.

  The oxygen electrode 130 is a layer formed of platinum (Pt) on the electrolyte layer 110. The thickness of the oxygen electrode 130 is about 0.1 μm. The material and film thickness of the oxygen electrode 130 can be arbitrarily selected and set.

  FIG. 2 is a perspective view showing a part of the laminated structure 100a. In FIG. 2, the upper side is the side on which the oxygen channel member 20 is attached, and the lower side is the side on which the hydrogen channel member 30 is attached (see FIG. 1). In addition, the thickness of each structure shown in figure does not reflect actual thickness.

  As shown in FIGS. 2 and 1, the beam portion 140 is formed in a lattice shape on the oxygen electrode 130. In the first embodiment, the beam portion 140 is made of titanium (Ti) and has a thickness of about 0.1 μm. The width of each beam constituting the lattice is about 1 μm. Although not shown, the distance between the centers of the beams parallel in the vertical and horizontal directions is about 5 μm in both the vertical and horizontal directions. The beam portion 140 can be formed of titanium alloy, stainless steel (SUS) in addition to titanium. The dimensions and thickness of the beam portion 140 can be determined according to the materials and thicknesses of the hydrogen separation membrane 120 and the electrolyte layer 110 and the materials of the hydrogen separation membrane 120, the electrolyte layer 110 and the beam portion 140.

  As shown in FIG. 1, the beam portion 140 is not provided on the outermost peripheral portion 132 on the upper surface of the oxygen electrode 130. On the other hand, the outermost wall portion 23 of the oxygen flow path member 20 is provided higher than the groove portion 21 and the wall portion 24 that divides the groove portion 21. As a result, the outermost peripheral wall portion 23 is in close contact with the outer peripheral portion 132 on the surface of the oxygen electrode 130, and airtightness to the outside of the oxygen gas flow path 22 is maintained. Therefore, the oxygen-containing gas does not leak from the oxygen flow path member 20. Note that there is no problem even if the oxygen-containing gas flows between the plurality of oxygen gas flow paths 22.

  The laminated structure 100a having such a configuration can be manufactured as follows. First, a hydrogen separation membrane 120 having a thickness of about 40 μm is prepared. The hydrogen separation membrane 120 may be formed in advance by a vapor deposition method or may be generated by another method.

Thereafter, the electrolyte layer 110 is formed on the hydrogen separation membrane 120. The film material for forming the electrolyte layer 110 is ceramic (BaCeO ₃ -based perovskite proton conductor compound). Then, film formation is performed by laser ablation. “Laser ablation” is a method of forming a thin film by evaporating a vapor deposition material with ultraviolet laser light and depositing the vapor on a member. The formation of the electrolyte layer 110 may be performed by other chemical vapor deposition methods or physical vapor deposition methods.

  Then, an oxygen electrode 130 is generated from above the electrolyte layer 110 by sputtering. Thereafter, masking is performed so that the beam portion 140 has a lattice shape, and the beam portion 140 is formed on the oxygen electrode 130 by ion plating. The beam portion 140 may be formed by other physical vapor deposition methods such as sputtering or chemical vapor deposition methods. The oxygen electrode 130 may also be formed by other physical vapor deposition methods or chemical vapor deposition methods.

  The fuel cell having such a laminated structure 100a is operated at a high temperature of 700 ° C. or higher, for example. If the electrolyte layer 110 and the hydrogen separation membrane 120 having different thermal expansion ratios are to expand or contract at different ratios as the temperature changes, the laminated structure 100a will warp at the joint surface between the electrolyte layer 110 and the hydrogen separation membrane 120. The power to work. If the laminated structure 100a is greatly warped, the electrolyte layer 110 may be cracked by bending accompanied by compression or tension due to warpage, and the electrolyte layer 110 and the oxygen electrode 130 formed thereon may be peeled off. The same applies when hydrogen is allowed to permeate through the electrolyte layer 110 and the hydrogen separation membrane 120. However, since the laminated structure 100 a includes the beam portion 140, the warpage deformation amount is suppressed by the beam portion 140. As a result, the possibility that the electrolyte layer 110 cracks and the electrolyte layer 110 and the oxygen electrode 130 are peeled off can be reduced.

B. Second embodiment:
FIG. 3 is a perspective view of the laminated structure 100b of the second embodiment. In FIG. 3, the oxygen electrode 130 is indicated by a broken line in order to clearly show the shape of the beam portion 140. The laminated structure 100 b of the second embodiment has a beam portion 140 between the electrolyte layer 110 and the oxygen electrode 130. The oxygen electrode 130 is formed so as to cover the electrolyte layer 110 and the beam portion 140, and includes the beam portion 140 inside as illustrated. The thickness of the oxygen electrode 130 is about 0.5 μm. The other points of the multilayer structure 100b of the second embodiment are the same as those of the multilayer structure 100a of the first embodiment. It should be noted that the thickness of the oxygen electrode 130 can be any dimension that is thicker than the thickness of the beam portion 140.

  The laminated structure 100b having such a configuration can be manufactured as follows. First, the hydrogen separation membrane 120 and the electrolyte layer 110 are formed in the same manner as in the case of manufacturing the laminated structure 100a of the first embodiment.

  Then, masking is performed so that the beam portion 140 has a lattice shape, and the beam portion 140 is formed on the electrolyte layer 110 by ion plating. The beam portion 140 may be formed by other physical vapor deposition methods such as sputtering or chemical vapor deposition methods. Thereafter, the oxygen electrode 130 is generated by sputtering so as to cover the beam 140 from above the electrolyte layer 110 and the beam 140.

  Even in the configuration of the second embodiment, the amount of warpage deformation of the laminated structure 100b is suppressed by the beam portion 140. As a result, it is possible to reduce the possibility that the electrolyte layer 110 is cracked by bending accompanied by compression or pulling due to warping, and the electrolyte layer 110 and the oxygen electrode 130 are peeled off.

C. Third embodiment:
FIG. 4 is a perspective view of the laminated structure 100c of the third embodiment. The laminated structure 100b of the third embodiment has a reinforcing layer 150 made of nickel (Ni) including voids communicating with each other on the upper surface of the oxygen electrode 130 (the side on which the oxygen flow path member 20 is provided). . The thickness of this reinforcing layer is about 1 μm. Further, the laminated structure 100c of the third embodiment does not have the beam portion 140 (see FIGS. 2 and 3). The other points of the laminated structure 100c of the third example are the same as those of the laminated structure 100a of the first example. The thickness of the reinforcing layer 150 can be set to an arbitrary dimension depending on the material and configuration of the reinforcing layer 150.

  The laminated structure 100c having such a configuration can be manufactured as follows. First, the hydrogen separation membrane 120, the electrolyte layer 110, and the oxygen electrode 130 are formed in the same manner as in the case of manufacturing the laminated structure 100a of the first embodiment.

  Thereafter, nickel particles having a predetermined particle size are stacked on the oxygen electrode 130 by sputtering to form the reinforcing layer 150. The reinforcing layer 150 may be formed by sticking a foam metal sheet or plate having bubbles communicating with each other on the oxygen electrode 130. The reinforcing layer 150 can be made of a material having predetermined voids communicating with each other, such as a sintered body or a foam metal.

  Even in the configuration of the third embodiment, the warping deformation amount of the laminated structure 100 c is suppressed by the reinforcing layer 150. As a result, it is possible to reduce the possibility that the electrolyte layer 110 is cracked by bending accompanied by compression or pulling due to warping, and the electrolyte layer 110 and the oxygen electrode 130 are peeled off.

  The reinforcing layer 150 has voids that communicate with each other. For this reason, oxygen passing through the oxygen gas flow path 22 (see FIG. 1) can pass through the voids of the reinforcing layer 150 and come into contact with the oxygen electrode 130. That is, when operating the fuel cell, the reaction at the oxygen electrode 130 is not hindered.

D. Fourth embodiment:
FIG. 5 is a perspective view of the laminated structure 100d of the fourth embodiment. A portion indicated by a lead line is an enlarged view in which a part of the electrolyte layer 110 is enlarged by cutting along a plane parallel to each layer. The laminated structure 100d of the fourth embodiment includes glass fibers 111 in the electrolyte layer 110. Further, the laminated structure 100d of the fourth embodiment does not have the beam portion 140 (see FIGS. 2 and 3). The other points of the laminated structure 100d of the fourth example are the same as those of the laminated structure 100a of the first example.

  The laminated structure 100d having such a configuration can be manufactured as follows. First, the hydrogen separation membrane 120 is prepared in the same manner as in the case of manufacturing the laminated structure 100a of the first embodiment.

  Then, the electrolyte layer 110 is formed by sputtering several times. Between each sputtering, the glass fiber 111 is spread | dispersed on the surface of the electrolyte layer 110 in the middle of formation. Then, an electrolyte layer 110 is further formed from above the dispersed glass fiber 111 by sputtering. Repeat this procedure several times. Thereafter, platinum is sputtered from above the completed electrolyte layer 110 to generate the oxygen electrode 130.

  If it is set as a structure like 4th Example, the deformation amount of the curvature of the laminated structure 100d will be suppressed by the glass fiber 111 in the electrolyte layer 110. FIG. As a result, it is possible to reduce the possibility that the electrolyte layer 110 is cracked by bending accompanied by compression or pulling due to warping, and the electrolyte layer 110 and the oxygen electrode 130 are peeled off.

  Further, in the conventional fuel cell, when the crack is formed in the electrolyte layer and a part of the electrolyte layer is surrounded by the crack, the part surrounded by the crack is peeled off from the laminated structure. However, in the electrolyte layer 110 of the fourth embodiment, even if the portion 110c surrounded by the crack Cr is formed, the portion 110c is connected to the periphery by the glass fiber 111 as shown in FIG. For this reason, the electrolyte layer 110 is difficult to peel off.

E. Example 5:
FIG. 6 is a perspective view of the laminated structure 100e of the fifth embodiment. In FIG. 6, in order to clearly show the shapes of the beam portion 170 and the electrolyte block 112, the oxygen electrode 130 is indicated by a broken line. The laminated structure 100e of the fifth embodiment has an insulating layer 160 between the hydrogen separation membrane 120 and the electrolyte layer 110. The electrolyte layer 110 includes a plurality of electrolyte blocks 112, and beam portions 170 are formed between the electrolyte blocks 112. An oxygen electrode 130 is provided on the electrolyte block 112 and the beam portion 170. The other points of the multilayer structure 100e of the fifth embodiment are the same as those of the multilayer structure 100a of the first embodiment.

The insulating layer 160 has a thickness of about 0.1 μm and is made of tungsten oxide (WO ₃ ). The insulating layer 160 can be made of any material having an insulating property, such as an oxide of another metal. The insulating layer 160 can be provided with an arbitrary thickness.

  As shown in FIG. 6, the beam portions 170 are formed in a lattice shape on the insulating layer 160. In the fifth embodiment, the beam portion 170 is made of a stainless alloy (SUS) and has a thickness of about 40 μm. The width of each beam constituting the lattice is about 10 μm. Although not shown, the distance between the centers of the beams parallel in the vertical and horizontal directions is about 50 μm in both the vertical and horizontal directions. The beam portion 170 can be formed of titanium (Ti) or a titanium alloy in addition to stainless steel. Further, the shape and dimensions of the beam portion 170 can be determined according to the materials and thicknesses of the hydrogen separation membrane 120 and the electrolyte layer 110 and the materials of the hydrogen separation membrane 120, the electrolyte layer 110 and the beam portion 140.

  The laminated structure 100e having such a configuration can be manufactured as follows. First, the hydrogen separation membrane 120 is prepared in the same manner as in the case of manufacturing the laminated structure 100a of the first embodiment. Then, tungsten oxide is deposited on the hydrogen separation film 120 by sputtering to form the insulating layer 160. Note that the insulating layer 160 may be formed by another physical vapor deposition method or a chemical vapor deposition method.

Thereafter, the beam portion 170 formed in advance is bonded onto the insulating layer 160. Then, the beam portion 170 is masked, and a BaCeO ₃ -based ceramic is laminated on the portion surrounded by each beam of the beam portion 170 to the same thickness as each beam of the beam portion 170 by sputtering. The ceramics may be laminated slightly thicker than each beam of the beam portion 170, and then the surface of the laminated ceramic may be ground to have the same height as each beam of the beam portion 170. In this way, the electrolyte block 112 surrounded by each beam of the beam portion 170 is formed.

  Thereafter, the oxygen electrode 130 is generated on each electrolyte block 112 and the beam portion 170 by sputtering. Note that the oxygen electrode 130 and the electrolyte block 112 (electrolyte layer 110) may be formed by other physical vapor deposition methods or chemical vapor deposition methods.

  Even in the configuration of the fifth embodiment, the amount of warpage deformation of the laminated structure 100e is suppressed by the beam portion 170. As a result, it is possible to reduce the possibility that the electrolyte layer 110 is cracked by bending accompanied by compression or pulling due to warping, and the electrolyte layer 110 and the oxygen electrode 130 are peeled off.

  In the fifth embodiment, the electrolyte layer 110 is divided into a plurality of electrolyte blocks 112. For this reason, even when the laminated structure 100e is warped, it is possible to reduce the possibility that the force applied to the entire electrolyte layer 110 is concentrated in one place and the electrolyte layer 110 is cracked.

  Furthermore, the laminated structure 100e of the fifth embodiment has an insulating layer 160 between the hydrogen separation membrane 120 made of metal and the beam portion 170. For this reason, even if the beam portion 170 is made of metal, a short circuit may occur between the beam portion 170 formed with the oxygen electrode 130 in contact therewith and the hydrogen separation membrane 120 functioning as a hydrogen electrode. Absent.

F. Example 6:
FIG. 7 is a perspective view of the laminated structure 100f of the sixth embodiment. In FIG. 7, in order to clearly show the shapes of the beam portion 180 and the electrolyte block 112, the oxygen electrode 130 is indicated by a broken line. In the laminated structure 100f of the sixth embodiment, a beam portion 180 made of ceramic (Al ₂ O ₃ ) is provided between the electrolyte blocks 112 instead of the beam portion 170 made of stainless alloy (see FIG. 6). Is formed. Each beam of the beam portion 180 has a T-shaped cross section, and is formed so as to partially cover the surface of the electrolyte block 112 located on both sides of each beam with portions 182 protruding on both sides. Yes. The other points of the laminated structure 100f of the sixth embodiment are the same as those of the laminated structure 100e of the fifth embodiment.

  As shown in FIG. 7, the beam portion 180 is formed in a lattice shape. The distance between the centers of the beams constituting the lattice is about 100 μm both vertically and horizontally. Each beam constituting the lattice is positioned above the electrolyte block 112 and the first portion 181 formed between the electrolyte blocks 112 of the electrolyte layer 110 and has a width wider than the interval between the adjacent electrolyte blocks 112. It has a wide second portion 182.

  The thickness of the first portion 181 is about 40 μm and the width is about 20 μm. On the other hand, the thickness of the second portion 182 is about 30 μm and the width is about 40 μm. The beam portion 180 can be formed of titanium (Ti) or a titanium alloy in addition to ceramic. The dimensions and shape of the beam portion 180 can be determined according to the materials and thicknesses of the hydrogen separation membrane 120 and the electrolyte layer 110 and the materials of the hydrogen separation membrane 120, the electrolyte layer 110, and the beam portion 140.

  The laminated structure 100f having such a configuration can be manufactured as follows. First, the hydrogen separation membrane 120 and the insulating layer 160 are formed in the same manner as in the case of manufacturing the laminated structure 100e of the fifth embodiment. Then, masking is performed, and each electrolyte block 112 of the electrolyte layer 110 is formed by sputtering.

  After that, the respective electrolyte blocks 112 are masked and the ceramic is sprayed to form the first portions 181 of the beam portions 180 between the respective electrolyte blocks 112. Thereafter, the mask is changed, and a second portion 182 having a width wider than that of the first portion 181 is formed on the first portion 181. Thereafter, the mask is further replaced, and the oxygen electrode 130 is formed to the same thickness as the second portion 182 of the beam portion 180 by sputtering. Note that platinum may be stacked slightly thicker than the second portion 182 of the beam portion 180, and then the surface of the stacked platinum may be ground to have the same height as the second portion 182.

  Even in the configuration of the sixth embodiment, the amount of warp deformation of the laminated structure 100f is suppressed by the beam portion 180. In particular, since the beam portion 180 of the sixth embodiment has the first portion 181 and the second portion 182 having different widths, the entire cross section of the beam has the same width as the second portion 182. Compared to the present embodiment, the deformation amount of the warp of the laminated structure 100f can be limited without reducing the size of the electrolyte block. As a result, it is possible to reduce the possibility that the electrolyte layer 110 is cracked by bending accompanied by compression or pulling due to warping, and the electrolyte layer 110 and the oxygen electrode 130 are peeled off.

  In the sixth embodiment, the beam portion 180 is formed such that the second portion 182 having a width wider than the interval between the adjacent electrolyte blocks 112 is positioned above the electrolyte block 112. For this reason, even if the electrolyte block 112 is cracked, a part of the electrolyte block 112 is pressed by the overhang of the second portion 182 of the beam portion 180, so that the electrolyte layer 110 is not easily peeled off.

G. Seventh embodiment:
FIG. 8 is a plan view showing the rigidity improving member 190 of the seventh embodiment. In FIG. 8, the rigidity improving member 190 is hatched in order to easily distinguish the rigidity improving member 190 and the oxygen electrode 130 located therebelow. The laminated structure 100g of the seventh embodiment has a rigidity improving member 190 on the oxygen electrode 130 instead of the beam portion 140 (see FIG. 1). The other points of the laminated structure 100g according to the seventh embodiment are the same as those of the laminated structure 100a according to the first embodiment.

  As shown in FIG. 8, the rigidity improving member 190 has a patchy hole 191. The oxygen electrode 130 is exposed to the oxygen gas flow path 22 through the hole. For this reason, the oxygen-containing gas flowing through the oxygen gas flow path 22 can come into contact with the surface of the electrolyte layer 110.

  Even in the configuration of the seventh embodiment, the deformation amount of the warp of the laminated structure 100g is suppressed by the rigidity improving member 190. As a result, it is possible to reduce the possibility that the electrolyte layer 110 is cracked by bending accompanied by compression or pulling due to warping, and the electrolyte layer 110 and the oxygen electrode 130 are peeled off.

H. Variations:
(1) The rigidity improving member that reduces the deformation amount of the electrolyte layer is provided as the beam portions 140, 170, and 180 in the first, second, fifth, and sixth embodiments. However, the rigidity improving member can be formed in an arbitrary shape other than the lattice-like shape. For example, in the seventh embodiment (see FIG. 8), the hole 191 of the rigidity improving member is substantially circular, but the rigidity improving member may be provided in a form having an indeterminate hole.

  Further, in the sixth embodiment, all the beams of the beam portion 180 are positioned above the first portion 181 formed between the electrolyte blocks 112 and the electrolyte block 112, and each block of the electrolyte layer 110. The second portion 182 having a width wider than that of the second portion 182 was included. However, some beams may not have the second portion. Furthermore, it can also be set as the aspect which has the location which has a 2nd part wider than the space | interval of the electrolyte block 112 in the middle of a beam, and the location which does not have a 2nd part.

  That is, the rigidity improving member can have any shape formed so as to directly or indirectly cover a part of the electrolyte layer that is any layer in the laminated structure. Note that the rigidity improving member “indirectly covers a part of the electrolyte layer” means that a part of the electrolyte layer is covered by the rigidity improving member when viewed along the direction from the oxygen electrode side to the hydrogen electrode side. However, it means that there is another layer or structure between the rigidity improving member and the electrolyte layer. On the other hand, the rigidity improving member “directly covers a part of the electrolyte layer” means that a part of the electrolyte layer is covered by the rigidity improving member when viewed from the oxygen electrode side to the hydrogen electrode side. This means that the rigidity improving member is formed on the electrolyte layer.

  Note that the rigidity improving member may be provided by a plurality of members. However, in the aspect in which the electrolyte layer 110 is composed of a plurality of electrolyte blocks 112, the rigidity improving member is preferably formed in an integral configuration adjacent to three or more electrolyte blocks 112. Moreover, in various aspects, it is more preferable that the rigidity improving member is integrally formed in the laminated structure.

  The laminated structure may include a plurality of types of rigidity improving members. For example, the laminated structure may be configured to include both the beam portion 140 shown in the first example and the reinforcing layer 150 shown in the third example. In addition to the rigidity improving member, the laminated structure further includes a fibrous substance (for example, glass fiber 111 shown in the fourth embodiment) as a rigidity improving member in any layer. You can also

(2) In the fourth embodiment, the rigidity improving member is formed in the electrolyte layer 110 as a fibrous substance (glass fiber 111). However, the rigidity improving member may be provided as a fibrous material disposed in a layer other than the electrolyte layer 110 in the stacked structure, such as provided in the hydrogen separation membrane 120.

(3) In each of the above embodiments, the hydrogen separation membrane 120 also functions as a hydrogen electrode. However, an embodiment having a hydrogen electrode separately from the hydrogen separation membrane 120 can be adopted. In such an embodiment, for example, the hydrogen separation membrane 120 is preferably formed of vanadium, and the hydrogen electrode formed between the hydrogen separation membrane 120 and the fuel gas flow channel 32 is preferably formed of palladium. That is, the hydrogen electrode is preferably formed of a metal that transmits hydrogen and is less likely to be oxidized than the electrolyte layer.

Sectional drawing which shows the laminated structure 100a used for the fuel cell of 1st Example. The perspective view which shows a part of laminated structure 100a. The perspective view of the laminated structure 100b of 2nd Example. The perspective view of the laminated structure 100c of 3rd Example. The perspective view of the laminated structure 100d of 4th Example. The perspective view of the laminated structure 100e of 5th Example. The perspective view of the laminated structure 100f of 6th Example. The top view which shows the rigidity improvement member 190 of 7th Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 20 ... Oxygen flow path member 21 ... Groove part 22 ... Oxidation gas flow path 30 ... Hydrogen flow path member 31 ... Groove part 32 ... Fuel gas flow path 100a-g ... Laminated structure 110 ... Electrolyte layer 110c ... Surrounded by crack among electrolyte layers 111 ... Glass fiber 112 ... Block 112 ... Electrolyte block 120 ... Hydrogen separation membrane (hydrogen electrode)
DESCRIPTION OF SYMBOLS 122 ... Antioxidation part 130 ... Oxygen electrode 131 ... The part which is the surface of an oxygen electrode and the beam part is not formed 140 ... Beam part 150 ... Strengthening layer 160 ... Insulating layer 170 ... Beam part 180 ... Beam part 181 ... 1st Part 182 ... second part 190 ... rigidity improving member 191 ... hole

Claims (8)

A hydrogen electrode that is supplied with the fuel gas from a fuel gas flow path through which a fuel gas containing hydrogen passes and selectively permeates hydrogen;
An oxygen electrode supplied with the oxidizing gas from an oxidizing gas flow path for passing an oxidizing gas containing oxygen;
An electrolyte layer located between the hydrogen electrode and the oxygen electrode, directly or indirectly joined to the hydrogen electrode and the oxygen electrode, and permeable to hydrogen ions;
A rigidity improving member for reducing the amount of deformation due to external force of the electrolyte layer;
A fuel cell comprising: The fuel cell according to claim 1, wherein
The rigidity improving member is
Located between the oxygen electrode and the electrolyte layer,
A fuel cell provided so as to cover a part of the electrolyte layer directly or indirectly. The fuel cell according to claim 2, wherein
The rigidity improving member is
A fuel cell provided in a lattice shape between the oxygen electrode and the electrolyte layer. The fuel cell according to claim 1, wherein
The rigidity improving member is
Located between the oxidizing gas flow path and the oxygen electrode,
A fuel cell provided with a configuration in which a part of the electrolyte layer is indirectly coated and at least a part of the oxygen electrode is exposed to the oxidizing gas channel. The fuel cell according to claim 1, wherein
The rigidity improving member is
Located between the oxidizing gas flow path and the oxygen electrode,
A fuel cell, which is a layer having voids communicating with each other. The fuel cell according to claim 1, wherein
The rigidity improving member is
A fuel cell, which is a glass fiber present in the electrolyte layer. The fuel cell according to claim 1, wherein
The electrolyte layer is
Arranged in a plane perpendicular to the direction from the oxygen electrode to the hydrogen electrode, each including a plurality of hydrogen ion permeable members that transmit hydrogen ions,
At least a part of the rigidity improving member is
A fuel cell provided integrally between the hydrogen electrode and the oxygen electrode and between the plurality of hydrogen ion permeable members. The fuel cell according to claim 7, wherein
The other part of the rigidity improving member is provided on the oxygen electrode side with respect to the electrolyte layer so as to cover a part of the hydrogen ion permeable member.

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