JP2021082484A

JP2021082484A - Intermediate of cell structure, cell structure, and manufacturing method thereof

Info

Publication number: JP2021082484A
Application number: JP2019209132A
Authority: JP
Inventors: 桂太入月; Keita Irizuki; 雄太郎三由; Yutaro Miyoshi
Original assignee: Nissan Motor Co Ltd
Current assignee: Nissan Motor Co Ltd
Priority date: 2019-11-19
Filing date: 2019-11-19
Publication date: 2021-05-27
Anticipated expiration: 2039-11-19
Also published as: JP7395981B2

Abstract

To provide an intermediate of a cell structure, a cell structure and a manufacturing method thereof that prevents a leak path in an electrolyte layer and improves cell performance.SOLUTION: An intermediate 10 of a cell structure 100, which is formed by laminating a metal support 1, an anode catalyst layer 2, and a solid oxide type electrolyte layer 3, is provided. The intermediate 10 of the cell structure 100 forms an electrolyte reinforcing portion 8 that enhances the cell performance in a defective portion 6 of the electrolyte layer 3. That is, the gap formed in the electrolyte layer 3 is closed by the electrolyte reinforcing portion 8 that enhances the cell performance.SELECTED DRAWING: Figure 3

Description

本発明は、セル構造体の中間体、セル構造体及びセル構造体の製造方法に関する。 The present invention relates to an intermediate of a cell structure, a cell structure, and a method for producing the cell structure.

従来、電解質層、アノード多孔質体、支持体を積層して焼成した中間体に、触媒溶液を含浸して、アノード触媒層を形成する固体酸化物型燃料電池セル（セル構造体）の製造方法が知られている。 Conventionally, a method for producing a solid oxide fuel cell (cell structure) in which a catalyst solution is impregnated into an intermediate body obtained by laminating and firing an electrolyte layer, an anode porous body, and a support to form an anode catalyst layer. It has been known.

ところで、固体酸化物型燃料電池セルの電解質層には薄膜セラミックスが用いられる。薄膜セラミックスは脆弱であるため、製造工程において焼成時の凝集度が不十分で電解質層の緻密性が十分に保たれない場合、電解質層内部に残存する微細な隙間が電解質クラックを誘発し、電解質層を貫通する隙間が形成され易い。電解質層に隙間が形成された燃料電池セルを用いると、燃料電池を作動させた際にガス漏れ（リークパス）を引き起こしてしまう可能性がある。 By the way, thin film ceramics are used for the electrolyte layer of the solid oxide fuel cell. Since thin-film ceramics are fragile, if the degree of cohesion during firing is insufficient in the manufacturing process and the electrolyte layer is not sufficiently dense, the minute gaps remaining inside the electrolyte layer induce electrolyte cracks, and the electrolyte. Gap penetrating the layer is likely to be formed. If a fuel cell with a gap formed in the electrolyte layer is used, a gas leak (leak path) may occur when the fuel cell is operated.

特許文献１には、多孔質構造を有するアノードと、アノードの多孔質構造内に担持された改質触媒と、カソードと、アノードとカソードの間に挟まれた電解質と、を有する燃料電池セルの製造方法が開示されている。この燃料電池セルの製造方法では、アノードと、カソードと、電解質と、を有する単セル（中間体）のアノード面上に、触媒溶液を滴下する滴下工程を設けている。 Patent Document 1 describes a fuel cell having an anode having a porous structure, a reforming catalyst supported in the porous structure of the anode, a cathode, and an electrolyte sandwiched between the anode and the cathode. The manufacturing method is disclosed. In this method for manufacturing a fuel cell, a dropping step of dropping a catalyst solution is provided on the anode surface of a single cell (intermediate) having an anode, a cathode, and an electrolyte.

特開２０１２−２０４２７７号公報Japanese Unexamined Patent Publication No. 2012-204277

特許文献１に記載された燃料電池セルの製造方法では、中間体に触媒溶液を滴下するため、触媒溶液により電解質に形成された隙間を閉塞する効果が期待できる。しかしながら、触媒溶液には導電性材料（貴金属）が含まれているため、電解質内部に導電パスが形成されてしまい、電解質の絶縁性が低下し、例えば燃料電池作動時に短絡するなどの恐れがある。即ち、電解質に形成された隙間を閉塞することで、燃料電池セルの性能が低下してしまう可能性がある。 In the method for manufacturing a fuel cell cell described in Patent Document 1, since the catalyst solution is dropped onto the intermediate, the effect of closing the gap formed in the electrolyte by the catalyst solution can be expected. However, since the catalyst solution contains a conductive material (precious metal), a conductive path is formed inside the electrolyte, which lowers the insulating property of the electrolyte and may cause a short circuit during operation of the fuel cell, for example. .. That is, there is a possibility that the performance of the fuel cell may deteriorate by closing the gap formed in the electrolyte.

本発明は上記課題に鑑みたものであり、電解質層のリークパス等を防止するとともに、セル性能を向上させたセル構造体の中間体、セル構造体及びセル構造体の製造方法を提供することを目的とする。 The present invention has been made in view of the above problems, and provides a method for producing an intermediate of a cell structure, a cell structure, and a cell structure in which a leak path or the like of an electrolyte layer is prevented and cell performance is improved. The purpose.

本発明の一態様によれば、セル構造体の中間体であって、金属支持体、アノード触媒層、固体酸化物型電解質層を積層してなる中間体が提供される。このセル構造体の中間体は、固体酸化物型電解質層の欠陥部位内にセル性能を高める電解質補強部を形成している。 According to one aspect of the present invention, there is provided an intermediate of a cell structure, which is formed by laminating a metal support, an anode catalyst layer, and a solid oxide type electrolyte layer. The intermediate of this cell structure forms an electrolyte reinforcing portion that enhances cell performance in the defective portion of the solid oxide type electrolyte layer.

本発明によれば、セル構造体の中間体は、金属支持体、アノード触媒層、固体酸化物型電解質層を積層してなり、固体酸化物型電解質層の欠陥部位内にセル性能を高める電解質補強部を形成している。即ち、セル性能を高める電解質補強部により、電解質層に形成された隙間が閉塞されている。従って、セル構造体（電解質層）のリークパス等を防止するとともに、セル構造体のセル性能を高めることができる。 According to the present invention, the intermediate of the cell structure is formed by laminating a metal support, an anode catalyst layer, and a solid oxide type electrolyte layer, and an electrolyte that enhances cell performance in a defective portion of the solid oxide type electrolyte layer. It forms a reinforcing part. That is, the gap formed in the electrolyte layer is closed by the electrolyte reinforcing portion that enhances the cell performance. Therefore, it is possible to prevent a leak path of the cell structure (electrolyte layer) and improve the cell performance of the cell structure.

図１は、セル構造体の製造工程の例を示す概略図である。FIG. 1 is a schematic view showing an example of a manufacturing process of a cell structure. 図２は、本発明の各実施形態に共通するセル構造体の製造方法を説明するフローチャートである。FIG. 2 is a flowchart illustrating a method for manufacturing a cell structure common to each embodiment of the present invention. 図３は、第１実施形態によるセル構造体の中間体を示す模式図である。FIG. 3 is a schematic view showing an intermediate of the cell structure according to the first embodiment. 図４は、プレ含浸工程を説明するフローチャートである。FIG. 4 is a flowchart illustrating the pre-impregnation process. 図５は、第２実施形態によるセル構造体の製造方法におけるプレ含浸工程を説明するフローチャートである。FIG. 5 is a flowchart illustrating a pre-impregnation step in the method for manufacturing a cell structure according to the second embodiment. 図６ａは、セル構造体の中間体のアノード層側からプレ含浸液を滴下した図である。FIG. 6a is a diagram in which the pre-impregnated liquid is dropped from the anode layer side of the intermediate of the cell structure. 図６ｂは、セル構造体の中間体の電解質層側からプレ含浸液を滴下した図である。FIG. 6b is a diagram in which the pre-impregnated liquid is dropped from the electrolyte layer side of the intermediate of the cell structure.

以下、図面等を参照しながら、本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings and the like.

（第１実施形態）
図１は、セル構造体１００の製造工程の例を示す概略図である。図２は、本発明の各実施形態に共通するセル構造体１００の製造方法を説明するフローチャートである。図３は、第１実施形態によるセル構造体の中間体を示す模式図であり、後述するプレ含浸工程を説明する図である。なお、セル構造体１００は、固体酸化物型燃料電池の単セルである。 (First Embodiment)
FIG. 1 is a schematic view showing an example of a manufacturing process of the cell structure 100. FIG. 2 is a flowchart illustrating a method for manufacturing the cell structure 100 common to each embodiment of the present invention. FIG. 3 is a schematic view showing an intermediate of the cell structure according to the first embodiment, and is a diagram for explaining the pre-impregnation step described later. The cell structure 100 is a single cell of a solid oxide fuel cell.

図１に示すように、セル構造体１００の製造工程には、積層工程と、還元焼成工程（焼成工程）と、含浸工程と、カソード積層工程が含まれる。セル構造体１００は、金属支持体１、アノード触媒層（アノード層）２、固体酸化物型電解質層３（以下、単に電解質層３と称する）、カソード層８を積層してなる。 As shown in FIG. 1, the manufacturing process of the cell structure 100 includes a laminating step, a reduction firing step (firing step), an impregnation step, and a cathode laminating step. The cell structure 100 is formed by laminating a metal support 1, an anode catalyst layer (anode layer) 2, a solid oxide type electrolyte layer 3 (hereinafter, simply referred to as an electrolyte layer 3), and a cathode layer 8.

図１、図２に示すように、積層工程（Ｓ１０〜Ｓ３０）には、インク調製工程（Ｓ１０）、塗工工程（Ｓ２０）、貼り合わせ工程（Ｓ３０）が含まれる。 As shown in FIGS. 1 and 2, the laminating step (S10 to S30) includes an ink preparing step (S10), a coating step (S20), and a laminating step (S30).

インク調製工程（Ｓ１０）において、金属支持体の前駆体である支持体用スラリー１１、アノード触媒層２の前駆体である燃料極スラリー２１、電解質層３の前駆体である電解質スラリー３１をそれぞれ湿式粉砕して各層のインクを調整する。各スラリーの調製は既知の方法を用いることができ、例えば原料粉末を有機溶剤、バインダー等と混練して調製する。金属支持体材料は、ステンレス鋼、鉄（Ｆｅ）、ニッケル（Ｎｉ）等の金属粒子が用いることができる。燃料極（アノード極）材料は、例えばジルコニア（硝酸ジルコニウム（II）二水和物（ＺｒＯ（ＮＯ₃）₂・２Ｈ₂Ｏ））にイットリウム（硝酸イットリウム（III）六水和物（Ｙ（ＮＯ₃）₃・６Ｈ₂Ｏ））を添加したものや、ニッケル（硝酸ニッケル（II）六水和物（Ｎｉ（ＮＯ₃）₂・６Ｈ₂Ｏ））等を用いることができる。電解質材料はセラミックスを用いることができ、例えばジルコニア（硝酸ジルコニウム（II）二水和物（ＺｒＯ（ＮＯ₃）₂・２Ｈ₂Ｏ））にイットリウム（硝酸イットリウム（III）六水和物（Ｙ（ＮＯ₃）₃・６Ｈ₂Ｏ））を添加したもの等を用いることができる。各スラリーは、それぞれ湿式粉砕装置により湿式粉砕され、金属支持体１、アノード触媒層２、固体酸化物型電解質層３を構成するためのインク１２，２２，３２が調製される。 In the ink preparation step (S10), the support slurry 11 which is the precursor of the metal support, the fuel electrode slurry 21 which is the precursor of the anode catalyst layer 2, and the electrolyte slurry 31 which is the precursor of the electrolyte layer 3 are wetted. Grind to adjust the ink in each layer. A known method can be used to prepare each slurry. For example, the raw material powder is kneaded with an organic solvent, a binder, or the like. As the metal support material, metal particles such as stainless steel, iron (Fe), and nickel (Ni) can be used. A fuel electrode (anode) materials, for example zirconia yttrium (zirconium nitrate (II) dihydrate _{_{(ZrO (NO 3) 2 ·}} 2H 2 O)) ( yttrium nitrate (III) hexahydrate (Y (NO _{_{_{3) 3 · 6H 2 O)}}} ) obtained by adding and, it is possible to use nickel (such as nickel (II) nitrate hexahydrate _{_{(Ni (NO 3) 2 ·}} 6H 2 O)). The electrolyte material may be used ceramics, for example zirconia yttrium (zirconium nitrate (II) dihydrate _{_{(ZrO (NO 3) 2 ·}} 2H 2 O)) ( yttrium nitrate (III) hexahydrate (Y ( _{_{_{NO 3) 3 · 6H 2 O}}} )) can be used or the like added. Each slurry is wet pulverized by a wet pulverizer to prepare inks 12, 22, and 32 for forming a metal support 1, an anode catalyst layer 2, and a solid oxide type electrolyte layer 3.

なお、電解質材料、燃料極材料、金属支持体材料は上記のものに限られず、それぞれ従来から用いられている既知のいずれの材料を用いてもよい。また、各スラリーには、界面活性剤、分散剤、増粘剤等を適宜添加してもよい。 The electrolyte material, fuel electrode material, and metal support material are not limited to those described above, and any known conventionally used material may be used. Further, a surfactant, a dispersant, a thickener and the like may be appropriately added to each slurry.

塗工工程（Ｓ２０）において、例えばテープキャスティング法により塗膜を形成する。具体的には、片側に延設部４１を有する容器４をローラ５により巻き取り可能なフィルム５１上に載せ、調製されたインク１２，２２，３２を個別の容器４にそれぞれ入れる。フィルム５１と延設部４１との間には僅かな隙間が形成されており、ローラ５によりフィルム５１を巻き取ることでフィルム５１が動かされ、フィルム５１の表面上に各インク１２，２２，３２が塗工される。これにより、フィルム５１上にそれぞれ塗膜１３，２３，３３が形成される。 In the coating step (S20), a coating film is formed by, for example, a tape casting method. Specifically, a container 4 having an extending portion 41 on one side is placed on a film 51 that can be wound by a roller 5, and the prepared inks 12, 22, and 32 are put into individual containers 4, respectively. A slight gap is formed between the film 51 and the extending portion 41, and the film 51 is moved by winding the film 51 by the roller 5, and the inks 12, 22, and 32 are on the surface of the film 51. Is painted. As a result, the coating films 13, 23, and 33 are formed on the film 51, respectively.

なお、塗膜の形成方法は上記のテープキャスティング法に限られず、既知のいずれの方法を用いてもよい。 The method for forming the coating film is not limited to the tape casting method described above, and any known method may be used.

貼り合わせ工程（Ｓ３０）において、各塗膜１３，２３，３３をロールプレスにより貼り合わせる。これにより、多孔質金属からなる金属支持体１、アノード多孔質層（アノード層）２、電解質層３の三層が積層された、セル構造体１００の中間生成物である中間体１０が形成される。貼り合わせは、金属支持体１、アノード多孔質層（アノード層）２、電解質層３の順になるように行われる。 In the bonding step (S30), the coating films 13, 23, and 33 are bonded by a roll press. As a result, an intermediate 10 which is an intermediate product of the cell structure 100 in which three layers of a metal support 1 made of a porous metal, an anode porous layer (anode layer) 2, and an electrolyte layer 3 are laminated is formed. To. The bonding is performed in the order of the metal support 1, the anode porous layer (anode layer) 2, and the electrolyte layer 3.

なお、塗膜の貼合方法は、ロールプレスに限られず、既知のいずれの方法を用いてもよい。 The method of laminating the coating film is not limited to the roll press, and any known method may be used.

次に、還元焼成工程（Ｓ４０）において、中間体１０を加熱し、還元焼成する。即ち、金属支持体１、アノード多孔質層（アノード層）２、電解質層３を共焼成する。 Next, in the reduction firing step (S40), the intermediate 10 is heated and reduction firing is performed. That is, the metal support 1, the anode porous layer (anode layer) 2, and the electrolyte layer 3 are co-fired.

前述のとおり、電解質層３はセラミックス材料からなり、塗工工程（Ｓ２０）及び貼り合わせ工程（Ｓ３０）を経て生成された電解質層３は薄膜セラミックスにより構成される。薄膜セラミックスは脆弱であるため、還元焼成工程（Ｓ４０）において焼成時の凝集度が不十分で電解質層３の緻密性が十分に保たれない場合、電解質層３の内部に残存する微細な隙間が電解質クラックを誘発し、電解質層３を貫通する隙間が形成され易い。即ち、図３に示すように、中間体１０の電解質層３に欠陥部位６が生じる恐れがある。電解質層３に隙間が形成されたまま、後述する含浸工程（Ｓ６０）及びカソード積層工程（Ｓ７０）を行い、セル構造体（燃料電池セル）１００が製造されると、燃料電池を作動させた際にガス漏れ（リークパス）を引き起こしてしまう。そこで、図２に示すように、本発明の各実施形態では、還元焼成後、含浸工程（Ｓ６０）を行う前に、電解質層３の欠陥部位６を閉塞する電解質補強部７を形成するためのプレ含浸工程（Ｓ５０）を行う。なお、ここでいう欠陥部位６とは電解質層３を貫通する隙間及び貫通していない隙間（クラック）のいずれをも含む。 As described above, the electrolyte layer 3 is made of a ceramic material, and the electrolyte layer 3 produced through the coating step (S20) and the bonding step (S30) is made of thin film ceramics. Since thin-film ceramics are fragile, if the degree of cohesion during firing is insufficient in the reduction firing step (S40) and the denseness of the electrolyte layer 3 is not sufficiently maintained, fine gaps remaining inside the electrolyte layer 3 will remain. It induces electrolyte cracks and easily forms gaps penetrating the electrolyte layer 3. That is, as shown in FIG. 3, there is a possibility that a defective portion 6 may occur in the electrolyte layer 3 of the intermediate 10. When the cell structure (fuel cell) 100 is manufactured by performing the impregnation step (S60) and the cathode lamination step (S70) described later with the gap formed in the electrolyte layer 3, when the fuel cell is operated. Causes a gas leak (leak path). Therefore, as shown in FIG. 2, in each embodiment of the present invention, after the reduction firing and before the impregnation step (S60), the electrolyte reinforcing portion 7 for closing the defective portion 6 of the electrolyte layer 3 is formed. The pre-impregnation step (S50) is performed. The defect portion 6 referred to here includes both a gap penetrating the electrolyte layer 3 and a gap (crack) that does not penetrate the electrolyte layer 3.

プレ含浸工程（Ｓ５０）において、プレ含浸液により中間体１０を含浸する。プレ含浸液は、例えばセリア等を含む非導電性のセラミックスを含み、プレ含浸液を中間体１０に含浸させることで、電解質層３の欠陥部位６内にプレ含浸液が充填される。電解質層３の欠陥部位６内にプレ含浸液が充填された状態で乾燥、か焼することにより、電解質層３の
欠陥部位６内に、電解質層３の欠陥部位６を閉塞する電解質補強部７が形成される。また、プレ含浸液には、非導電性のセラミックスが用いられているため、電解質補強部７により電解質層３の絶縁性が高められる。なお、プレ含浸工程（Ｓ５０）の詳細は後述する。 In the pre-impregnation step (S50), the intermediate 10 is impregnated with the pre-impregnation liquid. The pre-impregnated liquid contains non-conductive ceramics containing, for example, ceria, and by impregnating the intermediate 10 with the pre-impregnated liquid, the pre-impregnated liquid is filled in the defective portion 6 of the electrolyte layer 3. An electrolyte reinforcing portion 7 that closes the defective portion 6 of the electrolyte layer 3 into the defective portion 6 of the electrolyte layer 3 by drying and calcinating while the defective portion 6 of the electrolyte layer 3 is filled with the pre-impregnated liquid. Is formed. Further, since non-conductive ceramics are used for the pre-impregnated liquid, the insulating property of the electrolyte layer 3 is enhanced by the electrolyte reinforcing portion 7. The details of the pre-impregnation step (S50) will be described later.

プレ含浸工程（Ｓ５０）後には、含浸工程（Ｓ６０）が行われる。この含浸工程（Ｓ６０）において、触媒溶液により中間体１０（アノード層２）を含浸する。具体的には、含浸工程（Ｓ６０）は以下の手順で行われる。まず、例えば金属材料であるニッケル（硝酸ニッケル（II）六水和物（Ｎｉ（ＮＯ₃）₂・６Ｈ₂Ｏ））を含む触媒溶液を作製する。次に、エタノールでアノード多孔質層（アノード層）２を洗浄した後、真空引きにより中間体１０内のエタノール・油分を飛ばす。次に、触媒溶液をアノード多孔質層（アノード層）２側から中間体１０に含浸し、真空引きによりアノード多孔質層（アノード層）２内の空気を取り除き、触媒溶液を細部まで浸透させた後、か焼する。これにより、アノード多孔質層（アノード層）２は触媒溶液が浸透したアノード触媒層２を形成する。以下では、触媒溶液が滴下されるまでのアノード多孔質層と、触媒溶液滴下後のアノード触媒層とをいずれもアノード層２と称する。 After the pre-impregnation step (S50), the impregnation step (S60) is performed. In this impregnation step (S60), the intermediate 10 (anode layer 2) is impregnated with the catalyst solution. Specifically, the impregnation step (S60) is performed in the following procedure. First, for example, nickel is a metal material (nickel (II) nitrate hexahydrate _{_{(Ni (NO 3) 2 ·}} 6H 2 O)) to prepare a catalyst solution containing. Next, after washing the anode porous layer (anode layer) 2 with ethanol, the ethanol and oil in the intermediate 10 are removed by vacuuming. Next, the catalyst solution was impregnated into the intermediate 10 from the anode porous layer (anode layer) 2 side, the air in the anode porous layer (anode layer) 2 was removed by vacuuming, and the catalyst solution was permeated into detail. After that, bake. As a result, the anode porous layer (anode layer) 2 forms the anode catalyst layer 2 in which the catalyst solution has permeated. Hereinafter, both the porous anode layer until the catalyst solution is dropped and the anode catalyst layer after the catalyst solution is dropped are referred to as the anode layer 2.

上記のとおり、含浸工程（Ｓ６０）において、中間体１０に触媒溶液を滴下するため、特許文献１（特開２０１２−２０４２７７号公報）のように、還元焼成後、プレ含浸せずに含浸工程（Ｓ６０）を行っても、触媒溶液により電解質層３の欠陥部位６を閉塞し得る場合がある。しかしながら、触媒溶液にはニッケル等の導電性の金属材料が含まれており、欠陥部位６が閉塞されたとしても、電解質層３の内部に導電パスが形成されてしまい、電解質層３の絶縁性が低下する。そのため、セル構造体１００の性能が低下する恐れがある。しかしながら、本実施形態では、含浸工程（Ｓ６０）の前にプレ含浸を実施し、プレ含浸液には、非導電性のセラミックスが用いられているため、電解質補強部７により電解質層３の絶縁性が高められ、セル構造体１００のセル性能が高められる。ここで言うセル性能とは、電解質層３の絶縁性やイオン伝導度等を含む、セル構造体１００の発電性能に寄与する性質の総称である。 As described above, in the impregnation step (S60), since the catalyst solution is dropped onto the intermediate 10, the impregnation step (Japanese Patent Laid-Open No. 2012-204277) is performed without pre-impregnation after reduction firing as in Patent Document 1 (Japanese Patent Laid-Open No. 2012-204277). Even if S60) is performed, the defective portion 6 of the electrolyte layer 3 may be blocked by the catalyst solution. However, the catalyst solution contains a conductive metal material such as nickel, and even if the defective portion 6 is closed, a conductive path is formed inside the electrolyte layer 3, and the insulating property of the electrolyte layer 3 is increased. Decreases. Therefore, the performance of the cell structure 100 may deteriorate. However, in the present embodiment, the pre-impregnation is performed before the impregnation step (S60), and since non-conductive ceramics are used as the pre-impregnation liquid, the electrolyte reinforcing portion 7 provides the insulating property of the electrolyte layer 3. Is enhanced, and the cell performance of the cell structure 100 is enhanced. The cell performance referred to here is a general term for properties that contribute to the power generation performance of the cell structure 100, including the insulating property of the electrolyte layer 3 and the ionic conductivity.

なお、含浸工程（Ｓ６０）は上記の方法に限られず、既知のいずれの方法を用いてもよい。 The impregnation step (S60) is not limited to the above method, and any known method may be used.

含浸工程（Ｓ６０）の後、カソード積層工程（Ｓ７０）が実施される。このカソード積層工程（Ｓ７０）において、中間体１０の電解質層３上に、スパッタリング法などにより拡散防止層８１を形成し、既知の印刷法により、拡散防止層８１上にカソード層８を積層する。これにより、金属支持体１、アノード層２、電解質層３及びカソード層８が積層されたセル構造体１００が生成される。 After the impregnation step (S60), the cathode lamination step (S70) is carried out. In this cathode lamination step (S70), the diffusion prevention layer 81 is formed on the electrolyte layer 3 of the intermediate 10 by a sputtering method or the like, and the cathode layer 8 is laminated on the diffusion prevention layer 81 by a known printing method. As a result, the cell structure 100 in which the metal support 1, the anode layer 2, the electrolyte layer 3 and the cathode layer 8 are laminated is generated.

次に、プレ含浸工程の詳細を説明する。 Next, the details of the pre-impregnation step will be described.

図４は、プレ含浸工程を説明するフローチャートである。 FIG. 4 is a flowchart illustrating the pre-impregnation process.

図４に示す通り、プレ含浸工程では、まずプレ含浸液を作製する（Ｓ５０１）。プレ含浸液は、非導電性セラミックスのセリア（硝酸セリウム（III）六水和物（Ｃｅ（ＮＯ₃）
₃・６Ｈ₂Ｏ））、エタノール等を含む界面活性剤及び水を混合したものに、さらにガドリニウム（硝酸ガドリニウム（III）六水和物（Ｇｄ（ＮＯ₃）₃・６Ｈ₂Ｏ））を加えて作製する。プレ含浸液は、表面張力が、含浸工程（図２のＳ６０）において含浸する触媒溶液の表面張力よりも小さくなるように、界面活性剤の量を調整する。なお、好ましくは、プレ含浸液作製後に、エタノールで中間体１０を洗浄し、真空引きによりエタノール・油分を飛ばす。 As shown in FIG. 4, in the pre-impregnation step, a pre-impregnation liquid is first prepared (S501). The pre-impregnated liquid is ceria (cerium nitrate (III) hexahydrate (Ce (NO ₃ )), which is a non-conductive ceramic.
₃ · 6H ₂ O)), to a mixture of surfactant and water containing ethanol and the like, further gadolinium (gadolinium nitrate (III) hexahydrate _{_{(Gd (NO 3) 3 ·}} 6H 2 O)) was added To make. The amount of the surfactant of the pre-impregnated liquid is adjusted so that the surface tension becomes smaller than the surface tension of the catalyst solution impregnated in the impregnation step (S60 of FIG. 2). Preferably, after preparing the pre-impregnated liquid, the intermediate 10 is washed with ethanol, and ethanol and oil are removed by vacuuming.

次に、中間体１０を真空チャンバーに入れ、作製したプレ含浸液を中間体１０に含浸する（Ｓ５０２）。図３に示すように、プレ含浸液の含浸は、金属支持体１を介したアノード層２の側からプレ含浸液を滴下することにより行う。金属支持体１及びアノード層２はいずれも多孔質であるため、アノード層２の側から中間体１０にプレ含浸液を滴下すると、プレ含浸液は、金属支持体１及びアノード層を通り抜けて、電解質層３の欠陥部位６内に充填される。また、プレ含浸液をアノード層２の側から滴下して欠陥部位６を充填し、後述する乾燥・か焼（Ｓ５０４）により欠陥部位６内に電解質補強部７を形成することで、触媒溶液が電解質層３の欠陥部位６内に入ることを確実に防止する。即ち、含浸工程（Ｓ６０）において、触媒溶液はアノード層２の側から含浸されるが、プレ含浸液を先にアノード層２の側から滴下して欠陥部位６内に電解質補強部７を形成しておくため、導電性の金属材料を含む触媒溶液が電解質層３の欠陥部位６内に入ることを確実に防止できる。従って、導電パスを確実に防止し、燃料電池作動時の短絡をより確実に防止することができる。 Next, the intermediate 10 is placed in a vacuum chamber, and the prepared pre-impregnated liquid is impregnated into the intermediate 10 (S502). As shown in FIG. 3, the pre-impregnated liquid is impregnated by dropping the pre-impregnated liquid from the side of the anode layer 2 via the metal support 1. Since both the metal support 1 and the anode layer 2 are porous, when the pre-impregnated liquid is dropped onto the intermediate 10 from the side of the anode layer 2, the pre-impregnated liquid passes through the metal support 1 and the anode layer and passes through the metal support 1 and the anode layer. The defect portion 6 of the electrolyte layer 3 is filled. Further, the pre-impregnated liquid is dropped from the side of the anode layer 2 to fill the defective portion 6, and the electrolyte reinforcing portion 7 is formed in the defective portion 6 by drying / calcination (S504) described later, whereby the catalyst solution is formed. It surely prevents the electrolyte layer 3 from entering the defective portion 6. That is, in the impregnation step (S60), the catalyst solution is impregnated from the side of the anode layer 2, but the pre-impregnated solution is first dropped from the side of the anode layer 2 to form the electrolyte reinforcing portion 7 in the defective portion 6. Therefore, it is possible to reliably prevent the catalyst solution containing the conductive metal material from entering the defective portion 6 of the electrolyte layer 3. Therefore, it is possible to reliably prevent the conductive path and more reliably prevent a short circuit during fuel cell operation.

また、前述のとおり、プレ含浸液の表面張力は、含浸工程（図２のＳ６０）において含浸する触媒溶液の表面張力よりも小さいため、プレ含浸液は電解質層３の僅かな隙間である欠陥部位６内に入り易い。一方、プレ含浸液よりも表面張力の大きい触媒溶液はプレ含浸液が充填された欠陥部位６内に入り難くなる。従って、含浸工程（図２のＳ６０）において導電性の金属材料を含む触媒溶液が電解質層３の欠陥部位６内に入ることをより確実に防止できる。 Further, as described above, since the surface tension of the pre-impregnated liquid is smaller than the surface tension of the catalyst solution impregnated in the impregnation step (S60 of FIG. 2), the pre-impregnated liquid is a defect portion which is a slight gap in the electrolyte layer 3. Easy to get inside 6. On the other hand, the catalyst solution having a higher surface tension than the pre-impregnated liquid is less likely to enter the defective portion 6 filled with the pre-impregnated liquid. Therefore, in the impregnation step (S60 of FIG. 2), it is possible to more reliably prevent the catalyst solution containing the conductive metal material from entering the defective portion 6 of the electrolyte layer 3.

なお、プレ含浸液の滴下量は、含浸工程（図２のＳ６０）において中間体１０（アノード層２）に含浸する触媒溶液の量よりもできるだけ少なめにし、プレ含浸液により触媒溶液がアノード層２に入り難くなることを防止する。即ち、触媒金属を含まないプレ含浸液が中間体１０内に過剰に入ってしまうと、アノード層２がプレ含浸液によりコーティングされてしまい、触媒溶液がアノード層２内に付着し難くなってしまう虞がある。従って、本実施形態では、プレ含浸液の滴下量を含浸する触媒溶液の量よりも少なくし、アノード層２がプレ含浸液によりコーティングされるのを防止する。これにより、含浸工程（Ｓ６０）において触媒溶液をより確実にアノード層２に入れることができる。 The amount of the pre-impregnated liquid dropped is made as small as possible from the amount of the catalyst solution impregnated in the intermediate 10 (anode layer 2) in the impregnation step (S60 in FIG. 2), and the catalyst solution is made into the anode layer 2 by the pre-impregnated liquid. Prevents it from becoming difficult to enter. That is, if the pre-impregnated liquid containing no catalyst metal enters the intermediate 10 in excess, the anode layer 2 is coated with the pre-impregnated liquid, and it becomes difficult for the catalyst solution to adhere to the inside of the anode layer 2. There is a risk. Therefore, in the present embodiment, the dropping amount of the pre-impregnated liquid is made smaller than the amount of the catalyst solution to be impregnated, and the anode layer 2 is prevented from being coated with the pre-impregnated liquid. As a result, the catalyst solution can be more reliably put into the anode layer 2 in the impregnation step (S60).

プレ含浸液を滴下した後、真空チャンバー内で真空引きを行う（Ｓ５０３）。真空引きにより中間体１０内の空気が取り除かれ、プレ含浸液は電解質層３の欠陥部位６内の細部まで浸透する。また、プレ含浸液が確実に浸透するように、真空引きは、好ましくは複数回（例えば３〜４回程度）行う。 After dropping the pre-impregnated liquid, vacuuming is performed in the vacuum chamber (S503). The air in the intermediate 10 is removed by evacuation, and the pre-impregnated liquid penetrates into the details in the defective portion 6 of the electrolyte layer 3. Further, vacuuming is preferably performed a plurality of times (for example, about 3 to 4 times) so that the pre-impregnated liquid permeates reliably.

次に、真空チャンバー内で中間体１０を乾燥させ、か焼する（Ｓ５０４）。乾燥により
、プレ含浸液内のエタノール等の水気を飛ばし、か焼により、より沸点の高い溶媒を飛ば
してプレ含浸液内の物質（セリア）を析出させる。これにより、図３に示すように、電解質層３の欠陥部位６内に電解質補強部７が形成される。 Next, the intermediate 10 is dried and calcinated in the vacuum chamber (S504). Drying removes water such as ethanol in the pre-impregnated liquid, and calcination removes a solvent having a higher boiling point to precipitate a substance (ceria) in the pre-impregnated liquid. As a result, as shown in FIG. 3, the electrolyte reinforcing portion 7 is formed in the defective portion 6 of the electrolyte layer 3.

このように、還元焼成後、含浸工程（Ｓ６０）を行う前に、非導電性セラミックスのセリアからなるプレ含浸液を中間体１０に滴下するプレ含浸工程（Ｓ５０）を行うことで、電解質層３におけるガス漏れ（リークパス）を防止しつつ、電解質層３の電気的絶縁性（セル性能）を補強する。また、セリアは電解質材料に用いられるジルコニアよりも高い酸素イオン伝導度を有するため、電解質補強部７におけるオーム抵抗が低減し（セル性能）、セル構造体１００の発電性能が向上する。即ち、電解質補強部７は、リークパスの防止と、セル性能の向上という２つの効果を同時に発揮する。 As described above, after the reduction firing and before the impregnation step (S60), the pre-impregnation step (S50) of dropping the pre-impregnation liquid made of non-conductive ceramic ceria onto the intermediate 10 is performed to perform the pre-impregnation step (S50). The electrical insulation (cell performance) of the electrolyte layer 3 is reinforced while preventing gas leakage (leak path). Further, since ceria has higher oxygen ion conductivity than zirconia used as an electrolyte material, the ohm resistance in the electrolyte reinforcing portion 7 is reduced (cell performance), and the power generation performance of the cell structure 100 is improved. That is, the electrolyte reinforcing portion 7 simultaneously exerts two effects of preventing leak paths and improving cell performance.

なお、プレ含浸液の作製においてセリアに添加されたガドリニウムにも酸素イオン伝導度を高める働きがあるため、セル構造体１００の発電性能はさらに向上する。 Since gadolinium added to ceria also has a function of increasing oxygen ion conductivity in the preparation of the pre-impregnated liquid, the power generation performance of the cell structure 100 is further improved.

上記した第１実施形態のセル構造体１００及びセル構造体１００の製造方法によれば、以下の効果を得ることができる。 According to the cell structure 100 and the method for manufacturing the cell structure 100 of the first embodiment described above, the following effects can be obtained.

セル構造体１００の中間体１０は、金属支持体１、アノード触媒層２、電解質層（固体酸化物型電解質層）３を積層してなり、電解質層３の欠陥部位６内にセル性能を高める電解質補強部７を形成している。即ち、セル性能を高める電解質補強部７により、電解質層３に形成された隙間が閉塞されている。従って、セル構造体１００（電解質層３）のガス漏れ（リークパス）を防止するとともに、セル構造体１００のセル性能を高めることができる。 The intermediate 10 of the cell structure 100 is formed by laminating a metal support 1, an anode catalyst layer 2, and an electrolyte layer (solid oxide type electrolyte layer) 3, and enhances cell performance in the defective portion 6 of the electrolyte layer 3. The electrolyte reinforcing portion 7 is formed. That is, the gap formed in the electrolyte layer 3 is closed by the electrolyte reinforcing portion 7 that enhances the cell performance. Therefore, it is possible to prevent gas leakage (leak path) of the cell structure 100 (electrolyte layer 3) and improve the cell performance of the cell structure 100.

セル構造体１００において、中間体１０は、電解質層３の欠陥部位６内に非導電性のセラミックスからなる電解質補強部７を形成している。電解質層３の欠陥部位６を、例えば導電性の金属を含む触媒溶液等により閉塞すると、電解質層３の内部に導電パスが形成されてしまい、電解質層３の絶縁性が低下し、燃料電池作動時に短絡するなどの恐れがある。一方、セル構造体１００の中間体１０においては、電解質層３の欠陥部位６を非導電性のセラミックスからなる電解質補強部７により閉塞している。これにより、セル構造体１００（電解質層３）のリークパスを防止するとともに、電解質層３の電気的絶縁性を補強することができる。 In the cell structure 100, the intermediate 10 forms an electrolyte reinforcing portion 7 made of non-conductive ceramics in the defective portion 6 of the electrolyte layer 3. When the defective portion 6 of the electrolyte layer 3 is closed with, for example, a catalytic solution containing a conductive metal, a conductive path is formed inside the electrolyte layer 3, the insulating property of the electrolyte layer 3 is lowered, and the fuel cell is operated. There is a risk of short circuit at times. On the other hand, in the intermediate body 10 of the cell structure 100, the defective portion 6 of the electrolyte layer 3 is closed by the electrolyte reinforcing portion 7 made of non-conductive ceramics. As a result, the leak path of the cell structure 100 (electrolyte layer 3) can be prevented, and the electrical insulating property of the electrolyte layer 3 can be reinforced.

セル構造体１００において、中間体１０は、電解質層３の欠陥部位６内にセリアを含有する非導電性のセラミックスからなる電解質補強部７を形成している。セリアは電解質材料に用いられるジルコニアよりも高い酸素イオン伝導度を有する。従って、電解質補強部７におけるオーム抵抗が低減し、セル構造体１００の発電性能が向上する。即ち、セル構造体１００（電解質層３）のリークパスを防止するとともに、セル構造体１００のセル性能をさらに高めることができる。 In the cell structure 100, the intermediate 10 forms an electrolyte reinforcing portion 7 made of non-conductive ceramics containing ceria in the defective portion 6 of the electrolyte layer 3. Ceria has higher oxygen ion conductivity than zirconia used as an electrolyte material. Therefore, the ohmic resistance in the electrolyte reinforcing portion 7 is reduced, and the power generation performance of the cell structure 100 is improved. That is, it is possible to prevent the leak path of the cell structure 100 (electrolyte layer 3) and further enhance the cell performance of the cell structure 100.

セル構造体１００の製造方法によれば、積層工程（Ｓ１０〜Ｓ３０）と、焼成工程（Ｓ４０）と、プレ含浸工程（Ｓ５０）と、含浸工程（Ｓ６０）と、カソード積層工程（Ｓ７０）とを有する。そして、プレ含浸工程（Ｓ５０）において、セル構造体１００の中間体１０にプレ含浸液を含浸させて、電解質層３の欠陥部位６内にセル性能を高める電解質補強部７を形成する。薄膜セラミックスが用いられる電解質層３は、焼成時に電解質クラック（欠陥部位６）を誘発し、リークパスを引き起こす恐れがある。一方、含浸工程（Ｓ６０）において、導電性材料（貴金属）を含む触媒溶液により欠陥部位６を閉塞すると、電解質層３の内部に導電パスが形成され、短絡等、セル性能の低下を引き起こす恐れがある。これに対し、本実施形態の製造方法では、焼成工程（Ｓ４０）後、含浸工程（Ｓ６０）前に電解質層３の欠陥部位６内にセル性能を高める電解質補強部７を形成するプレ含浸工程（Ｓ５０）を設けている。従って、セル構造体１００（電解質層３）のリークパスを防止するとともに、セル構造体１００のセル性能を高めることができる。 According to the method for manufacturing the cell structure 100, the laminating step (S10 to S30), the firing step (S40), the pre-impregnation step (S50), the impregnation step (S60), and the cathode laminating step (S70) are performed. Have. Then, in the pre-impregnation step (S50), the intermediate 10 of the cell structure 100 is impregnated with the pre-impregnation liquid to form the electrolyte reinforcing portion 7 that enhances the cell performance in the defective portion 6 of the electrolyte layer 3. The electrolyte layer 3 in which thin-film ceramics are used may induce electrolyte cracks (defect sites 6) during firing, causing a leak path. On the other hand, in the impregnation step (S60), if the defective portion 6 is closed with a catalyst solution containing a conductive material (precious metal), a conductive path is formed inside the electrolyte layer 3, which may cause a decrease in cell performance such as a short circuit. is there. On the other hand, in the manufacturing method of the present embodiment, after the firing step (S40) and before the impregnation step (S60), the pre-impregnation step (pre-impregnation step 7) of forming the electrolyte reinforcing portion 7 for enhancing the cell performance in the defective portion 6 of the electrolyte layer 3 (S60). S50) is provided. Therefore, it is possible to prevent the leak path of the cell structure 100 (electrolyte layer 3) and improve the cell performance of the cell structure 100.

セル構造体１００の製造方法によれば、プレ含浸工程（Ｓ５０）において、セル構造体１００の中間体１０にプレ含浸液を滴下して電解質補強部７を形成する。このように、中間体１０にプレ含浸液を滴下することで、重力の効果により電解質層３の欠陥部位６内にプレ含浸液が確実に充填され、欠陥部位６内に電解質補強部７を確実に形成させることができる。 According to the method for manufacturing the cell structure 100, in the pre-impregnation step (S50), the pre-impregnation liquid is dropped onto the intermediate 10 of the cell structure 100 to form the electrolyte reinforcing portion 7. By dropping the pre-impregnated liquid onto the intermediate 10 in this way, the pre-impregnated liquid is surely filled in the defective portion 6 of the electrolyte layer 3 due to the effect of gravity, and the electrolyte reinforcing portion 7 is surely filled in the defective portion 6. Can be formed into.

セル構造体１００の製造方法によれば、プレ含浸工程（Ｓ５０）において、非導電性のセラミックスからなるプレ含浸液を含浸させる。これにより、電解質層３の欠陥部位６内にプレ含浸液が充填され、欠陥部位６内に欠陥部位６を閉塞する非導電性のセラミックスからなる電解質補強部７が形成される。従って、セル構造体１００（電解質層３）のリークパスを防止するとともに、電解質層３の電気的絶縁性を補強することができる。 According to the method for producing the cell structure 100, in the pre-impregnation step (S50), the pre-impregnation liquid made of non-conductive ceramics is impregnated. As a result, the defective portion 6 of the electrolyte layer 3 is filled with the pre-impregnated liquid, and the electrolyte reinforcing portion 7 made of non-conductive ceramics that closes the defective portion 6 is formed in the defective portion 6. Therefore, it is possible to prevent the leak path of the cell structure 100 (electrolyte layer 3) and to reinforce the electrical insulating property of the electrolyte layer 3.

セル構造体１００の製造方法によれば、プレ含浸工程（Ｓ５０）において、セリアを含有するプレ含浸液を含浸させる。これにより、電解質層３の欠陥部位６内に、セリアを含有する電解質補強部７が形成され、電解質補強部７におけるオーム抵抗が低減し、セル構造体１００の発電性能が向上する。即ち、セル構造体１００（電解質層３）のリークパスを防止するとともに、セル構造体１００のセル性能をさらに高めることができる。 According to the method for producing the cell structure 100, in the pre-impregnation step (S50), the pre-impregnation liquid containing ceria is impregnated. As a result, the electrolyte reinforcing portion 7 containing ceria is formed in the defective portion 6 of the electrolyte layer 3, the ohmic resistance in the electrolyte reinforcing portion 7 is reduced, and the power generation performance of the cell structure 100 is improved. That is, it is possible to prevent the leak path of the cell structure 100 (electrolyte layer 3) and further enhance the cell performance of the cell structure 100.

セル構造体１００の製造方法によれば、プレ含浸工程（Ｓ５０）において、アノード層２の側からセル構造体１００の中間体１０にプレ含浸液を滴下して電解質補強部７を形成する。このように、アノード層２の側から先にプレ含浸液を滴下し、欠陥部位６内に電解質補強部７を形成しておくことで、アノード層２の側から触媒溶液を含浸する含浸工程（Ｓ６０）において導電性の金属材料を含む触媒溶液が電解質層３の欠陥部位６内に入ることを確実に防止できる。即ち、電解質層３内の導電パスを確実に防止し、燃料電池作動時の短絡をより確実に防止することができる。 According to the method for manufacturing the cell structure 100, in the pre-impregnation step (S50), the pre-impregnation liquid is dropped onto the intermediate 10 of the cell structure 100 from the anode layer 2 side to form the electrolyte reinforcing portion 7. In this way, the pre-impregnation liquid is dropped first from the anode layer 2 side to form the electrolyte reinforcing portion 7 in the defective portion 6, so that the impregnation step of impregnating the catalyst solution from the anode layer 2 side ( In S60), it is possible to reliably prevent the catalyst solution containing the conductive metal material from entering the defective portion 6 of the electrolyte layer 3. That is, it is possible to reliably prevent the conductive path in the electrolyte layer 3 and more reliably prevent a short circuit during operation of the fuel cell.

セル構造体１００の製造方法によれば、プレ含浸工程（Ｓ５０）は、含浸工程（Ｓ６０）においてアノード層２に含浸する触媒溶液の量よりも少ない量のプレ含浸液をセル構造体１００の中間体１０に滴下する。これにより、アノード層２がプレ含浸液によりコーティングされて触媒溶液がアノード層２に入り難くなることを防止できる。即ち、含浸工程（Ｓ６０）において、触媒溶液をより確実にアノード層２に入れることができる。 According to the method for producing the cell structure 100, in the pre-impregnation step (S50), an intermediate amount of the pre-impregnated liquid in the cell structure 100 is smaller than the amount of the catalyst solution impregnated in the anode layer 2 in the impregnation step (S60). Drop on body 10. This makes it possible to prevent the anode layer 2 from being coated with the pre-impregnated liquid and making it difficult for the catalyst solution to enter the anode layer 2. That is, in the impregnation step (S60), the catalyst solution can be more reliably put into the anode layer 2.

セル構造体１００の製造方法によれば、プレ含浸工程（Ｓ５０）において含浸するプレ含浸液の表面張力は、含浸工程（Ｓ６０）において含浸する触媒溶液の表面張力よりも小さい。従って、プレ含浸液は触媒溶液よりも電解質層３の欠陥部位６内に入り易く、触媒溶液はプレ含浸液が充填された欠陥部位６内に入り難い。従って、欠陥部位６内に電解質補強部７を確実に形成させるとともに、含浸工程（Ｓ６０）において導電性の金属材料を含む触媒溶液が電解質層３の欠陥部位６内に入ることを確実に防止できる。 According to the method for producing the cell structure 100, the surface tension of the pre-impregnated liquid impregnated in the pre-impregnated step (S50) is smaller than the surface tension of the catalyst solution impregnated in the pre-impregnated step (S60). Therefore, the pre-impregnated solution is more likely to enter the defective portion 6 of the electrolyte layer 3 than the catalyst solution, and the catalyst solution is less likely to enter the defective portion 6 filled with the pre-impregnated liquid. Therefore, the electrolyte reinforcing portion 7 can be reliably formed in the defective portion 6, and the catalyst solution containing the conductive metal material can be reliably prevented from entering the defective portion 6 of the electrolyte layer 3 in the impregnation step (S60). ..

なお、本実施形態において、プレ含浸液はセリアを用いているが、必ずしもこれに限られない。例えば、セリアに代えてジルコニア（硝酸ジルコニウム（II）二水和物（ＺｒＯ
（ＮＯ₃）₂・２Ｈ₂Ｏ））にイットリウム（硝酸イットリウム（III）六水和物（Ｙ（ＮＯ₃）₃・６Ｈ₂Ｏ））を加えたものを用い、これに界面活性剤及び水を混合して作製してもよい。また、セリアに代えてアルミナ（硝酸アルミニウム（III）九水和物（Ａｌ（ＮＯ₃）₃・９Ｈ₂Ｏ））を用い、これに界面活性剤及び水を混合して作製してもよい。より絶縁性の高いジルコニアやアルミナを含むプレ含浸液により電解質補強部７を形成することで、電解質層３の電気的絶縁性をより補強することができる。従って、セル構造体１００（電解質層３）のリークパスを防止するとともに、電解質層３の絶縁性をより補強することができる。また、プレ含浸液はジルコニアやアルミナ以外にも、例えば、マグネシア（硝酸マグネシウム（II）六水和物（Ｍｇ（ＮＯ₃）₂・６Ｈ₂Ｏ））などを用いてもよい。 In this embodiment, ceria is used as the pre-impregnated liquid, but the pre-impregnated liquid is not necessarily limited to this. For example, instead of ceria, zirconia (zirconium nitrate (II) dihydrate (ZrO)
_{_{_{(NO 3) 2 · 2H 2}}} O)) in using the plus yttrium (yttrium nitrate (III) hexahydrate _{_{(Y (NO 3) 3 ·}} 6H 2 O)), which the surfactant and water May be mixed and produced. In place of the ceria using alumina (aluminum nitrate (III) nonahydrate _{_{(Al (NO 3) 3 ·}} 9H 2 O)), it may be made thereto by mixing a surfactant and water. By forming the electrolyte reinforcing portion 7 with a pre-impregnated liquid containing zirconia or alumina having higher insulating properties, the electrical insulating properties of the electrolyte layer 3 can be further reinforced. Therefore, the leak path of the cell structure 100 (electrolyte layer 3) can be prevented, and the insulating property of the electrolyte layer 3 can be further reinforced. Also, the pre-impregnation liquid is in addition to zirconia and alumina, for example, magnesia (magnesium nitrate (II) hexahydrate _{_{(Mg (NO 3) 2 ·}} 6H 2 O)) or the like may be used.

また、本実施形態において、アノード層２の側から滴下される触媒溶液が電解質層３の欠陥部位６内に入ることを確実に防止するために、プレ含浸液をアノード層２の側から滴下することが好ましいが、必ずしもこれに限られず、プレ含浸液を電解質層３の側から滴下してもよい。 Further, in the present embodiment, the pre-impregnated solution is dropped from the anode layer 2 side in order to surely prevent the catalyst solution dropped from the anode layer 2 side from entering the defective portion 6 of the electrolyte layer 3. It is preferable, but not necessarily limited to this, and the pre-impregnated solution may be dropped from the side of the electrolyte layer 3.

（第２実施形態）
図５、図６ａ、図６ｂを参照して、第２実施形態によるセル構造体１００の中間体１０を説明する。本実施形態においては、アノード層２の側と、電解質層３の側との両方の側からプレ含浸液を滴下する点が第１実施形態と異なる。なお、第１実施形態と同様の要素には同一の符号を付し、その説明を省略する。 (Second Embodiment)
The intermediate 10 of the cell structure 100 according to the second embodiment will be described with reference to FIGS. 5, 6a and 6b. The present embodiment is different from the first embodiment in that the pre-impregnated liquid is dropped from both the anode layer 2 side and the electrolyte layer 3 side. The same elements as those in the first embodiment are designated by the same reference numerals, and the description thereof will be omitted.

本実施形態のセル構造体１００の製造方法においても、積層工程（インク調製工程（Ｓ１０）、塗工工程（Ｓ２０）、貼り合わせ工程（Ｓ３０））、焼成工程（Ｓ４０）、プレ含浸工程（Ｓ５０）、含浸工程（Ｓ６０）、カソード積層工程（Ｓ７０）が含まれる。積層工程（Ｓ１０〜Ｓ３０）、焼成工程（Ｓ４０）、含浸工程（Ｓ６０）、カソード積層工程（Ｓ７０）については、第１実施形態と同様であるため、説明を省略する。 Also in the method for producing the cell structure 100 of the present embodiment, a laminating step (ink preparation step (S10), coating step (S20), laminating step (S30)), firing step (S40), pre-impregnation step (S50). ), Impregnation step (S60), and cathode lamination step (S70). Since the laminating step (S10 to S30), the firing step (S40), the impregnation step (S60), and the cathode laminating step (S70) are the same as those in the first embodiment, the description thereof will be omitted.

図５は、第２実施形態によるセル構造体１００の製造方法におけるプレ含浸工程を説明するフローチャートである。図６ａは、中間体１０のアノード層２の側からプレ含浸液を滴下した図であり、図６ｂは、中間体１０の電解質層３の側からのプレ含浸液を滴下した図である。 FIG. 5 is a flowchart illustrating a pre-impregnation step in the method for manufacturing the cell structure 100 according to the second embodiment. FIG. 6a is a diagram in which the pre-impregnated liquid is dropped from the side of the anode layer 2 of the intermediate 10, and FIG. 6b is a diagram in which the pre-impregnated liquid is dropped from the side of the electrolyte layer 3 of the intermediate 10.

図５に示す通り、プレ含浸工程において、まずプレ含浸液を作製する（Ｓ５１１）。本実施形態では、２種のプレ含浸液を作製する。第１のプレ含浸液は、非導電性セラミックスのジルコニア（硝酸ジルコニウム（II）二水和物（ＺｒＯ（ＮＯ₃）₂・２Ｈ₂Ｏ））にイットリウム（硝酸イットリウム（III）六水和物（Ｙ（ＮＯ₃）₃・６Ｈ₂Ｏ））を加えたものに、エタノール等を含む界面活性剤及び水を混合して作成する。第２のプレ含浸液は、非導電性セラミックスのセリア（硝酸セリウム（III）六水和物（Ｃｅ（ＮＯ₃）₃・６Ｈ₂Ｏ））、エタノール等を含む界面活性剤及び水を混合したものに、ガドリニウム（硝酸ガドリニウム（III）六水和物（Ｇｄ（ＮＯ₃）₃・６Ｈ₂Ｏ））を加えて作製する。第１実施形態と同様に、プレ含浸液は、表面張力が、含浸工程（図２のＳ６０）において含浸する触媒溶液の表面張力よりも小さくなるように、界面活性剤の量を調整する。なお、好ましくは、プレ含浸液作製後に、エタノールで中間体１０を洗浄し、真空引きによりエタノール・油分を飛ばす。 As shown in FIG. 5, in the pre-impregnation step, a pre-impregnation liquid is first prepared (S511). In this embodiment, two kinds of pre-impregnated liquids are prepared. First pre-impregnation liquid, zirconia nonconductive ceramic (zirconium (II) dihydrate _{_{(ZrO (NO 3) 2 ·}} 2H 2 O)) to yttrium (yttrium nitrate (III) hexahydrate ( Y (NO ₃₎ the ₃ · 6H ₂ O)) plus, is prepared by mixing a surfactant and water containing ethanol. Second pre-impregnation liquid, a non-conductive ceramic ceria (cerium (III) nitrate hexahydrate _{_{(Ce (NO 3) 3 ·}} 6H 2 O)), was mixed with surfactant and water containing ethanol, etc. things, gadolinium (gadolinium nitrate (III) hexahydrate _{_{(Gd (NO 3) 3 ·}} 6H 2 O)) is added to fabricated. Similar to the first embodiment, the amount of the surfactant of the pre-impregnated liquid is adjusted so that the surface tension of the pre-impregnated liquid is smaller than the surface tension of the catalyst solution to be impregnated in the impregnation step (S60 of FIG. 2). Preferably, after preparing the pre-impregnated liquid, the intermediate 10 is washed with ethanol, and ethanol and oil are removed by vacuuming.

次に、セル構造体１００の中間体１０を真空チャンバーに入れ、作製した第１のプレ含浸液を中間体１０に含浸する（Ｓ５１２）。図６ａに示すように、ここでは金属支持体１を介したアノード層２の側からジルコニアを含む第１のプレ含浸液を滴下する。これにより、第１のプレ含浸液は、多孔質の金属支持体１及びアノード層２を通り抜けて、電解質層３の欠陥部位６内に充填される。なお、アノード層がコーティングされるのを防止するため、第１のプレ含浸液の滴下量は、含浸工程（Ｓ６０）において含浸する触媒溶液の量よりも少なくする。 Next, the intermediate 10 of the cell structure 100 is placed in a vacuum chamber, and the prepared first pre-impregnated liquid is impregnated into the intermediate 10 (S512). As shown in FIG. 6a, here, the first pre-impregnated liquid containing zirconia is dropped from the side of the anode layer 2 via the metal support 1. As a result, the first pre-impregnated liquid passes through the porous metal support 1 and the anode layer 2 and is filled in the defective portion 6 of the electrolyte layer 3. In order to prevent the anode layer from being coated, the amount of the first pre-impregnated liquid dropped is smaller than the amount of the catalyst solution impregnated in the impregnation step (S60).

続いて真空チャンバー内で真空引き（Ｓ５１３）を行う。真空引きは、好ましくは複数回（例えば３〜４回程度）行う。 Subsequently, evacuation (S513) is performed in the vacuum chamber. Evacuation is preferably performed a plurality of times (for example, about 3 to 4 times).

次に、真空チャンバー内で中間体１０を乾燥させ、か焼する（Ｓ５１４）。これにより
、図６ａに示すように、電解質層３の欠陥部位６内に第１のプレ含浸液による電解質補強部７’が形成される。 Next, the intermediate 10 is dried and calcinated in the vacuum chamber (S514). As a result, as shown in FIG. 6a, the electrolyte reinforcing portion 7'by the first pre-impregnated liquid is formed in the defective portion 6 of the electrolyte layer 3.

次に、セル構造体１００の中間体１０を反転させ、作製した第２のプレ含浸液を中間体１０に含浸する（Ｓ５１５）。図６ｂに示すように、ここでは電解質層３の側からセリアを含む第２のプレ含浸液を滴下する。これにより、第２のプレ含浸液は、電解質層３の欠陥部位６内に充填される。なお、アノード層がコーティングされるのを防止するため、第２のプレ含浸液の滴下量は、含浸工程（Ｓ６０）において含浸する触媒溶液の量よりも少なくする。 Next, the intermediate 10 of the cell structure 100 is inverted, and the prepared second pre-impregnated liquid is impregnated into the intermediate 10 (S515). As shown in FIG. 6b, here, the second pre-impregnated liquid containing ceria is dropped from the side of the electrolyte layer 3. As a result, the second pre-impregnated liquid is filled in the defective portion 6 of the electrolyte layer 3. In order to prevent the anode layer from being coated, the amount of the second pre-impregnated liquid dropped is smaller than the amount of the catalyst solution impregnated in the impregnation step (S60).

続いて真空チャンバー内で真空引き（Ｓ５１６）を行う。真空引きは、好ましくは複数回（例えば３〜４回程度）行う。 Subsequently, evacuation (S516) is performed in the vacuum chamber. Evacuation is preferably performed a plurality of times (for example, about 3 to 4 times).

次に、真空チャンバー内で中間体１０を乾燥させ、か焼する（Ｓ５１７）。これにより
、図６ｂに示すように、電解質層３の欠陥部位６内に第２のプレ含浸液による電解質補強部７’’が形成される。 Next, the intermediate 10 is dried and calcinated in the vacuum chamber (S517). As a result, as shown in FIG. 6b, the electrolyte reinforcing portion 7'' by the second pre-impregnated liquid is formed in the defective portion 6 of the electrolyte layer 3.

このように、アノード層２の側と、電解質層３の側との両方の側からプレ含浸液を滴下することで、電解質層３に生じた一方の側から滴下しただけでは充填されないような隙間（欠陥部位６）も、確実に充填することができる。即ち、電解質補強部７’，７’’により、電解質層３の欠陥部位６を確実に閉塞することができる。 In this way, by dropping the pre-impregnated liquid from both the anode layer 2 side and the electrolyte layer 3 side, a gap that is not filled only by dropping from one side generated in the electrolyte layer 3 (Defect site 6) can also be reliably filled. That is, the electrolyte reinforcing portions 7 ″ and 7 ″ can reliably close the defective portion 6 of the electrolyte layer 3.

また、アノード層２の側から絶縁性の高いジルコニアを含む第１のプレ含浸液を滴下して電解質補強部７’を形成するため、アノード層２から電解質層３への電気的絶縁性がより補強される。一方、電解質層３の側からは、電解質材料に用いられるジルコニアよりも高い酸素イオン伝導度を有するセリアを含む第２のプレ含浸液を滴下して電解質補強部７’’を形成するため、電解質補強部７’’におけるオーム抵抗が低減し、電解質補強部７’’におけるイオン伝導性が向上する。即ち、アノード層２の側からジルコニアを含む第１のプレ含浸液を滴下し、電解質層３の側からセリアを含む第２のプレ含浸液を滴下して電解質補強部７’，７’’を形成することで、セル構造体１００の触媒反応が促進され、セル構造体１００の発電性能が向上する。 Further, since the first pre-impregnated liquid containing zirconia having high insulating properties is dropped from the anode layer 2 side to form the electrolyte reinforcing portion 7', the electrical insulating property from the anode layer 2 to the electrolyte layer 3 is improved. It will be reinforced. On the other hand, from the side of the electrolyte layer 3, a second pre-impregnated liquid containing ceria having higher oxygen ion conductivity than zirconia used for the electrolyte material is dropped to form the electrolyte reinforcing portion 7'', so that the electrolyte is formed. The ohm resistance in the reinforcing portion 7'' is reduced, and the ionic conductivity in the electrolyte reinforcing portion 7'' is improved. That is, the first pre-impregnated liquid containing zirconia is dropped from the anode layer 2 side, and the second pre-impregnated liquid containing ceria is dropped from the electrolyte layer 3 side to form the electrolyte reinforcing portions 7', 7''. By forming the cell structure 100, the catalytic reaction of the cell structure 100 is promoted, and the power generation performance of the cell structure 100 is improved.

上記した第２実施形態のセル構造体１００及びセル構造体１００の製造方法によれば、以下の効果を得ることができる。 According to the cell structure 100 and the method for manufacturing the cell structure 100 of the second embodiment described above, the following effects can be obtained.

セル構造体１００の製造方法によれば、プレ含浸工程において、アノード層２の側と電解質層３の側の両方の側からセル構造体１００の中間体１０にプレ含浸液を含浸させて、電解質層３の欠陥部位６内にセル性能を高める電解質補強部７’，７’’を形成する。このように、中間体１０の両側からプレ含浸液を含浸させることにより、電解質層３に生じた一方の側から含浸させただけでは充填されないような隙間（欠陥部位６）も、プレ含浸液で確実に充填することができる。従って、電解質層３の欠陥部位６内に、電解質補強部７’，７’’を確実に形成させることができ、電解質層３の欠陥部位６を確実に閉塞することができる。 According to the method for producing the cell structure 100, in the pre-impregnation step, the intermediate 10 of the cell structure 100 is impregnated with the pre-impregnated liquid from both the anode layer 2 side and the electrolyte layer 3 side to impregnate the electrolyte. Electrolyte reinforcing portions 7', 7'that enhance cell performance are formed in the defective portion 6 of the layer 3. In this way, by impregnating the pre-impregnated liquid from both sides of the intermediate 10, gaps (defect sites 6) that are not filled only by impregnating the electrolyte layer 3 from one side are also formed by the pre-impregnated liquid. It can be reliably filled. Therefore, the electrolyte reinforcing portions 7 ″ and 7 ″ can be reliably formed in the defective portion 6 of the electrolyte layer 3, and the defective portion 6 of the electrolyte layer 3 can be reliably closed.

セル構造体１００の製造方法によれば、プレ含浸工程において、セル構造体１００の中間体１０の一方の側からプレ含浸液を滴下した後、中間体１０を反転させて中間体１０の他方の側からプレ含浸液を滴下して電解質層３の欠陥部位６内に電解質補強部７’，７’’を形成する。このように、中間体１０の両側からプレ含浸液を滴下することにより、一方の側から滴下しただけでは充填されないような電解質層３の隙間（欠陥部位６）も、プレ含浸液で確実に充填することができる。従って、電解質層３の欠陥部位６内に、電解質補強部７’，７’’を確実に形成させることができ、電解質層３の欠陥部位６を確実に閉塞することができる。 According to the method for producing the cell structure 100, in the pre-impregnation step, after dropping the pre-impregnated liquid from one side of the intermediate 10 of the cell structure 100, the intermediate 10 is inverted and the other of the intermediate 10 is inverted. The pre-impregnated liquid is dropped from the side to form the electrolyte reinforcing portions 7 ′ and 7 ″ in the defective portion 6 of the electrolyte layer 3. By dropping the pre-impregnated liquid from both sides of the intermediate 10 in this way, the gap (defective portion 6) of the electrolyte layer 3 that cannot be filled only by dropping from one side is surely filled with the pre-impregnated liquid. can do. Therefore, the electrolyte reinforcing portions 7 ″ and 7 ″ can be reliably formed in the defective portion 6 of the electrolyte layer 3, and the defective portion 6 of the electrolyte layer 3 can be reliably closed.

セル構造体１００の製造方法によれば、プレ含浸工程において、セル構造体１００の中間体１０にアノード層２の側からジルコニアを含有する第１のプレ含浸液を滴下して、電解質層３の欠陥部位６内に電解質補強部７’を形成する。また、電解質層３の側からセリアを含有する第２のプレ含浸液を滴下して、電解質層３の欠陥部位６内に電解質補強部７’’を形成する。これにより、アノード層２から電解質層３への電気的絶縁性がより補強されるとともに、電解質補強部７’’におけるイオン伝導性が向上する。従って、セル構造体１００の触媒反応が促進され、セル構造体１００の発電性能が向上する。即ち、中間体１０の両側からプレ含浸液を滴下することで、電解質補強部７’，７’’により電解質層３の欠陥部位６を確実に閉塞するとともに、セル構造体１００のセル性能をより向上させることができる。 According to the method for producing the cell structure 100, in the pre-impregnation step, the first pre-impregnation solution containing zirconia is dropped onto the intermediate 10 of the cell structure 100 from the side of the anode layer 2 to form the electrolyte layer 3. An electrolyte reinforcing portion 7'is formed in the defective portion 6. Further, a second pre-impregnated liquid containing ceria is dropped from the side of the electrolyte layer 3 to form an electrolyte reinforcing portion 7 ″ in the defective portion 6 of the electrolyte layer 3. As a result, the electrical insulation from the anode layer 2 to the electrolyte layer 3 is further reinforced, and the ionic conductivity in the electrolyte reinforcing portion 7 ″ is improved. Therefore, the catalytic reaction of the cell structure 100 is promoted, and the power generation performance of the cell structure 100 is improved. That is, by dropping the pre-impregnated liquid from both sides of the intermediate 10, the defective portion 6 of the electrolyte layer 3 is surely closed by the electrolyte reinforcing portions 7', 7'', and the cell performance of the cell structure 100 is further improved. Can be improved.

なお、本実施形態においては、第１のプレ含浸液にはジルコニアを、第２のプレ含浸液にはセリアを用いているがこれに限られない。例えば、第１のプレ含浸液は、ジルコニアと同様に絶縁性の高いアルミナ（硝酸アルミニウム（III）九水和物（Ａｌ（ＮＯ₃）₃・
９Ｈ₂Ｏ））を用い、これに界面活性剤及び水を混合して作製してもよい。また、第１のプレ含浸液及び第２のプレ含浸液を同様の材料により作製してもよい。 In the present embodiment, zirconia is used as the first pre-impregnated liquid and ceria is used as the second pre-impregnated liquid, but the present invention is not limited to this. For example, the first pre-impregnated solution contains alumina (aluminum nitrate (III) nine hydrate (Al (NO ₃ ) _{3), which has high insulating properties like zirconia.}
9H ₂ O)) may be used, and a surfactant and water may be mixed thereto to prepare the product. Further, the first pre-impregnated liquid and the second pre-impregnated liquid may be prepared from the same material.

また、本実施形態においては、アノード層２の側から第１のプレ含浸液を滴下した後、電解質層３の側から第２のプレ含浸液を滴下しているが、滴下の順序はこれに限られず、電解質層３の側から先にプレ含浸液を滴下してもよい。 Further, in the present embodiment, the first pre-impregnated liquid is dropped from the anode layer 2 side, and then the second pre-impregnated liquid is dropped from the electrolyte layer 3 side. Not limited to this, the pre-impregnated liquid may be dropped from the side of the electrolyte layer 3 first.

また、本実施形態においては、第１のプレ含浸液の含浸（Ｓ５１２）後、真空引き（Ｓ５１３）、乾燥・か焼（Ｓ５１４）を行ってから第２のプレ含浸液の含浸（Ｓ５１５）を
行っているが、必ずしもこれに限られない。例えば、第１のプレ含浸液の含浸（Ｓ５１２）後、第２のプレ含浸液の含浸（Ｓ５１５）を行ってから真空引き（Ｓ５１３）、乾燥・か焼（Ｓ５１４）を行ってもよい。また、例えば、第１のプレ含浸液の含浸（Ｓ５１２）、真空引き（Ｓ５１３）、第２のプレ含浸液の含浸（Ｓ５１５）、真空引き（Ｓ５１６）、乾燥・か焼（Ｓ５１４，Ｓ５１７）の順に行ってもよい。 Further, in the present embodiment, after impregnation with the first pre-impregnated liquid (S512), vacuuming (S513), drying and calcination (S514) are performed, and then impregnation with the second pre-impregnated liquid (S515) is performed. I have done it, but it is not always limited to this. For example, after impregnation with the first pre-impregnated liquid (S512), impregnation with the second pre-impregnated liquid (S515) may be performed, followed by evacuation (S513) and drying / calcination (S514). Further, for example, impregnation of the first pre-impregnated liquid (S512), evacuation (S513), impregnation of the second pre-impregnated liquid (S515), evacuation (S516), drying / calcination (S514, S517). You may go in order.

また、いずれの実施形態においても、電解質層３の内部に導電パスが形成されることを防止するため、プレ含浸液は非導電性セラミックスにより作製することが好ましいが、必ずしもこれに限られず、プレ含浸液は、セル性能を高めるような物質を含むものであればよい。セル性能を高める物質により電解質補強部７を形成すれば、セル構造体１００（電解質層３）のリークパスの防止と、セル性能の向上という効果を同時に達成することができる。 Further, in any of the embodiments, the pre-impregnated liquid is preferably made of non-conductive ceramics in order to prevent the formation of a conductive path inside the electrolyte layer 3, but the pre-impregnation liquid is not necessarily limited to this. The impregnating liquid may contain a substance that enhances cell performance. If the electrolyte reinforcing portion 7 is formed of a substance that enhances the cell performance, the effects of preventing the leak path of the cell structure 100 (electrolyte layer 3) and improving the cell performance can be achieved at the same time.

また、いずれの実施形態においても、プレ含浸工程（Ｓ５０）においてプレ含浸液を作製しているが、これに限られず、プレ含浸液の作製はプレ含浸液の含浸前であればどのタイミングで作成してもよい。例えば、プレ含浸工程（Ｓ５０）に入る前に、予めプレ含浸液を作製しておき、プレ含浸工程（Ｓ５０）をプレ含浸液の含浸（Ｓ５０２，Ｓ５１２）から始めてもよい。 Further, in any of the embodiments, the pre-impregnated liquid is prepared in the pre-impregnated step (S50), but the present invention is not limited to this, and the pre-impregnated liquid is prepared at any timing before the pre-impregnated liquid is impregnated. You may. For example, the pre-impregnation liquid may be prepared in advance before entering the pre-impregnation step (S50), and the pre-impregnation step (S50) may be started from the impregnation of the pre-impregnation liquid (S502, S512).

また、いずれの実施形態においても、欠陥部位６内にプレ含浸液が確実に充填されるように、プレ含浸工程において、プレ含浸液を中間体１０に滴下することが好ましいが、プレ含浸液の含浸方法は必ずしもこれに限られず、既知の含浸方法のいずれの方法を用いてもよい。 Further, in any of the embodiments, it is preferable to drop the pre-impregnated liquid onto the intermediate 10 in the pre-impregnated step so that the defective portion 6 is surely filled with the pre-impregnated liquid. The impregnation method is not necessarily limited to this, and any known impregnation method may be used.

また、いずれの実施形態においても、プレ含浸液が欠陥部位６内に充填され易く、触媒溶液が欠陥部位６内に充填され難くするために、プレ含浸液は、表面張力が触媒溶液の表面張力よりも小さくなるように調製することが好ましいが、必ずしもこれに限られない。例えばプレ含浸液と触媒溶液の表面張力をほぼ同等にしてもよい。 Further, in any of the embodiments, the surface tension of the pre-impregnated liquid is the surface tension of the catalyst solution so that the pre-impregnated liquid is easily filled in the defective portion 6 and the catalyst solution is difficult to be filled in the defective portion 6. It is preferable, but not necessarily limited to, to be prepared to be smaller than. For example, the surface tensions of the pre-impregnated solution and the catalyst solution may be substantially the same.

また、いずれの実施形態においても、アノード層がコーティングされるのを防止するため、プレ含浸液の滴下量は、含浸工程（Ｓ６０）において含浸する触媒溶液の量よりも少なくすることが好ましいが、必ずしもこれに限られず、任意の量を滴下してもよい。 Further, in any of the embodiments, in order to prevent the anode layer from being coated, the amount of the pre-impregnated liquid dropped is preferably smaller than the amount of the catalyst solution impregnated in the impregnation step (S60). Not necessarily limited to this, an arbitrary amount may be dropped.

また、いずれの実施形態においても、セル構造体１００の中間体１０は、金属支持体１、アノード触媒層２、電解質層３の順に積層されているが、積層順はこれに限らない。例えば、金属支持体１、電解質層３、アノード触媒層２の順に積層してもよい。 Further, in any of the embodiments, the intermediate 10 of the cell structure 100 is laminated in the order of the metal support 1, the anode catalyst layer 2, and the electrolyte layer 3, but the stacking order is not limited to this. For example, the metal support 1, the electrolyte layer 3, and the anode catalyst layer 2 may be laminated in this order.

また、いずれの実施形態においても、プレ含浸液の滴下（Ｓ５０２，Ｓ５１２，Ｓ５１５）、真空引き（Ｓ５０３，Ｓ５１３，Ｓ５１６）、乾燥・か焼（Ｓ５０４，Ｓ５１４，
Ｓ５１７）は真空チャンバー内で行っているが、これに限られない。例えばプレ含浸液の滴下や乾燥・か焼を真空チャンバー外で行ってもよい。 Further, in any of the embodiments, the pre-impregnated liquid is dropped (S502, S512, S515), evacuated (S503, S513, S516), and dried / calcinated (S504, S514).
S517) is performed in a vacuum chamber, but is not limited to this. For example, the pre-impregnated liquid may be dropped or dried / calcinated outside the vacuum chamber.

以上、本発明の実施形態について説明したが、上記実施形態は本発明の適用例の一部を示したに過ぎず、本発明の技術的範囲を上記実施形態の具体的構成に限定する趣旨ではない。 Although the embodiments of the present invention have been described above, the above embodiments are only a part of the application examples of the present invention, and the technical scope of the present invention is limited to the specific configurations of the above embodiments. Absent.

また、上記した各実施形態は、それぞれ単独の実施形態として説明したが、適宜組み合わせてもよい。 Moreover, although each of the above-described embodiments has been described as a single embodiment, they may be combined as appropriate.

１金属支持体
２アノード層
３固体酸化物型電解質層
６欠陥部位
７電解質補強部
８カソード層
１０中間体
１００セル構造体 1 Metal support 2 Anode layer 3 Solid oxide type electrolyte layer 6 Defect site 7 Electrolyte reinforcement 8 Cathode layer 10 Intermediate 100 Cell structure

Claims

It is an intermediate of the cell structure
It is made by laminating a metal support, an anode layer, and a solid oxide type electrolyte layer.
An electrolyte reinforcing portion for enhancing cell performance was formed in the defective portion of the solid oxide type electrolyte layer.
Intermediate of cell structure.

An intermediate of the cell structure according to claim 1.
The electrolyte reinforcing portion is made of non-conductive ceramics.
Intermediate of cell structure.

An intermediate of the cell structure according to claim 2.
The ceramics contain ceria or zirconia,
Intermediate of cell structure.

A cell structure produced from an intermediate of the cell structure according to any one of claims 1 to 3.
The cell structure is composed of a metal support, an anode layer, a solid oxide type electrolyte layer, and a cathode layer laminated.
An electrolyte reinforcing portion for enhancing cell performance was formed in the defective portion of the solid oxide type electrolyte layer.
Cell structure.

A method for manufacturing a cell structure in which a metal support, an anode layer, a solid oxide type electrolyte layer, and a cathode layer are laminated.
The step of laminating the metal support, the anode layer, and the solid oxide type electrolyte layer, and
A step of firing the laminated metal support, the anode layer, and the solid oxide type electrolyte layer, and
A pre-impregnation step of impregnating an intermediate of the cell structure with a pre-impregnation liquid to form an electrolyte reinforcing portion for enhancing cell performance in a defective portion of the solid oxide type electrolyte layer.
An impregnation step of impregnating the anode layer with a catalyst solution and
It has a step of laminating the cathode layer.
A method for manufacturing a cell structure.

The method for manufacturing a cell structure according to claim 5.
In the pre-impregnation step, the pre-impregnation liquid is dropped onto the intermediate of the cell structure to form the electrolyte reinforcing portion.
A method for manufacturing a cell structure.

The method for producing a cell structure according to claim 5 or 6.
The pre-impregnated liquid is made of non-conductive ceramics.
A method for manufacturing a cell structure.

The method for manufacturing a cell structure according to claim 7.
The pre-impregnated liquid contains ceria or zirconia.
A method for manufacturing a cell structure.

The method for manufacturing a cell structure according to any one of claims 5 to 8.
In the pre-impregnation step, the pre-impregnation liquid is dropped from the anode layer side onto the intermediate of the cell structure to form the electrolyte reinforcing portion.
A method for manufacturing a cell structure.

The method for manufacturing a cell structure according to any one of claims 5 to 8.
In the pre-impregnation step, the pre-impregnation liquid is dropped from the electrolyte layer side onto the intermediate of the cell structure to form the electrolyte reinforcing portion.
A method for manufacturing a cell structure.

The method for manufacturing a cell structure according to any one of claims 5 to 7.
In the pre-impregnation step, the intermediate of the cell structure is impregnated with the pre-impregnation liquid from both the anode layer side and the electrolyte layer side to form the electrolyte reinforcing portion.
A method for manufacturing a cell structure.

The method for manufacturing a cell structure according to claim 11.
In the pre-impregnation step, after dropping the pre-impregnated liquid from one side of the intermediate of the cell structure, the intermediate is inverted and the pre-impregnated liquid is dropped from the other side of the intermediate to drop the electrolyte. Form a reinforcement,
A method for manufacturing a cell structure.

The method for producing a cell structure according to claim 11 or 12.
In the pre-impregnation step, the pre-impregnated liquid containing zirconia is dropped from the anode layer side to the intermediate of the cell structure, and the pre-impregnated liquid containing ceria is dropped from the electrolyte layer side to the electrolyte reinforcing portion. Form,
A method for manufacturing a cell structure.

The method for manufacturing a cell structure according to any one of claims 5 to 13.
The amount of the pre-impregnated liquid dropped is smaller than the amount of the catalyst solution impregnated in the anode layer in the impregnation step.
A method for manufacturing a cell structure.

The method for manufacturing a cell structure according to any one of claims 5 to 14.
The surface tension of the pre-impregnated solution is smaller than the surface tension of the catalytic solution.
A method for manufacturing a cell structure.