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JP5273584B2 - Solid oxide fuel cell, solid oxide fuel cell unit, and fuel cell module including the same - Google Patents

Solid oxide fuel cell, solid oxide fuel cell unit, and fuel cell module including the same Download PDF

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JP5273584B2
JP5273584B2 JP2008174397A JP2008174397A JP5273584B2 JP 5273584 B2 JP5273584 B2 JP 5273584B2 JP 2008174397 A JP2008174397 A JP 2008174397A JP 2008174397 A JP2008174397 A JP 2008174397A JP 5273584 B2 JP5273584 B2 JP 5273584B2
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fuel cell
current collector
solid oxide
oxide fuel
air electrode
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JP2010015807A (en
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泰之 新美
晃 川上
大 籾山
修一郎 西願
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

<P>PROBLEM TO BE SOLVED: To eliminate a fault that the power generation performance in initial stage is low owing to insufficient adhesion between a current collection member and an air electrode. <P>SOLUTION: A solid oxide fuel cell is manufactured by a manufacturing process wherein a first solution containing Ag/Pd alloy is applied to a solid oxide fuel cell, then a second solution containing Ag/Pd alloy in which quantity of Ag is more than that of the first solution is applied, and finally calcination is carried out. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

本発明は、固体酸化物形燃料電池セルと固体酸化物形燃料電池セルユニット、及びそれを備える燃料電池モジュールに関する。   The present invention relates to a solid oxide fuel cell, a solid oxide fuel cell unit, and a fuel cell module including the same.

従来から、管状の燃料電池セルを有する燃料電池セルが知られている（例えば、特許文献１参照）。まず、特許文献１に記載された従来の固体酸化物形燃料電池セルの一例を説明する。特許文献１に記載された固体酸化物形燃料電池セルユニットは、空気極に銀ペーストが塗布されている。銀は、空気に露出している。   Conventionally, a fuel battery cell having a tubular fuel battery cell is known (see, for example, Patent Document 1). First, an example of a conventional solid oxide fuel cell described in Patent Document 1 will be described. In the solid oxide fuel cell unit described in Patent Document 1, a silver paste is applied to the air electrode. Silver is exposed to the air.

また、特許文献２には、平板状の固体酸化物形燃料電池セルが記載され、この固体酸化物形燃料電池セルの内側の空気極集電体は、セパレーターと空気極に挟まれている。空気極集電体は、銀の多孔質体、表面に酸化物層を形成した銀の多孔質体、銀の素地中に酸化物が分散した分散強化形銀の多孔質体、または銀よりも高温強度の優れた合金の多孔質体の少なくとも片面に銀メッキした多孔質体の何れかからなる固体酸化物形燃料電池の空気極集電体である。   Patent Document 2 describes a flat solid oxide fuel cell, and an air electrode current collector inside the solid oxide fuel cell is sandwiched between a separator and an air electrode. The air electrode current collector is a silver porous body, a silver porous body having an oxide layer formed on its surface, a dispersion-strengthened silver porous body in which an oxide is dispersed in a silver substrate, or a silver porous body. This is an air electrode current collector of a solid oxide fuel cell comprising any one of a porous body of silver alloy plated on at least one surface of a porous body of an alloy having excellent high temperature strength.

また、特許文献３には、扁平状の固体酸化物形燃料電池セルが記載され、この固体酸化物形燃料電池セルの酸素極は、Ag又はAgを含有する合金が分散された導電性セラミックスからなっている。
特開２００７−９５４４２号公報 特許３９２４７７２号公報 特開２００６−１００００７号公報 Patent Document 3 describes a flat solid oxide fuel cell, and the oxygen electrode of the solid oxide fuel cell is made of conductive ceramics in which Ag or an Ag-containing alloy is dispersed. It has become.
JP 2007-95442 A Japanese Patent No. 3924772 JP 2006-100007 A

特許文献１〜３にあるように集電部にAgやAg/Pd合金を用いることが知られていた。しかし、集電部としての機能は良いが、空気極に対して集電部が密着する性能が不十分であり、密着性を向上した集電部が望まれていた。   As described in Patent Documents 1 to 3, it has been known to use Ag or an Ag / Pd alloy for the current collector. However, although the function as a current collector is good, the performance of the current collector closely contacting the air electrode is insufficient, and a current collector with improved adhesion has been desired.

そこで本発明者らは、集電部が空気極と密着性が確保でき、かつ発電性能が良好な固体酸化物形燃料電池セルを提供するために検討を行なった。   Therefore, the present inventors have studied in order to provide a solid oxide fuel cell in which the current collecting part can ensure adhesion with the air electrode and has good power generation performance.

上記課題を解決するために本発明に係る固体酸化物形燃料電池セルは、固体酸化物形燃料電池セルにAg/Pd合金を含む第一溶液を適用し、次に第一溶液よりもAg量が多いAg/Pd合金を含む第二溶液を適用し、焼成することを特徴とする固体酸化物形燃料電池セルを提供する。   In order to solve the above-mentioned problem, a solid oxide fuel cell according to the present invention applies a first solution containing an Ag / Pd alloy to a solid oxide fuel cell, and then the amount of Ag is higher than that of the first solution. A solid oxide fuel cell characterized by applying a second solution containing a large amount of Ag / Pd alloy and firing it.

本発明によれば、集電部と空気極の密着性が良好な固体酸化物形燃料電池セルと固体酸化物形燃料電池セルユニット、及びそれを備える燃料電池モジュールを提供可能となる。   ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide a solid oxide fuel cell unit and a solid oxide fuel cell unit having good adhesion between the current collector and the air electrode, and a fuel cell module including the same.

本発明を実施するための最良の形態を説明するに先立って、本発明の作用効果について説明する。   Before describing the best mode for carrying out the present invention, the function and effect of the present invention will be described.

更に、本発明に係る固体酸化物形燃料電池セルは、燃料極と、前記燃料極に配置される電解質と、前記電解質に配置される空気極と、を備える固体酸化物形燃料電池セルであって、前記空気極に配置される集電部を備え、前記集電部はAg/Pd合金であり、前記Ag/PdのAg割合が前記集電部の表側の方が高いことを特徴とする固体酸化物形燃料電池セルを提供する。   Furthermore, a solid oxide fuel cell according to the present invention is a solid oxide fuel cell comprising a fuel electrode, an electrolyte disposed on the fuel electrode, and an air electrode disposed on the electrolyte. A current collector disposed on the air electrode, the current collector is an Ag / Pd alloy, and the Ag ratio of the Ag / Pd is higher on the front side of the current collector. A solid oxide fuel cell is provided.

本発明によれば、集電部はAg/Pd合金であり、Ag/PdのAg割合が前記集電部の表側の方が高い。従って、集電部と空気極の密着性を確保でき、抵抗の低いAgの割合が表層に多くあるため、電気を流す通り道が表層に確保でき発電性能が良好である固体酸化物形燃料電池セルを提供することができる。   According to the present invention, the current collector is an Ag / Pd alloy, and the Ag ratio of Ag / Pd is higher on the front side of the current collector. Therefore, the adhesion between the current collector and the air electrode can be ensured, and since the ratio of Ag with low resistance is large in the surface layer, a solid oxide fuel cell having good power generation performance with a passage for electricity to be secured in the surface layer Can be provided.

更に、本発明に係る固体酸化物形燃料電池セルは、燃料極と、前記燃料極に配置される電解質と、前記電解質に配置される空気極と、を備える固体酸化物形燃料電池セルであって、前記空気極に配置される集電部を備え、前記集電部はAg/Pd合金であり、また表側にはPdが露出せず、Agのみが露出していることを特徴とする固体酸化物形燃料電池セルを提供する。   Furthermore, a solid oxide fuel cell according to the present invention is a solid oxide fuel cell comprising a fuel electrode, an electrolyte disposed on the fuel electrode, and an air electrode disposed on the electrolyte. And a current collector disposed on the air electrode, wherein the current collector is an Ag / Pd alloy, and Pd is not exposed on the front side, and only Ag is exposed. An oxide fuel cell is provided.

本発明によれば、空気極側の集電部はAg/Pd合金であり、表側にはPdが露出せず、Agのみが露出している。従って、集電部と空気極の密着性を確保でき、Ag/Pd合金より抵抗の低いAgが露出しているため、Ag/Pd合金に比べAgにより多くの電気が流れ、発電性能が良好である固体酸化物形燃料電池セルを提供することができる。   According to the present invention, the current collector on the air electrode side is an Ag / Pd alloy, and Pd is not exposed on the front side, and only Ag is exposed. Therefore, the adhesion between the current collector and the air electrode can be ensured, and Ag with lower resistance than the Ag / Pd alloy is exposed, so more electricity flows through Ag compared to the Ag / Pd alloy, and the power generation performance is good. A certain solid oxide fuel cell can be provided.

更に、本発明に係る固体酸化物形燃料電池セルユニットは、空気極に配置される集電部を備え、集電部はAg/Pd合金であり、Ag/PdのAg割合が集電部の表側の方が高いことを特徴とする固体酸化物形燃料電池セルと、空気極に配置される集電部と、集電部と電気的に接続され、固体酸化物形燃料電池セルの軸方向から電流を取り出すための端子と、を備えることを特徴とする固体酸化物形燃料電池セルユニットを提供する。本発明によれば、集電部にAg/Pd合金を用いた固体酸化物形燃料電池セルユニットを提供するので、集電部と空気極の密着性を確保し、かつ発電性能が良好である固体酸化物形燃料電池セルユニットを提供することができる。     Furthermore, the solid oxide fuel cell unit according to the present invention includes a current collector disposed in the air electrode, the current collector is an Ag / Pd alloy, and the Ag ratio of Ag / Pd is that of the current collector. Solid oxide fuel cell characterized in that the front side is higher, a current collector disposed in the air electrode, and an axial direction of the solid oxide fuel cell electrically connected to the current collector A solid oxide fuel cell unit, comprising: a terminal for taking out a current from the terminal; According to the present invention, since the solid oxide fuel cell unit using an Ag / Pd alloy for the current collector is provided, the adhesion between the current collector and the air electrode is ensured, and the power generation performance is good. A solid oxide fuel cell unit can be provided.

更に、本発明の一形態は、固体酸化物形燃料電池セルユニットを備えた燃料電池モジュールを提供する。本発明によれば、固体酸化物形燃料電池セルユニットの集電部にAg/Pd合金を用いた燃料電池モジュールを提供するので、集電部と空気極の密着性を確保し、かつ発電性能が良好である燃料電池モジュールを提供することができる。     Furthermore, one form of this invention provides the fuel cell module provided with the solid oxide fuel cell unit. According to the present invention, since the fuel cell module using the Ag / Pd alloy is provided for the current collector of the solid oxide fuel cell unit, the adhesion between the current collector and the air electrode is ensured, and the power generation performance It is possible to provide a fuel cell module that is excellent in.

更に、本発明の一形態は、空気極に配置される集電部を備え、集電部はAg/Pd合金であり、Ag/PdのAg割合が集電部の表側の方が高いことを特徴とする固体酸化物形燃料電池セルを備えた燃料電池モジュールを提供する。本発明によれば、固体酸化物形燃料電池セルの集電部にAg/Pd合金を用いた燃料電池モジュールを提供するので、集電部と空気極の密着性を確保し、かつ発電性能が良好である燃料電池モジュールを提供することができる。   Furthermore, one aspect of the present invention is provided with a current collector disposed on the air electrode, the current collector is an Ag / Pd alloy, and the Ag ratio of Ag / Pd is higher on the front side of the current collector. Provided is a fuel cell module including the solid oxide fuel cell. According to the present invention, since the fuel cell module using the Ag / Pd alloy is provided for the current collector of the solid oxide fuel cell, the adhesion between the current collector and the air electrode is ensured, and the power generation performance is improved. A fuel cell module that is good can be provided.

以下、添付図面を参照しながら本発明の好適な実施の形態について説明する。説明の理解を容易にするため、各図面において同一の構成要素に対しては可能な限り同一の符号を付して、重複する説明は省略する。 DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described with reference to the accompanying drawings. In order to facilitate the understanding of the description, the same constituent elements in the drawings will be denoted by the same reference numerals as much as possible, and redundant description will be omitted.

まず、図１を参照して、本発明による固体酸化物形燃料電池セルユニットの実施形態を説明する。図１は、本実施形態に係る固体酸化物形燃料電池セルユニットの断面図である。   First, an embodiment of a solid oxide fuel cell unit according to the present invention will be described with reference to FIG. FIG. 1 is a cross-sectional view of a solid oxide fuel cell unit according to this embodiment.

図１に示すように、本実施形態に係る固体酸化物形燃料電池セルユニット１は、１本の管状の固体酸化物形燃料電池セルを有している。本実施形態では、固体酸化物形燃料電池セルは、１本の固体酸化物形燃料電池セル６（管状体）からなり、固体酸化物形燃料電池セル６は、円筒形である。   As shown in FIG. 1, the solid oxide fuel cell unit 1 according to this embodiment has one tubular solid oxide fuel cell. In the present embodiment, the solid oxide fuel cell is composed of one solid oxide fuel cell 6 (tubular body), and the solid oxide fuel cell 6 is cylindrical.

固体酸化物形燃料電池セル６は、酸化剤ガスにさらされている面から集電部４４a、空気極２０、電解質１８、燃料極１６の積層構造になっており、燃料極１６の内側に構成される燃料ガスの通路となる貫通流路１５を有している。集電部４４aは固体酸化物形燃料電池セル６の他方の端部６ｂに固定された空気極端子２６に接続されいる。空気極２０全体又は一部は、集電部４４aで覆われており、空気極で発生した電気は、集電部４４aのセルの軸方向に流れ、空気極端子２６から電気を取り出す。
なおセルの軸方向とは、貫通流路１５に流れる燃料ガスの方向と同一方向を示す。即ち、図中の矢印Aの方向を示す。 The solid oxide fuel cell 6 has a stacked structure of a current collector 44 a, an air electrode 20, an electrolyte 18, and a fuel electrode 16 from the surface exposed to the oxidant gas, and is configured inside the fuel electrode 16. It has a through flow passage 15 that serves as a passage for the fuel gas to be produced. The current collector 44 a is connected to the air electrode terminal 26 fixed to the other end 6 b of the solid oxide fuel cell 6. The whole or a part of the air electrode 20 is covered with a current collector 44 a, and electricity generated at the air electrode flows in the axial direction of the cell of the current collector 44 a and takes out electricity from the air electrode terminal 26.
The axial direction of the cell indicates the same direction as the direction of the fuel gas flowing through the through passage 15. That is, the direction of arrow A in the figure is shown.

一方、固体酸化物形燃料電池セル６の一方の端部６ａに固定された燃料極端子２４は、燃料極１６と接しており、燃料極１６で発生した電気を燃料極端子２４から取り出す。   On the other hand, the fuel electrode terminal 24 fixed to one end 6 a of the solid oxide fuel cell 6 is in contact with the fuel electrode 16, and electricity generated at the fuel electrode 16 is taken out from the fuel electrode terminal 24.

集電部４４ａは、導電性膜であって、より具体的には、AgとPdを備えている。集電部４４ａの厚さは、０．１〜５０μｍであることが好ましく、より好ましくは0．５〜３０μｍであることが好ましい。集電部４４ａは、空気極２０が薄くて電気を通しにくい場合や導電率の低い材料で構成されている場合に電気の通路として機能している。   The current collector 44a is a conductive film, and more specifically includes Ag and Pd. The thickness of the current collector 44a is preferably 0.1 to 50 μm, more preferably 0.5 to 30 μm. The current collector 44a functions as an electrical path when the air electrode 20 is thin and difficult to conduct electricity or when it is made of a material with low conductivity.

燃料極１６は、例えば、Ｎｉと、ＣａやＹ、Ｓｃ等の希土類元素から選ばれる少なくとも一種をドープしたジルコニアとの混合体、Ｎｉと、希土類元素から選ばれる少なくとも一種をドープしたセリアとの混合体、Ｎｉと、Ｓｒ、Ｍｇ、Ｃｏ、Ｆｅ、Ｃｕから選ばれる少なくとも一種をドープしたランタンガレートとの混合体、の少なくとも一種から形成される。   The fuel electrode 16 is, for example, a mixture of Ni and zirconia doped with at least one selected from rare earth elements such as Ca, Y, and Sc, and a mixture of Ni and ceria doped with at least one selected from rare earth elements. And a mixture of Ni and lanthanum gallate doped with at least one selected from Sr, Mg, Co, Fe, and Cu.

電解質１８は、例えば、Ｙ、Ｓｃ等の希土類元素から選ばれる少なくとも一種をドープしたジルコニア、希土類元素から選ばれる少なくとも一種をドープしたセリア、Ｓｒ、Ｍｇから選ばれる少なくとも一種をドープしたランタンガレート、の少なくとも一種から形成される。   The electrolyte 18 is, for example, zirconia doped with at least one selected from rare earth elements such as Y and Sc, ceria doped with at least one selected from rare earth elements, and lanthanum gallate doped with at least one selected from Sr and Mg. It is formed from at least one kind.

空気極２０は、例えば、Ｓｒ、Ｃａから選ばれる少なくとも一種をドープしたランタンマンガナイト、Ｓｒ、Ｃｏ、Ｎｉ、Ｃｕから選ばれる少なくとも一種をドープしたランタンフェライト、Ｓｒ、Ｆｅ、Ｎｉ、Ｃｕから選ばれる少なくとも一種をドープしたサマリウムコバルト、銀、などの少なくとも一種から形成される。燃料極１６の厚さは、例えば、１ｍｍであり、電解質１８の厚さは、例えば、３０μｍであり、空気極２０の厚さは、例えば、３０μｍである。   The air electrode 20 is selected from, for example, lanthanum manganite doped with at least one selected from Sr and Ca, lanthanum ferrite doped with at least one selected from Sr, Co, Ni, and Cu, Sr, Fe, Ni, and Cu. It is formed from at least one of samarium cobalt, silver, etc. doped with at least one. The thickness of the fuel electrode 16 is, for example, 1 mm, the thickness of the electrolyte 18 is, for example, 30 μm, and the thickness of the air electrode 20 is, for example, 30 μm.

固体酸化物形燃料電池セル６の一方の端部６ａに、燃料極１６が電解質１８及び空気極２０に対して突出した燃料極突出周面１６ａと、電解質１８が空気極２０に対して突出した電解質突出周面１８ａとが設けられ、燃料極突出周面１６ａ及び電解質突出周面１８ａは、固体酸化物形燃料電池セル６の外周面を構成している。固体酸化物形燃料電池セル６の他方の端部６ｂを含む残部の外周面は、空気極２０が集電部４４aで覆われている。本実施形態では、燃料極突出周面１６ａは、燃料極１６と電気的に通じる燃料極外周面２１でもある。   A fuel electrode protruding peripheral surface 16a in which the fuel electrode 16 protrudes from the electrolyte 18 and the air electrode 20 and an electrolyte 18 protrudes from the air electrode 20 at one end 6a of the solid oxide fuel cell 6. An electrolyte protruding peripheral surface 18 a is provided, and the fuel electrode protruding peripheral surface 16 a and the electrolyte protruding peripheral surface 18 a constitute an outer peripheral surface of the solid oxide fuel cell 6. The air electrode 20 is covered with a current collector 44 a on the remaining outer peripheral surface including the other end 6 b of the solid oxide fuel cell 6. In the present embodiment, the fuel electrode protruding peripheral surface 16 a is also the fuel electrode outer peripheral surface 21 that is in electrical communication with the fuel electrode 16.

燃料極端子２４は、燃料極外周面２１を全周にわたって外側から覆うように配置され且つそれと電気的に接続された本体部分２４ａと、固体酸化物形燃料電池セル６から遠ざかるように固体酸化物形燃料電池セル６の長手方向に延びる管状部分２４ｂとを有している。好ましくは、本体部分２４ａ及び管状部分２４ｂは、円筒形であり且つ同心に配置され、管状部分２４ｂの管径は、本体部分２４ａの管径よりも細い。本体部分２４ａ及び管状部分２４ｂは、貫通流路１５と連通し且つ外部と通じる接続流路２４ｃを有している。本体部分２４ａと管状部分２４ｂとの間の段部２４ｄは、燃料極１６の端面１６ｂと当接している。   The fuel electrode terminal 24 is disposed so as to cover the outer peripheral surface 21 of the fuel electrode from the outside over the entire circumference and is electrically connected to the main body portion 24 a, and the solid oxide so as to be away from the solid oxide fuel cell 6. The tubular fuel cell 6 has a tubular portion 24b extending in the longitudinal direction. Preferably, the body portion 24a and the tubular portion 24b are cylindrical and arranged concentrically, and the tube diameter of the tubular portion 24b is smaller than the tube diameter of the body portion 24a. The main body portion 24a and the tubular portion 24b have a connection channel 24c that communicates with the through channel 15 and communicates with the outside. A step portion 24 d between the main body portion 24 a and the tubular portion 24 b is in contact with the end face 16 b of the fuel electrode 16.

尚、本発明の一形態に用いる空気極端子２６は、空気極外周面２２を全周にわたって外側から覆うように配置され且つそれと電気的に接続された本体部分２６ａと、固体酸化物形燃料電池セル６から遠ざかるように固体酸化物形燃料電池セル６の長手方向に延びる管状部分２６ｂとを有している。好ましくは、本体部分２６ａ及び管状部分２６ｂは、円筒形であり且つ同心であり、管状部分２６ｂの管径は、本体部分２６ａの管径よりも細い。本体部分２６ａ及び管状部分２６ｂは、貫通流路１５と連通し且つ外部と通じる接続流路２６ｃを有している。本体部分２６ａと管状部分２６ｂとの間の段部２６ｄは、環状の絶縁部材２８を介して集電部４４a、空気極２０、電解質１８及び燃料極１６の端面１６ｃと当接している。   The air electrode terminal 26 used in one embodiment of the present invention is disposed so as to cover the outer peripheral surface 22 of the air electrode from the outside over the entire circumference and is electrically connected thereto, and a solid oxide fuel cell. The solid oxide fuel cell 6 has a tubular portion 26 b extending in the longitudinal direction so as to be away from the cell 6. Preferably, the body portion 26a and the tubular portion 26b are cylindrical and concentric, and the tube diameter of the tubular portion 26b is smaller than the tube diameter of the body portion 26a. The main body portion 26a and the tubular portion 26b have a connection channel 26c that communicates with the through channel 15 and communicates with the outside. A step portion 26 d between the main body portion 26 a and the tubular portion 26 b is in contact with the current collector 44 a, the air electrode 20, the electrolyte 18, and the end surface 16 c of the fuel electrode 16 via the annular insulating member 28.

燃料極端子２４及び空気極端子２６の管状部分２４ｂ、２６ｂは、好ましくは、それらの外輪郭断面形状が同一である。更に好ましくは、燃料極端子２４及び空気極端子２６の全体形状が同一である。燃料極端子２４及び空気極端子２６は、例えばAg、ステンレス鋼、ニッケル基合金、クロム基合金などの耐熱金属である。   The tubular portions 24b and 26b of the fuel electrode terminal 24 and the air electrode terminal 26 preferably have the same outer contour cross-sectional shape. More preferably, the fuel electrode terminal 24 and the air electrode terminal 26 have the same overall shape. The fuel electrode terminal 24 and the air electrode terminal 26 are heat-resistant metals such as Ag, stainless steel, nickel-base alloy, and chromium-base alloy.

燃料極端子２４と固体酸化物形燃料電池セル６、及び、空気極端子２６と燃料電池セル６とは、その全周にわたって導電性のシール材３２によってシールされ且つ固定されている。   The fuel electrode terminal 24 and the solid oxide fuel cell 6, and the air electrode terminal 26 and the fuel cell 6 are sealed and fixed by a conductive sealing material 32 over the entire circumference.

一方の端部６ａにおいて、燃料極突出周面１６ａ及び電解質突出周面１８ａは、固体酸化物形燃料電池セル６の全周にわたって延び、互いに長手方向Ａに隣接している。また、燃料極突出周面１６ａは、固体酸化物形燃料電池セル６の先端部６ｃに位置している。燃料極突出周面１６ａと電解質突出周面１８ａとの間の境界３４は、燃料極端子２４の本体部分２４ａの内部にあり、電解質突出周面１８と集電部突出周面４４との間の境界３６は、本体部分２４ａの外側に位置している。また、電解質突出周面１８ａは、燃料極突出周面１６ａに向かって薄肉となるテーパ部１８ｂを有している。   At one end 6a, the fuel electrode protruding peripheral surface 16a and the electrolyte protruding peripheral surface 18a extend over the entire circumference of the solid oxide fuel cell 6 and are adjacent to each other in the longitudinal direction A. Further, the fuel electrode protruding peripheral surface 16 a is located at the front end portion 6 c of the solid oxide fuel cell 6. A boundary 34 between the fuel electrode protruding peripheral surface 16a and the electrolyte protruding peripheral surface 18a is inside the main body portion 24a of the fuel electrode terminal 24, and between the electrolyte protruding peripheral surface 18 and the current collector protruding peripheral surface 44. The boundary 36 is located outside the main body portion 24a. The electrolyte projecting peripheral surface 18a has a tapered portion 18b that becomes thinner toward the fuel electrode projecting peripheral surface 16a.

一方の端部６ａにおいて、シール材３２は、燃料極突出周面１６ａ及び電解質突出周面１８ａに跨がって全周にわたって延び、燃料極端子２４の本体部分２４ａに充填され、電解質突出周面１８ａを介して空気極２０と間隔をおいている。また、他方の端部６ｂにおいて、シール材３２は、空気極突出周面２０ａの上を全周にわたって延び、空気極端子２６の本体部分２６ａと絶縁部材２８との間の空間に充填されている。シール材３２は、燃料極１６と作用するガスの領域、即ち、貫通流路１５及び接続流路２４ｃ、２６ｃと、空気極２０と作用するガスの領域とを仕切るように設けられている。シール材３２は、例えば、銀、銀とガラスの混合物、金、ニッケル、銅、チタンなどを含む各種ロウ材である。   At one end 6a, the sealing material 32 extends over the entire circumference across the fuel electrode protruding peripheral surface 16a and the electrolyte protruding peripheral surface 18a, and is filled in the main body portion 24a of the fuel electrode terminal 24. It is spaced from the air electrode 20 via 18a. At the other end 6b, the sealing material 32 extends over the entire circumference of the air electrode protruding peripheral surface 20a and fills the space between the main body portion 26a of the air electrode terminal 26 and the insulating member 28. . The sealing material 32 is provided so as to partition the gas region acting with the fuel electrode 16, that is, the gas flow region acting with the air electrode 20 from the through flow channel 15 and the connection flow channels 24 c and 26 c. The sealing material 32 is various brazing materials including, for example, silver, a mixture of silver and glass, gold, nickel, copper, and titanium.

ここで固体酸化物形燃料電池の作動原理を以下に記す。空気極側に酸化剤ガスを流し、燃料極側に燃料ガス（Ｈ2、ＣＯなど）を流すと酸化剤ガス中の酸素が、空気極と固体電解質との界面近傍で酸素イオンに変わり、この酸素イオンが固体電解質を通って燃料極に達する。そして燃料ガスと酸素イオンが反応して水および二酸化炭素になる。これらの反応は(1)、(2)および(3)式で表される。発生した電子は、空気極または燃料極へと移動し、端子に集電されるので、電流は管状セルの長軸方向を流れることになる。空気極と燃料極を外部回路で接続することによって、外部に電気を取り出すことが出来る。
H 2 ＋ O 2 - → H 2 O＋ 2 e - （1）
C O＋ O 2 - → C O 2 ＋ 2 e - （2）
1 / 2 O２ ＋ 2 e - → O 2 - （3） Here, the operation principle of the solid oxide fuel cell will be described. When oxidant gas is flowed to the air electrode side and fuel gas (H 2 , CO, etc.) is flowed to the fuel electrode side, oxygen in the oxidant gas changes to oxygen ions in the vicinity of the interface between the air electrode and the solid electrolyte. Oxygen ions pass through the solid electrolyte and reach the fuel electrode. The fuel gas and oxygen ions react to form water and carbon dioxide. These reactions are represented by the formulas (1), (2) and (3). The generated electrons move to the air electrode or the fuel electrode and are collected at the terminal, so that the current flows in the long axis direction of the tubular cell. By connecting the air electrode and the fuel electrode with an external circuit, electricity can be taken out to the outside.
H 2 + O 2- → H 2 O + 2 e-(1)
C O + O 2- → CO 2 + 2 e-(2)
1/2 O 2 + 2 e-→ O 2- (3)

より具体的には、図１において燃料極１６と作用するガス（燃料ガス）を、貫通流路１５及び接続流路２４ｃ、２６ｃに通す。また、空気極２０と作用するガス（酸化剤ガス）を、空気極２０の周りに流す。それにより、燃料電池セルユニット１が作動する。また、燃料極１６の電気をシール材３２及び燃料極端子２４を介して取出し、空気極２０の電気をシール材３２及び空気極端子２６を介して取出す。   More specifically, the gas (fuel gas) that acts on the fuel electrode 16 in FIG. 1 is passed through the through passage 15 and the connection passages 24c and 26c. In addition, a gas (oxidant gas) that acts on the air electrode 20 flows around the air electrode 20. Thereby, the fuel cell unit 1 operates. Further, the electricity of the fuel electrode 16 is taken out via the sealing material 32 and the fuel electrode terminal 24, and the electricity of the air electrode 20 is taken out via the sealing material 32 and the air electrode terminal 26.

図２は、固体酸化物形燃料電池セルユニットの変形例である。このセルユニット２はセル７と2つの端子からなっている。セルの構成は、内部に貫通流路を有する燃料極支持体の外側に配置された固体電解質と、該固体電解質の外側に配置された空気極とから構成され、空気極の更に外側には集電部が配置されたものである。固体酸化物形燃料電池セル７には一方の端部５６aと他方の端部５６ｂを備え、他方の端部５６ｂの内側に燃料極端子１０４、および外側に空気極端子１０６の2つの端子が設けられている。図３は、内側の燃料極端子１０４を示す。燃料極端子１０４は、燃料極の貫通流路に挿入され、燃料極と接する。燃料極端子１０４は、中心部に固体酸化物形燃料電池セル７との接触面積を増やすため略円筒形をしている。図４は、外側の空気極端子１０６を示す。空気極端子１０６は、空気極の外側に覆われた集電部１４４aと接する。空気極端子１０６は、中心部に固体酸化物形燃料電池セル７を挿入できるように略円筒形をしている。それぞれの端子は、Ag、ステンレス鋼、ニッケル基合金、クロム基合金などの耐熱金属からなり、金属の持つバネ力により端子とセルが固定される。図１の仕様と同様に空気極側に酸化剤ガスを流し、燃料極側に燃料ガス（Ｈ2、ＣＯなど）を流した時、空気極と燃料極で電気が発生し、それぞれの端子に集電されるので、電流は管状セルの長軸方向を流れることになる。 FIG. 2 is a modification of the solid oxide fuel cell unit. The cell unit 2 includes a cell 7 and two terminals. The cell is composed of a solid electrolyte disposed outside a fuel electrode support having a through-flow passage inside, and an air electrode disposed outside the solid electrolyte. The electric part is arranged. The solid oxide fuel cell 7 includes one end 56a and the other end 56b. The fuel electrode terminal 104 is provided on the inner side of the other end 56b, and the air electrode terminal 106 is provided on the outer side. It has been. FIG. 3 shows the inner fuel electrode terminal 104. The fuel electrode terminal 104 is inserted into the through-flow passage of the fuel electrode and is in contact with the fuel electrode. The fuel electrode terminal 104 has a substantially cylindrical shape in order to increase the contact area with the solid oxide fuel cell 7 at the center. FIG. 4 shows the outer cathode terminal 106. The air electrode terminal 106 is in contact with the current collector 144a covered outside the air electrode. The air electrode terminal 106 has a substantially cylindrical shape so that the solid oxide fuel cell 7 can be inserted into the center thereof. Each terminal is made of a heat-resistant metal such as Ag, stainless steel, nickel-base alloy, or chromium-base alloy, and the terminal and the cell are fixed by the spring force of the metal. As in the specification of FIG. 1, when an oxidant gas is flowed to the air electrode side and a fuel gas (H 2 , CO, etc.) is flowed to the fuel electrode side, electricity is generated at the air electrode and the fuel electrode, Since the current is collected, the current flows in the long axis direction of the tubular cell.

更に、図５は、別の変形例である固体酸化物形燃料電池セルユニット３である。セルの構成は、内部に貫通流路を有する燃料極支持体の外側に配置された固体電解質と、該固体電解質の外側に配置された空気極とから構成され、空気極の更に外側には集電部が配置されたものである。固体酸化物形燃料電池セル８には一方の端部６６aと他方の端部６６ｂをもち、一方の端部６６aには電解質が空気極に対して突出した電解質突出部２１４を備える。空気極端子２０６であるAgワイヤは、集電部２４４aの外周に巻きつけられ、固体酸化物形燃料電池セル８の中心付近に形成した。外周に巻きつける位置は、中心付近に限定されず、固体酸化物形燃料電池セル８の他方の端部６６ｂでも良い。燃料極端子２０４は、貫通流路の内径より大きな円筒状のAgメッシュを備えている。燃料極端子２０４は、固体酸化物形燃料電池セル８に一方の端部６６aから10〜100mmの深さまで挿入し、Agメッシュのバネ力により燃料極と接している。図１の仕様と同様に空気極側に酸化剤ガスを流し、燃料極側に燃料ガス（Ｈ2、ＣＯなど）を流した時、空気極と燃料極で電気が発生し、それぞれの端子に集電されるので、電流は管状セルの長軸方向を流れることになる。 FIG. 5 shows a solid oxide fuel cell unit 3 which is another modified example. The cell is composed of a solid electrolyte disposed outside a fuel electrode support having a through-flow passage inside, and an air electrode disposed outside the solid electrolyte. The electric part is arranged. The solid oxide fuel cell 8 has one end portion 66a and the other end portion 66b, and one end portion 66a includes an electrolyte protrusion 214 in which an electrolyte protrudes from the air electrode. The Ag wire that is the air electrode terminal 206 was wound around the outer periphery of the current collector 244 a and formed near the center of the solid oxide fuel cell 8. The position wound around the outer periphery is not limited to the vicinity of the center, and may be the other end 66b of the solid oxide fuel cell 8. The fuel electrode terminal 204 includes a cylindrical Ag mesh larger than the inner diameter of the through channel. The fuel electrode terminal 204 is inserted into the solid oxide fuel cell 8 to a depth of 10 to 100 mm from one end 66a, and is in contact with the fuel electrode by the spring force of Ag mesh. As in the specification of FIG. 1, when an oxidant gas is flowed to the air electrode side and a fuel gas (H 2 , CO, etc.) is flowed to the fuel electrode side, electricity is generated at the air electrode and the fuel electrode, Since the current is collected, the current flows in the long axis direction of the tubular cell.

これまで説明してきたのは固体酸化物形燃料電池セルユニットであるが、端子を除くと本発明の固体酸化物形燃料電池セルに相当する。   What has been described so far is the solid oxide fuel cell unit, which corresponds to the solid oxide fuel cell of the present invention except for the terminals.

また、これまで説明してきた固体酸化物形燃料電池セルユニットまたは固体酸化物形燃料電池セルの周囲を覆う断熱容器を備えた燃料電池モジュールに適用されても良い。   Moreover, you may apply to the fuel cell module provided with the heat insulation container which covers the circumference | surroundings of the solid oxide fuel cell unit or solid oxide fuel cell unit demonstrated so far.

また、これまで説明した固体酸化物形燃料電池セルは円筒形状であるが、本発明の実施形態は円筒形状に限定されず、扁平形状などに適用されても良い。   Moreover, although the solid oxide fuel cell described so far has a cylindrical shape, the embodiment of the present invention is not limited to the cylindrical shape, and may be applied to a flat shape or the like.

以下、実施例を挙げて、本発明をより具体的に説明する。
燃料極支持体の外側に配置された固体電解質と、該固体電解質の外側に配置された空気極とから構成され、空気極の更に外側には集電部が配置されたものである。以下に作製手順について示した。 Hereinafter, the present invention will be described more specifically with reference to examples.
It is composed of a solid electrolyte disposed outside the fuel electrode support and an air electrode disposed outside the solid electrolyte, and a current collector is disposed further outside the air electrode. The production procedure is shown below.

（実施例１）
N i O粉末と、(ZrO2)0.90(Y2O3)0.10(以下YSZと略称する)粉末の混合物を湿式混合法で作製後、熱処理、粉砕を行い燃料極支持体原料粉末を得た。NiO粉末とYSZ粉末の混合比は重量比で65/35とした。該粉末を押出し成形法によって円筒状成形体を作製した。成形体を900℃で熱処理して仮焼体とした。仮焼体の表面に、スラリーコート法により固体電解質を成形した。この支持体を1300℃で焼成した。次に、固体電解質の表面にスラリーコート法により空気極を形成し、1100℃で焼成した。なお、燃料極支持体は、焼成後の寸法で、外径10.4mm、肉厚1.5mm、有効セル長100mmとした。空気極の面積は、25.2cm2になるようにした。 Example 1
A mixture of NiO powder and (ZrO 2 ) 0.90 (Y 2 O 3 ) 0.10 (hereinafter abbreviated as YSZ) powder was prepared by a wet mixing method, followed by heat treatment and pulverization to obtain a fuel electrode support raw material powder . The mixing ratio of NiO powder and YSZ powder was 65/35 by weight. A cylindrical molded body was produced by extruding the powder. The molded body was heat treated at 900 ° C. to obtain a calcined body. A solid electrolyte was formed on the surface of the calcined body by a slurry coating method. The support was fired at 1300 ° C. Next, an air electrode was formed on the surface of the solid electrolyte by a slurry coating method and fired at 1100 ° C. The fuel electrode support had dimensions after firing, an outer diameter of 10.4 mm, a wall thickness of 1.5 mm, and an effective cell length of 100 mm. The area of the air electrode was 25.2 cm 2 .

表１に示すように空気極としてLa０．６Sr０．４Co０．２Fe０．８O3(略称：LSCF)を用い、その上に集電部を塗布した。
本実施例での集電部の溶液として、次に挙げる樹脂と溶剤と金属粉を備えている。樹脂としてアクリル樹脂を用い、溶剤としてα-テルピネオールを用い、金属粉としてAgおよびPdを用いた。表１に示す割合、すなわち第一溶液の金属粉としてAg90.0重量% 、Pd10.0重量%で秤量し、第一溶液が塗布された表面に塗布する第二溶液として、第一溶液に混合されている同種類の樹脂と溶剤、Ag99.5重量% とPd0.5重量%を秤量した。樹脂、溶剤、金属粉を調合したコーティング液は、混合攪拌した。尚、ここでいう金属粉の割合とは、集電部を100重量％としたときに含まれる金属粉（Ag、Pd）の割合を示す。
空気極上への集電部の形成方法としては、本発明における固体電解質の作製方法については、特に制限はなく、スラリーコート法、テープキャスティング法、ドクターブレード法、スクリーン印刷法、スピンコート法、スプレー法、フローコート法、ロールコート法ならびにこれらの併用など、既知の塗布手段を適宜採用することができる。
固体酸化物形燃料電池セルにスクリーン印刷法でコーティング液を塗布後、80℃30分乾燥し、室温にて冷却後700℃１時間焼成し、空気極の外側に集電部を形成した固体酸化物形燃料電池セルを得た。よって、集電部は、ＡｇとＰｄを備える合金となった。
なお、得られた集電部のAgとPdを含有する合金の割合は、このセル集電部表面または断面をEPMA分析により定量値を求めることができる。この割合は、後述する表１に示す割合と等しいものであった。即ち、第一溶液を塗布された箇所は、Ag90.0重量% 、Pd10.0重量%のAg／Pd合金になり、第二溶液を塗布された箇所は、Ag99.5重量% 、Pd0.5重量%のAg／Pd合金になった。 As shown in Table 1, La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (abbreviation: LSCF) was used as an air electrode, and a current collector was applied thereon.
As the solution of the current collector in this embodiment, the following resin, solvent and metal powder are provided. An acrylic resin was used as the resin, α-terpineol was used as the solvent, and Ag and Pd were used as the metal powder. The ratio shown in Table 1, that is, weighed 90.0 wt% Ag as metal powder of the first solution and 10.0 wt% Pd, and mixed with the first solution as the second solution to be applied to the surface on which the first solution was applied. The same type of resin and solvent, Ag 99.5 wt% and Pd 0.5 wt% were weighed. The coating liquid prepared by mixing the resin, solvent, and metal powder was mixed and stirred. In addition, the ratio of metal powder here shows the ratio of metal powder (Ag, Pd) contained when a current collection part is 100 weight%.
The method for forming the current collector on the air electrode is not particularly limited as to the method for producing the solid electrolyte in the present invention, and is a slurry coating method, a tape casting method, a doctor blade method, a screen printing method, a spin coating method, a spray. Known coating means such as a method, a flow coating method, a roll coating method, and a combination thereof can be appropriately employed.
After applying the coating solution to the solid oxide fuel cell by screen printing method, drying at 80 ° C for 30 minutes, cooling at room temperature and then firing at 700 ° C for 1 hour to form a current collector outside the air electrode A physical fuel cell was obtained. Therefore, the current collector was an alloy comprising Ag and Pd.
In addition, the ratio of the alloy containing Ag and Pd in the obtained current collecting part can be determined quantitatively by EPMA analysis of the surface or cross section of the cell current collecting part. This ratio was equal to the ratio shown in Table 1 described later. That is, the portion where the first solution was applied was an Ag / Pd alloy of Ag 90.0 wt% and Pd 10.0 wt%, and the portion where the second solution was applied was Ag 99.5 wt%, Pd 0.5 A weight percent Ag / Pd alloy was obtained.

（実施例２）
表１に示すように集電部の第一溶液 にAg90.0重量% 、Pd10.0重量%、集電部第二溶液にAg99.0重量%、 Pd1.0重量%、集電部第三溶液にAg99.5重量% 、Pd0.5重量%を用い、塗り回数を3回にした以外は、実施例１と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Example 2)
As shown in Table 1, Ag 90.0 wt% and Pd 10.0 wt% in the first solution of the current collector section, Ag 99.0 wt%, Pd 1.0 wt% in the second solution of the current collector section, current collector section 3rd A solid oxide fuel cell in which a current collector was disposed outside the air electrode in the same manner as in Example 1 except that Ag 99.5 wt% and Pd 0.5 wt% were used in the solution, and the number of coatings was three. I got a cell.

（実施例３）
表１に示すように集電部の第一溶液に Ag97.0重量%、 Pd3.0重量%、集電部第二溶液にAg99.0重量%、 Pd1.0重量%、集電部第三溶液にAg99.5重量% 、Pd0.5重量%を用い、塗り回数を3回にした以外は、実施例１と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Example 3)
As shown in Table 1, Ag 97.0% by weight, Pd 3.0% by weight in the first solution of the current collector, Ag 99.0% by weight, Pd 1.0% by weight in the second solution of the current collector, current collector 3rd A solid oxide fuel cell in which a current collector was disposed outside the air electrode in the same manner as in Example 1 except that Ag 99.5 wt% and Pd 0.5 wt% were used in the solution, and the number of coatings was three. I got a cell.

（比較例１）
表１に示すように集電部のAg100重量%溶液、集電部第二溶液にAg99.8重量% 、Pd0.2重量%を用いた以外は、実施例１と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Comparative Example 1)
As shown in Table 1, the outer side of the air electrode was the same as in Example 1 except that Ag 100 wt% solution in the current collector and Ag 99.8 wt% and Pd 0.2 wt% were used in the current collector second solution. Thus, a solid oxide fuel cell having a current collector disposed therein was obtained.

（比較例２）
表１に示すように集電部の第一溶液 にAg99.5重量% 、Pd0.5重量%、集電部第二溶液にAg90.0重量% 、Pd10.0重量%を用いた以外は、実施例１と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Comparative Example 2)
As shown in Table 1, except that Ag 99.5 wt% and Pd 0.5 wt% were used for the first solution of the current collector, and Ag 90.0 wt% and Pd 10.0 wt% were used for the current collector second solution. In the same manner as in Example 1, a solid oxide fuel cell having a current collector disposed outside the air electrode was obtained.

（比較例３）
表１に示すように集電部の第一溶液に Ag99.5重量%、 Pd0.5重量%、集電部第二溶液にAg99.0重量%、 Pd1.0重量%、集電部第三溶液にAg90.0重量% 、Pd10.0重量%を用いた以外は、実施例１と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Comparative Example 3)
As shown in Table 1, Ag 99.5 wt%, Pd 0.5 wt% in the current collector first solution, Ag 99.0 wt%, Pd 1.0 wt% in the current collector second solution, current collector third A solid oxide fuel cell in which a current collector was disposed outside the air electrode was obtained in the same manner as in Example 1 except that Ag 90.0 wt% and Pd 10.0 wt% were used in the solution.

次に表２に関する説明を行なう。 Next, Table 2 will be described.

（実施例４）
N i O粉末と、(ZrO2)0.90(Y2O3)0.10(以下YSZと略称する)粉末の混合物を湿式混合法で作製後、熱処理、粉砕を行い燃料極支持体原料粉末を得た。NiO粉末とYSZ粉末の混合比は重量比で65/35とした。該粉末を押出し成形法によって円筒状成形体を作製した。成形体を900℃で熱処理して仮焼体とした。仮焼体の表面に、スラリーコート法により固体電解質を成形した。この支持体を1300℃で焼成した。次に、固体電解質の表面にスラリーコート法により空気極を形成し、1100℃で焼成した。なお、燃料極支持体は、焼成後の寸法で、外径10.4mm、肉厚1.5mm、有効セル長100mmとした。空気極の面積は、25.2cm2になるようにした。 Example 4
A mixture of NiO powder and (ZrO 2 ) 0.90 (Y 2 O 3 ) 0.10 (hereinafter abbreviated as YSZ) powder was prepared by a wet mixing method, followed by heat treatment and pulverization to obtain a fuel electrode support raw material powder . The mixing ratio of NiO powder and YSZ powder was 65/35 by weight. A cylindrical molded body was produced by extruding the powder. The molded body was heat treated at 900 ° C. to obtain a calcined body. A solid electrolyte was formed on the surface of the calcined body by a slurry coating method. The support was fired at 1300 ° C. Next, an air electrode was formed on the surface of the solid electrolyte by a slurry coating method and fired at 1100 ° C. The fuel electrode support had dimensions after firing, an outer diameter of 10.4 mm, a wall thickness of 1.5 mm, and an effective cell length of 100 mm. The area of the air electrode was 25.2 cm 2 .

表２に示すように空気極としてLa０．６Sr０．４Co０．２Fe０．８O3(略称：LSCF)を用い、その上に集電部を塗布した。
本実施例での集電部の溶液として、次に挙げる樹脂と溶剤と金属粉を備えている。
樹脂としてアクリル樹脂を用い、溶剤としてα-テルピネオールを用い、金属粉としてAgおよびPdを用いた。表２に示す割合、すなわち第一溶液の金属粉としてAg99.8重量%、 Pd0.2重量%で秤量し、第一溶液の上に塗布する溶液としてAg100重量%溶液を準備し、第一溶液に混合されている同種類の樹脂と溶剤とAg100重量%を秤量した。樹脂、溶剤、金属粉を調合したコーティング液は、混合攪拌した。尚、ここでいう金属粉の割合とは、集電部を100重量％としたときに含まれる金属粉（Ag、Pd）の割合を示す。
空気極上への集電部の形成方法としては、スラリーコート法、テープキャスティング法、ドクターブレード法、スクリーン印刷法、スピンコート法、スプレー法、フローコート法、ロールコート法ならびにこれらの併用など、既知の塗布手段を適宜採用することができる。
固体酸化物形燃料電池セルにスクリーン印刷法でコーティング液を塗布後、８０℃３０分乾燥し、室温にて冷却後７００℃１時間焼成し、空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。
固体酸化物形燃料電池セルの空気極に第一溶液を塗布後、８０℃３０分乾燥し、室温にて冷却後、集電部Ag100重量%溶液を塗布し、８０℃３０分乾燥し、室温にて冷却後、７００℃１時間焼成し、空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。前記集電部は、AgとPdを備える合金である。前記集電部は、Ag/Pd合金であり、また表側にはPdが露出せず、Agのみが露出している固体酸化物形燃料電池セルを得た。
なお、得られた集電部のAgとPdを含有する合金の割合は、このセル集電部表面または断面をEPMA分析により定量値を求めることができる。この割合は、後述する表２に示す割合と等しいものであった。即ち、第一溶液を塗布された箇所は、Ag99.8重量% 、Pd0.2重量%のAg／Pd合金になり、Ag100重量%溶液を塗布された箇所は、Ag100重量%になった。 As shown in Table 2, La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (abbreviation: LSCF) was used as an air electrode, and a current collector was applied thereon.
As the solution of the current collector in this embodiment, the following resin, solvent and metal powder are provided.
An acrylic resin was used as the resin, α-terpineol was used as the solvent, and Ag and Pd were used as the metal powder. The ratio shown in Table 2, that is, weighed 99.8 wt% Ag and 0.2 wt% Pd as the metal powder of the first solution, and prepared a 100 wt% Ag solution as a solution to be applied on the first solution. The same kind of resin, solvent, and Ag 100% by weight mixed in the above were weighed. The coating liquid prepared by mixing the resin, solvent, and metal powder was mixed and stirred. In addition, the ratio of metal powder here shows the ratio of metal powder (Ag, Pd) contained when a current collection part is 100 weight%.
Known methods for forming the current collector on the air electrode include slurry coating, tape casting, doctor blade, screen printing, spin coating, spray coating, flow coating, roll coating, and combinations thereof. The application means can be appropriately employed.
After applying the coating liquid to the solid oxide fuel cell by screen printing method, drying at 80 ° C for 30 minutes, cooling at room temperature and baking at 700 ° C for 1 hour, solid oxidation with the current collector located outside the air electrode A physical fuel cell was obtained.
After applying the first solution to the air electrode of the solid oxide fuel cell, drying at 80 ° C. for 30 minutes, cooling at room temperature, applying the 100% by weight Ag collector solution, drying at 80 ° C. for 30 minutes, and room temperature After cooling at 700 ° C., firing was performed at 700 ° C. for 1 hour to obtain a solid oxide fuel cell having a current collector disposed outside the air electrode. The current collector is an alloy including Ag and Pd. The current collector was an Ag / Pd alloy, and Pd was not exposed on the front side, and a solid oxide fuel cell with only Ag exposed was obtained.
In addition, the ratio of the alloy containing Ag and Pd in the obtained current collecting part can be determined quantitatively by EPMA analysis of the surface or cross section of the cell current collecting part. This ratio was equal to the ratio shown in Table 2 described later. That is, the portion where the first solution was applied was an Ag / Pd alloy of Ag 99.8 wt% and Pd 0.2 wt%, and the portion where the Ag 100 wt% solution was applied was Ag 100 wt%.

（実施例５）
表２に示すように集電部の第一溶液をAg99.5重量% 、Pd0.5重量%にした以外は、実施例４と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Example 5)
As shown in Table 2, solid oxidation in which the current collector was disposed outside the air electrode in the same manner as in Example 4 except that the first solution of the current collector was Ag 99.5 wt% and Pd 0.5 wt%. A physical fuel cell was obtained.

（実施例６）
表２に示すように集電部の第一溶液をAg99.0重量% 、Pd1.0重量%にした以外は、実施例４と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Example 6)
As shown in Table 2, solid oxidation in which the current collector was placed outside the air electrode in the same manner as in Example 4 except that the first solution in the current collector was Ag 99.0 wt% and Pd 1.0 wt%. A physical fuel cell was obtained.

（実施例７）
表２に示すように集電部の第一溶液をAg98.5重量% 、Pd1.5重量%にした以外は、実施例４と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Example 7)
As shown in Table 2, solid oxidation in which the current collector was disposed outside the air electrode in the same manner as in Example 4 except that the first solution in the current collector was Ag 98.5 wt% and Pd 1.5 wt%. A physical fuel cell was obtained.

（実施例８）
表２に示すように集電部の第一溶液をAg98.0重量% 、Pd2.0重量%にした以外は、実施例４と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Example 8)
As shown in Table 2, solid oxidation in which the current collector was disposed outside the air electrode in the same manner as in Example 4 except that the first solution in the current collector was Ag 98.0 wt% and Pd 2.0 wt%. A physical fuel cell was obtained.

（実施例９）
表２に示すように集電部の第一溶液をAg95.0重量% 、Pd5.0重量%にした以外は、実施例４と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 Example 9
As shown in Table 2, solid oxidation in which the current collector was placed outside the air electrode in the same manner as in Example 4 except that the first solution of the current collector was Ag 95.0 wt% and Pd 5.0 wt%. A physical fuel cell was obtained.

（比較例４）
表２に示すように集電部第一溶液をAg100重量%にした以外は、実施例４と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。即ち、Ag100重量％溶液を塗布した後に乾燥させ、再度Ag100重量％溶液を塗布した。 (Comparative Example 4)
As shown in Table 2, a solid oxide fuel cell having a current collector disposed outside the air electrode was obtained in the same manner as in Example 4 except that the current collector first solution was changed to 100% by weight of Ag. That is, the Ag 100 wt% solution was applied and then dried, and the Ag 100 wt% solution was applied again.

（比較例５）
表２に示すように集電部の第一溶液及び第二溶液をAg99.9重量%、 Pd0.1重量%にした以外は、実施例４と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。即ち、Ag99.9重量%、 Pd0.1重量%溶液を塗布した後に乾燥させ、再度Ag99.9重量%、 Pd0.1重量%溶液を塗布した。 (Comparative Example 5)
As shown in Table 2, the collector part was placed outside the air electrode in the same manner as in Example 4 except that the first and second solutions of the collector part were changed to Ag 99.9% by weight and Pd 0.1% by weight. An arranged solid oxide fuel cell was obtained. That is, after applying a 99.9 wt% Ag and 0.1 wt% Pd solution, the solution was dried and then again applied with an Ag99.9 wt% and Pd0.1 wt% solution.

（比較例６）
表２に示すように集電部の第一溶液及び第二溶液をAg90.0重量% 、Pd10.0 重量%にした以外は、実施例４と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。即ち、Ag90.0重量%、 Pd10.0重量%溶液を塗布した後に乾燥させ、再度Ag90.0重量%、 Pd10.0重量%溶液を塗布した。 (Comparative Example 6)
As shown in Table 2, the current collector was placed outside the air electrode in the same manner as in Example 4 except that the first solution and the second solution in the current collector were Ag 90.0 wt% and Pd 10.0 wt%. An arranged solid oxide fuel cell was obtained. That is, an Ag 90.0 wt% and Pd 10.0 wt% solution was applied and then dried, and an Ag 90.0 wt% and Pd 10.0 wt% solution was applied again.

次に表３に関する説明を行なう。 Next, Table 3 will be described.

（実施例１０）
N i O粉末と、(ZrO2)0.90(Y2O3)0.10(以下YSZと略称する)粉末の混合物を湿式混合法で作製後、熱処理、粉砕を行い燃料極支持体原料粉末を得た。NiO粉末とYSZ粉末の混合比は重量比で65/35とした。該粉末を押出し成形法によって円筒状成形体を作製した。成形体を900℃で熱処理して仮焼体とした。仮焼体の表面に、スラリーコート法により固体電解質を成形した。この支持体を1300℃で焼成した。次に、固体電解質の表面にスラリーコート法により空気極を形成し、1100℃で焼成した。なお、燃料極支持体は、焼成後の寸法で、外径10.4mm、肉厚1.5mm、有効セル長100mmとした。空気極の面積は、25.2cm2になるようにした。 (Example 10)
A mixture of NiO powder and (ZrO 2 ) 0.90 (Y 2 O 3 ) 0.10 (hereinafter abbreviated as YSZ) powder was prepared by a wet mixing method, followed by heat treatment and pulverization to obtain a fuel electrode support raw material powder . The mixing ratio of NiO powder and YSZ powder was 65/35 by weight. A cylindrical molded body was produced by extruding the powder. The molded body was heat treated at 900 ° C. to obtain a calcined body. A solid electrolyte was formed on the surface of the calcined body by a slurry coating method. The support was fired at 1300 ° C. Next, an air electrode was formed on the surface of the solid electrolyte by a slurry coating method and fired at 1100 ° C. The fuel electrode support had dimensions after firing, an outer diameter of 10.4 mm, a wall thickness of 1.5 mm, and an effective cell length of 100 mm. The area of the air electrode was 25.2 cm 2 .

表３に示すように空気極としてSm0.5Sr0.5CoO3 (略称：SSC)を用い、その上に集電部を塗布した。
本実施例での集電部の溶液として、次に挙げる樹脂と溶剤と金属粉を備えている。
樹脂としてアクリル樹脂を用い、溶剤としてα-テルピネオールを用い、金属粉としてAgおよびPdを用いた。表３に示す割合、すなわち第一溶液の金属粉としてAg90.0重量% 、Pd10.0重量%で秤量し、第一溶液の上に塗布する第二溶液として、第一溶液に混合されている同種類の樹脂と溶剤とAg99.5重量% とPd0.5重量%を秤量した。樹脂、溶剤、金属粉を調合したコーティング液は、混合攪拌した。尚、ここでいう金属粉の割合とは、集電部を100重量％としたときに含まれる金属粉（Ag、Pd）の割合を示す。
空気極上への集電部の形成方法としては、スラリーコート法、テープキャスティング法、ドクターブレード法、スクリーン印刷法、スピンコート法、スプレー法、フローコート法、ロールコート法ならびにこれらの併用など、既知の塗布手段を適宜採用することができる。
固体酸化物形燃料電池セルにスクリーン印刷法でコーティング液を塗布後、８０℃３０分乾燥し、室温にて冷却後７００℃１時間焼成し、空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。
固体酸化物形燃料電池セルの空気極に第一溶液を塗布後、８０℃３０分乾燥し、室温にて冷却後、第二溶液を塗布し、８０℃３０分乾燥し、室温にて冷却後、７００℃１時間焼成し、空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。集電部は、AgとPdを備える合金である。すなわち Ag/Pd合金であり、Ag/PdのAg割合が集電部の表側の方が高い固体酸化物形燃料電池セルを得た。
なお、得られた集電部のAgとPdを含有する合金の割合は、このセル集電部表面または断面をEPMA分析により定量値を求めることができる。この割合は、後述する表３に示す割合と等しいものであった。即ち、第一溶液を塗布された箇所は、Ag90.0重量% 、Pd10.0重量%のAg／Pd合金になり、第二溶液を塗布された箇所は、Ag99.5重量% 、Pd0.5重量%のAg／Pd合金になった。 As shown in Table 3, Sm 0.5 Sr 0.5 CoO 3 (abbreviation: SSC) was used as an air electrode, and a current collector was applied thereon.
As the solution of the current collector in this embodiment, the following resin, solvent and metal powder are provided.
An acrylic resin was used as the resin, α-terpineol was used as the solvent, and Ag and Pd were used as the metal powder. The ratio shown in Table 3, ie, 90.0 wt% Ag as the metal powder of the first solution and 10.0 wt% Pd, is weighed in the first solution as the second solution to be applied on the first solution. The same kind of resin, solvent, Ag 99.5 wt% and Pd 0.5 wt% were weighed. The coating liquid prepared by mixing the resin, solvent, and metal powder was mixed and stirred. In addition, the ratio of metal powder here shows the ratio of metal powder (Ag, Pd) contained when a current collection part is 100 weight%.
Known methods for forming the current collector on the air electrode include slurry coating, tape casting, doctor blade, screen printing, spin coating, spray coating, flow coating, roll coating, and combinations thereof. The application means can be appropriately employed.
After applying the coating liquid to the solid oxide fuel cell by screen printing method, drying at 80 ° C for 30 minutes, cooling at room temperature and baking at 700 ° C for 1 hour, solid oxidation with the current collector located outside the air electrode A physical fuel cell was obtained.
After applying the first solution to the air electrode of the solid oxide fuel cell, drying at 80 ° C. for 30 minutes, cooling at room temperature, applying the second solution, drying at 80 ° C. for 30 minutes, and cooling at room temperature Baked at 700 ° C. for 1 hour to obtain a solid oxide fuel cell having a current collector disposed outside the air electrode. The current collector is an alloy comprising Ag and Pd. That is, a solid oxide fuel cell was obtained which was an Ag / Pd alloy and had a higher Ag ratio of Ag / Pd on the front side of the current collector.
In addition, the ratio of the alloy containing Ag and Pd in the obtained current collecting part can be determined quantitatively by EPMA analysis of the surface or cross section of the cell current collecting part. This ratio was equal to the ratio shown in Table 3 described later. That is, the portion where the first solution was applied was an Ag / Pd alloy of Ag 90.0 wt% and Pd 10.0 wt%, and the portion where the second solution was applied was Ag 99.5 wt%, Pd 0.5 A weight percent Ag / Pd alloy was obtained.

（実施例１１）
表３に示すように集電部の第一溶液 にAg90.0重量% 、Pd10.0重量%、集電部第二溶液にAg99.0重量%、 Pd1.0重量%、集電部第三溶液にAg99.5重量% 、Pd0.5重量%を用い、塗り回数を3回にした以外は、実施例１０と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Example 11)
As shown in Table 3, Ag 90.0 wt% and Pd 10.0 wt% in the first solution of the current collector section, Ag 99.0 wt%, Pd 1.0 wt% in the second solution of the current collector section, current collector section 3 A solid oxide fuel cell in which a current collector was disposed outside the air electrode in the same manner as in Example 10 except that Ag 99.5 wt% and Pd 0.5 wt% were used for the solution, and the number of coatings was three. I got a cell.

（実施例１２）
表３に示すように集電部の第一溶液に Ag97.0重量%、 Pd3.0重量%、集電部第二溶液にAg99.0重量%、 Pd1.0重量%、集電部第三溶液にAg99.5重量% 、Pd0.5重量%を用い、塗り回数を3回にした以外は、実施例１０と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Example 12)
As shown in Table 3, Ag 97.0 wt%, Pd 3.0 wt% in the current collector first solution, Ag 99.0 wt%, Pd 1.0 wt% in the current collector second solution, current collector third A solid oxide fuel cell in which a current collector was disposed outside the air electrode in the same manner as in Example 10 except that Ag 99.5 wt% and Pd 0.5 wt% were used for the solution, and the number of coatings was three. I got a cell.

（比較例７）
表３に示すように集電部にAg100重量%溶液、集電部第二溶液にAg99.8重量% 、Pd0.2重量%を用いた以外は、実施例１０と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Comparative Example 7)
As shown in Table 3, the outer side of the air electrode was the same as in Example 10 except that Ag 100 wt% solution was used for the current collector and Ag 99.8 wt% and Pd 0.2 wt% were used for the current collector second solution. Thus, a solid oxide fuel cell having a current collector disposed therein was obtained.

次に表４に関する説明を行なう。 Next, Table 4 will be described.

（実施例１３）
N i O粉末と、(ZrO2)0.90(Y2O3)0.10(以下YSZと略称する)粉末の混合物を湿式混合法で作製後、熱処理、粉砕を行い燃料極支持体原料粉末を得た。NiO粉末とYSZ粉末の混合比は重量比で65/35とした。該粉末を押出し成形法によって円筒状成形体を作製した。成形体を900℃で熱処理して仮焼体とした。仮焼体の表面に、スラリーコート法により固体電解質を成形した。この支持体を1300℃で焼成した。次に、固体電解質の表面にスラリーコート法により空気極を形成し、1100℃で焼成した。なお、燃料極支持体は、焼成後の寸法で、外径10.4mm、肉厚1.5mm、有効セル長100mmとした。空気極の面積は、25.2cm2になるようにした。 (Example 13)
A mixture of NiO powder and (ZrO 2 ) 0.90 (Y 2 O 3 ) 0.10 (hereinafter abbreviated as YSZ) powder was prepared by a wet mixing method, followed by heat treatment and pulverization to obtain a fuel electrode support raw material powder . The mixing ratio of NiO powder and YSZ powder was 65/35 by weight. A cylindrical molded body was produced by extruding the powder. The molded body was heat treated at 900 ° C. to obtain a calcined body. A solid electrolyte was formed on the surface of the calcined body by a slurry coating method. The support was fired at 1300 ° C. Next, an air electrode was formed on the surface of the solid electrolyte by a slurry coating method and fired at 1100 ° C. The fuel electrode support had dimensions after firing, an outer diameter of 10.4 mm, a wall thickness of 1.5 mm, and an effective cell length of 100 mm. The area of the air electrode was 25.2 cm 2 .

表４に示すように空気極としてSm0.5Sr0.5CoO3 (略称：SSC)を用い、その上に集電部を塗布した。
本実施例での集電部の溶液として、次に挙げる樹脂と溶剤と金属粉を備えている。
樹脂としてアクリル樹脂を用い、溶剤としてα-テルピネオールを用い、金属粉としてAgおよびPdを用いた。表４に示す割合、すなわち第一溶液の金属粉としてAg99.8重量%、 Pd0.2重量%で秤量し、第一溶液の上に塗布する溶液としてAg100重量%溶液を準備し、第一溶液に混合されている同種類の樹脂と溶剤とAg100重量%を秤量した。樹脂、溶剤、金属粉を調合したコーティング液は、混合攪拌した。尚、ここでいう金属粉の割合とは、集電部を100重量％としたときに含まれる金属粉（Ag、Pd）の割合を示す。
空気極上への集電部の形成方法としては、スラリーコート法、テープキャスティング法、ドクターブレード法、スクリーン印刷法、スピンコート法、スプレー法、フローコート法、ロールコート法ならびにこれらの併用など、既知の塗布手段を適宜採用することができる。
固体酸化物形燃料電池セルにスクリーン印刷法でコーティング液を塗布後、８０℃３０分乾燥し、室温にて冷却後７００℃１時間焼成し、空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。
固体酸化物形燃料電池セルの空気極に第一溶液を塗布後、８０℃３０分乾燥し、室温にて冷却後、集電部Ag100重量%溶液を塗布し、８０℃３０分乾燥し、室温にて冷却後、７００℃１時間焼成し、空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。前記集電部は、AgとPdを備える合金である。前記集電部は、Ag/Pd合金であり、また表側にはPdが露出せず、Agのみが露出している固体酸化物形燃料電池セルを得た。
なお、得られた集電部のAgとPdを含有する合金の割合は、このセル集電部表面または断面をEPMA分析により定量値を求めることができる。この割合は、後述する表４に示す割合と等しいものであった。即ち、第一溶液を塗布された箇所は、Ag99.8重量% 、Pd0.2重量%のAg／Pd合金になり、Ag100重量%溶液を塗布された箇所は、Ag100重量%になった。 As shown in Table 4, Sm 0.5 Sr 0.5 CoO 3 (abbreviation: SSC) was used as an air electrode, and a current collector was applied thereon.
As the solution of the current collector in this embodiment, the following resin, solvent and metal powder are provided.
An acrylic resin was used as the resin, α-terpineol was used as the solvent, and Ag and Pd were used as the metal powder. The ratio shown in Table 4, ie, 99.8% by weight of Ag as the metal powder of the first solution and 0.2% by weight of Pd was weighed, and a 100% by weight Ag solution was prepared as a solution to be applied on the first solution. The same kind of resin, solvent, and Ag 100% by weight mixed in the above were weighed. The coating liquid prepared by mixing the resin, solvent, and metal powder was mixed and stirred. In addition, the ratio of metal powder here shows the ratio of metal powder (Ag, Pd) contained when a current collection part is 100 weight%.
Known methods for forming the current collector on the air electrode include slurry coating, tape casting, doctor blade, screen printing, spin coating, spray coating, flow coating, roll coating, and combinations thereof. The application means can be appropriately employed.
After applying the coating liquid to the solid oxide fuel cell by screen printing method, drying at 80 ° C for 30 minutes, cooling at room temperature and baking at 700 ° C for 1 hour, solid oxidation with the current collector located outside the air electrode A physical fuel cell was obtained.
After applying the first solution to the air electrode of the solid oxide fuel cell, drying at 80 ° C. for 30 minutes, cooling at room temperature, applying the 100% by weight Ag collector solution, drying at 80 ° C. for 30 minutes, and room temperature After cooling at 700 ° C., firing was performed at 700 ° C. for 1 hour to obtain a solid oxide fuel cell having a current collector disposed outside the air electrode. The current collector is an alloy including Ag and Pd. The current collector was an Ag / Pd alloy, and Pd was not exposed on the front side, and a solid oxide fuel cell with only Ag exposed was obtained.
In addition, the ratio of the alloy containing Ag and Pd in the obtained current collecting part can be determined quantitatively by EPMA analysis of the surface or cross section of the cell current collecting part. This ratio was equal to the ratio shown in Table 4 described later. That is, the portion where the first solution was applied was an Ag / Pd alloy of Ag 99.8 wt% and Pd 0.2 wt%, and the portion where the Ag 100 wt% solution was applied was Ag 100 wt%.

（実施例１４）
表４に示すように集電部の第一溶液をAg99.5重量% 、Pd0.5重量%にした以外は、実施例１３と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Example 14)
As shown in Table 4, solid oxidation in which the current collector was disposed outside the air electrode in the same manner as in Example 13 except that the first solution in the current collector was Ag 99.5 wt% and Pd 0.5 wt%. A physical fuel cell was obtained.

（実施例１５）
表４に示すように集電部の第一溶液をAg99.0重量% 、Pd1.0重量%にした以外は、実施例１３と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Example 15)
As shown in Table 4, solid oxidation in which the current collector was disposed outside the air electrode in the same manner as in Example 13 except that the first solution in the current collector was Ag 99.0 wt% and Pd 1.0 wt%. A physical fuel cell was obtained.

（実施例１６）
表４に示すように集電部の第一溶液をAg98.5重量% 、Pd1.5重量%にした以外は、実施例１３と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Example 16)
As shown in Table 4, solid oxidation in which the current collector was disposed outside the air electrode was performed in the same manner as in Example 13 except that the first solution in the current collector was Ag 98.5 wt% and Pd 1.5 wt%. A physical fuel cell was obtained.

（実施例１７）
表４に示すように集電部の第一溶液をAg98.0重量% 、Pd2.0重量%にした以外は、実施例１３と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Example 17)
As shown in Table 4, solid oxidation in which the current collector was disposed outside the air electrode in the same manner as in Example 13 except that the first solution in the current collector was Ag 98.0 wt% and Pd 2.0 wt%. A physical fuel cell was obtained.

（実施例１８）
表４に示すように集電部の第一溶液をAg95.0重量% 、Pd5.0重量%にした以外は、実施例１３と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。 (Example 18)
As shown in Table 4, solid oxidation in which the current collector was disposed outside the air electrode in the same manner as in Example 13 except that the first solution of the current collector was Ag 95.0 wt% and Pd 5.0 wt%. A physical fuel cell was obtained.

（比較例８）
表４に示すように集電部第一溶液をAg100重量%にした以外は、実施例１３と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。即ち、Ag100重量％溶液を塗布した後に乾燥させ、再度Ag100重量％溶液を塗布した。 (Comparative Example 8)
As shown in Table 4, a solid oxide fuel cell having a current collector disposed outside the air electrode was obtained in the same manner as in Example 13 except that the current collector first solution was changed to 100% by weight of Ag. That is, the Ag 100 wt% solution was applied and then dried, and the Ag 100 wt% solution was applied again.

（比較例９）
表４に示すように集電部の第一溶液及び第二溶液をAg99.9重量%、 Pd0.1重量%にした以外は、実施例１３と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。即ち、Ag99.9重量%、 Pd0.1重量%溶液を塗布した後に乾燥させ、再度Ag99.9重量%、 Pd0.1重量%溶液を塗布した。 (Comparative Example 9)
As shown in Table 4, the collector part was placed outside the air electrode in the same manner as in Example 13 except that the first solution and the second solution of the collector part were changed to Ag 99.9% by weight and Pd 0.1% by weight. An arranged solid oxide fuel cell was obtained. That is, after applying a 99.9 wt% Ag and 0.1 wt% Pd solution, the solution was dried and then again applied with an Ag99.9 wt% and Pd0.1 wt% solution.

（比較例１０）
表４に示すように集電部の第一溶液及び第二溶液をAg90.0重量% 、Pd10.0 重量%にした以外は、実施例１３と同様にして空気極の外側に集電部を配置した固体酸化物形燃料電池セルを得た。即ち、Ag90.0重量%、 Pd10.0重量%溶液を塗布した後に乾燥させ、再度Ag90.0重量%、 Pd10.0重量%溶液を塗布した。 (Comparative Example 10)
As shown in Table 4, the current collector was placed outside the air electrode in the same manner as in Example 13 except that the first solution and the second solution of the current collector were Ag 90.0 wt% and Pd 10.0 wt%. An arranged solid oxide fuel cell was obtained. That is, an Ag 90.0 wt% and Pd 10.0 wt% solution was applied and then dried, and an Ag 90.0 wt% and Pd 10.0 wt% solution was applied again.

（評価方法）
集電部の密着性試験
コーティング液を塗布し、焼成した後、固体酸化物形燃料電池セルの半周に市販のセロハンテープを気泡が入らないように貼り付け、剥離させた。その際に、セル表面に集電部が残っているか否かを目視で判定した。
2． 固体酸化物形燃料電池セルユニットの発電試験
得られた固体酸化物形燃料電池セルユニット(電極有効面積：25.2cm2 )を用いて発電試験を行った。燃料極側の集電は、図１に示す燃料極端子２４にAg線を外周に巻きつけ行った。空気極側の集電も、空気極端子２６にAg線を外周に巻きつけ行った。発電条件としては、燃料は（ H2 ＋ 3%H2O）とN2の混合ガスとした。燃料利用率は80%とした。酸化剤ガスは空気とした。測定温度は700℃ とし、電流密度0.2A/cm2での発電電位を測定した。
(Evaluation method)
After coating and baking the adhesion test coating solution for the current collector, a commercially available cellophane tape was applied to the half circumference of the solid oxide fuel cell so that no air bubbles would enter and peeled off. At that time, it was visually determined whether or not the current collector remained on the cell surface.
2． Power Generation Test of Solid Oxide Fuel Cell Unit A power generation test was performed using the obtained solid oxide fuel cell unit (electrode effective area: 25.2 cm 2). The current collection on the fuel electrode side was performed by winding an Ag wire around the fuel electrode terminal 24 shown in FIG. The air electrode side current collection was also performed by winding an Ag wire around the air electrode terminal 26 around the outer periphery. The power generation condition, the fuel was mixed gas (H 2 + 3% H 2 O) and N2. The fuel utilization rate was 80%. The oxidant gas was air. The power generation potential was measured at a measurement temperature of 700 ° C. and a current density of 0.2 A / cm 2.

表１〜４に本発明の実施例および比較例を示し、以下に説明する。 Tables 1 to 4 show examples and comparative examples of the present invention, which will be described below.

Figure 0005273584
Figure 0005273584

表１を用い、空気極にＬＳＣＦを用い、固体酸化物形燃料電池セルにAg/Pd合金を含む第一溶液を適用し、次に第一溶液よりもAg量が多いAg/Pd合金を含む第二溶液を適用し、焼成することを特徴とする固体酸化物形燃料電池セルについて説明する。より詳しくは、集電部はAg/Pd合金であり、前記Ag/PdのAg割合が前記集電部の表側の方が高い固体酸化物形燃料電池セルについて説明する。実施例１〜３は集電部と空気極の密着性評価が良好であった。それに対して、比較例１はAg100重量%溶液を用い、第二溶液にAgにPdを少量加えたAg99.8重量%、Pd0.2重量%を用いたが、空気極と集電部との密着性が確保できなかった。比較例２は第一溶液にAg99.5重量%、Pd0.5重量%溶液を用い、第二溶液にAgにPdを少量加えたAg90.0重量%、Pd10.0重量%を用いたが、空気極と集電部との密着性が確保できず、初期発電電位も低い値になった。比較例３は第一溶液にAg99.5重量%、Pd0.5重量%溶液を用い、第二溶液にAg99.0重量%、Pd1.0重量%を用い、第三溶液にAg90.0重量%、Pd10.0重量%を用いたが、空気極と集電部との密着性が確保できず、初期発電電位も低い値になった。 Using Table 1, using LSCF for the air electrode, applying a first solution containing an Ag / Pd alloy to the solid oxide fuel cell, and then containing an Ag / Pd alloy having a higher Ag content than the first solution A solid oxide fuel cell characterized by applying a second solution and firing will be described. More specifically, a description will be given of a solid oxide fuel cell in which the current collector is an Ag / Pd alloy and the Ag ratio of Ag / Pd is higher on the front side of the current collector. In Examples 1 to 3, adhesion evaluation between the current collector and the air electrode was good. In contrast, Comparative Example 1 used a 100 wt% Ag solution, and used 99.8 wt% Ag and 0.2 wt% Pd with a small amount of Pd added to Ag in the second solution. Adhesion could not be secured. In Comparative Example 2, Ag 99.5 wt% and Pd 0.5 wt% solution were used for the first solution, and Ag 90.0 wt% and Pd 10.0 wt% obtained by adding a small amount of Pd to Ag were used for the second solution. Adhesion between the air electrode and the current collector could not be ensured, and the initial power generation potential was low. Comparative Example 3 uses Ag 99.5 wt% and Pd 0.5 wt% solution for the first solution, Ag 99.0 wt% and Pd 1.0 wt% for the second solution, and Ag 90.0 wt% for the third solution. However, although Pd10.0% by weight was used, the adhesion between the air electrode and the current collector could not be secured, and the initial power generation potential was also low.

Figure 0005273584
Figure 0005273584

表２を用い、空気極がＬＳＣＦであり、固体酸化物形燃料電池セルにAg/Pd合金を含む第一溶液を適用し、次にAg100重量%である溶液を適用し、焼成する固体酸化物形燃料電池セルに関する。集電部はAg/Pd合金であり、また表側にはPdが露出せず、Agのみが露出している固体酸化物形燃料電池セルについて説明する。実施例４〜９は集電部と空気極の密着性評価が良好であり、初期発電電位を高くすることができた。それに対して比較例４は、空気極LSCFに配置する集電部にAg100重量%溶液を用いたところ、空気極と集電部との密着性が確保できなかった。比較例５は、第一溶液、第二溶液ともにAgにPd を少量加えたAg99.9重量%、Pd0.1重量%を用いたが、空気極と集電部との密着性が確保できなかった。比較例６は、第一溶液、第二溶液ともにAgに更に多くのPdを加えたAg90.0重量%、Pd10.0重量%を用いたところ、空気極と集電部との密着性は確保したが、セルの発電電位が低い結果となり燃料電池としての性能を満たさないものとなった。 Using Table 2, a solid oxide to be calcined by applying a first solution containing Ag / Pd alloy to a solid oxide fuel cell having an air electrode of LSCF and then applying a solution containing 100% by weight of Ag. The present invention relates to a fuel cell. A solid oxide fuel cell in which the current collector is an Ag / Pd alloy and Pd is not exposed on the front side and only Ag is exposed will be described. In Examples 4 to 9, the evaluation of adhesion between the current collector and the air electrode was good, and the initial power generation potential could be increased. On the other hand, in Comparative Example 4, when an Ag 100% by weight solution was used for the current collector disposed in the air electrode LSCF, the adhesion between the air electrode and the current collector could not be ensured. In Comparative Example 5, 99.9 wt% Ag and 0.1 wt% Pd with a small amount of Pd added to Ag were used for both the first solution and the second solution, but the adhesion between the air electrode and the current collector could not be secured. It was. In Comparative Example 6, the adhesion between the air electrode and the current collector was ensured when Ag 90.0 wt% and Pd 10.0 wt%, in which more Pd was added to Ag, were used for both the first solution and the second solution. However, as a result of the low power generation potential of the cell, the performance as a fuel cell was not satisfied.

Figure 0005273584
Figure 0005273584

表３を用い、空気極がＳＳＣであり、固体酸化物形燃料電池セルにAg/Pd合金を含む第一溶液を適用し、次に第一溶液よりもAg量が多いAg/Pd合金を含む第二溶液を適用し、焼成する固体酸化物形燃料電池セルについて説明する。より詳しくは、集電部はAg/Pd合金であり、前記Ag/PdのAg割合が前記集電部の表側の方が高い固体酸化物形燃料電池セルについて説明する。実施例１０〜１２は集電部と空気極の密着性評価が良好であった。それに対して比較例５は、比較例１と同様に集電部にAg100重量%溶液を用い、第二溶液にAgと少量のＰｄを加えたAg99.8重量%、Pd0.2重量%を用いたが、空気極と集電部との密着性が確保できなかった。 Using Table 3, the air electrode is SSC, the first solution containing the Ag / Pd alloy is applied to the solid oxide fuel cell, and then the Ag / Pd alloy having a higher Ag amount than the first solution is included. A solid oxide fuel cell that is fired by applying the second solution will be described. More specifically, a description will be given of a solid oxide fuel cell in which the current collector is an Ag / Pd alloy and the Ag ratio of Ag / Pd is higher on the front side of the current collector. In Examples 10 to 12, the evaluation of adhesion between the current collector and the air electrode was good. On the other hand, Comparative Example 5 uses Ag 100 wt% solution for the current collector as in Comparative Example 1, and uses 99.8 wt% Ag and 0.2 wt% Pd with Ag and a small amount of Pd added to the second solution. However, the adhesion between the air electrode and the current collector could not be secured.

Figure 0005273584
Figure 0005273584

表４を用い、空気極がＳＳＣであり、固体酸化物形燃料電池セルにAg/Pd合金を含む第一溶液を適用し、次にAg100重量%である溶液を適用し、焼成する固体酸化物形燃料電池セルに関して説明する。より詳しくは集電部はAg/Pd合金であり、また表側にはPdが露出せず、Agのみが露出している固体酸化物形燃料電池セルについて説明する。実施例１３〜１８は集電部と空気極の密着性評価が良好であった。それに対して比較例８は、比較例４と同様に溶液にAg100重量%を用いたところ空気極と集電部との密着性が確保できなかった。比較例９は、比較例５と同様に第一溶液、第二溶液ともにAg99.9重量%、Pd0.1重量%を用いたところ空気極と集電部との密着性が確保できなかった。比較例１０は、比較例６と同様に第一溶液、第二溶液ともにAg90.0重量%、Pd10.0重量%を用いたところ、空気極SSCと集電部の密着性が確保できたが、発電電位が低い結果となり、使用には適さない結果となった。 Using Table 4, the cathode is SSC, the first solution containing the Ag / Pd alloy is applied to the solid oxide fuel cell, and then the solution of 100% by weight of Ag is applied, followed by firing the solid oxide The fuel cell will be described. More specifically, a solid oxide fuel cell in which the current collector is an Ag / Pd alloy and Pd is not exposed on the front side and only Ag is exposed will be described. In Examples 13 to 18, the evaluation of adhesion between the current collector and the air electrode was good. On the other hand, in Comparative Example 8, as in Comparative Example 4, when 100% by weight of Ag was used in the solution, the adhesion between the air electrode and the current collector could not be ensured. In Comparative Example 9, as in Comparative Example 5, when 99.9% by weight of Ag and 0.1% by weight of Pd were used for both the first solution and the second solution, the adhesion between the air electrode and the current collector could not be ensured. In Comparative Example 10, as in Comparative Example 6, when using Ag 90.0 wt% and Pd 10.0 wt% for both the first solution and the second solution, the adhesion between the air electrode SSC and the current collector could be secured. As a result, the power generation potential was low, and the result was not suitable for use.

本実施形態に係る固体酸化物形燃料電池セルユニットを示す図である。It is a figure which shows the solid oxide fuel cell unit concerning this embodiment. 本実施形態に係る固体酸化物形燃料電池セルユニットの変形例を示す図である。It is a figure which shows the modification of the solid oxide fuel cell unit which concerns on this embodiment. 本実施形態に係る燃料極端子の変形例を示す図である。It is a figure which shows the modification of the fuel electrode terminal which concerns on this embodiment. 本実施形態に係る空気極端子の変形例を示す図である。It is a figure which shows the modification of the air electrode terminal which concerns on this embodiment. 本実施形態に係る固体酸化物形燃料電池セルユニットの変形例を示す図である。It is a figure which shows the modification of the solid oxide fuel cell unit which concerns on this embodiment.

符号の説明Explanation of symbols

１…燃料電池セルユニット、６…固体酸化物形燃料電池セル（固体酸化物形燃料電池セル体）、６ａ…一方の端部、６ｂ…他方の端部、１５…貫通流路、１６…燃料極、１６ａ…燃料極突出周面、１８…電解質、２０…空気極、２１…燃料極外周面、２２…空気極外周面、２４…燃料極端子、２４ｂ…管状部分、２４ｃ…接続流路、２６…空気極端子、２６ｂ…管状部分、２６ｃ…接続流路、３２…シール材、４４ａ…集電部、 ２…燃料電池セルユニット、７…固体酸化物形燃料電池セル、５６ａ…一方の端部、５６ｂ…他方の端部、１４４ａ…集電部、１０４…燃料極端子、１０６…空気極端子、 ３…燃料電池セルユニット、８…固体酸化物形燃料電池セル、６６ａ…一方の端部、６６ｂ…他方の端部、２４４ａ…集電部、２０４…燃料極端子、２０６…空気極端子、２１４…電解質突出部   DESCRIPTION OF SYMBOLS 1 ... Fuel cell unit, 6 ... Solid oxide fuel cell (solid oxide fuel cell body), 6a ... One end, 6b ... The other end, 15 ... Through flow path, 16 ... Fuel Electrode, 16a ... Fuel electrode protruding peripheral surface, 18 ... Electrolyte, 20 ... Air electrode, 21 ... Fuel electrode outer peripheral surface, 22 ... Air electrode outer peripheral surface, 24 ... Fuel electrode terminal, 24b ... Tubular portion, 24c ... Connection flow path, 26 ... Air electrode terminal, 26b ... Tubular portion, 26c ... Connection flow path, 32 ... Sealing material, 44a ... Current collector, 2 ... Fuel cell unit, 7 ... Solid oxide fuel cell, 56a ... One end , 56b ... the other end, 144a ... current collector, 104 ... fuel electrode terminal, 106 ... air electrode terminal, 3 ... fuel cell unit, 8 ... solid oxide fuel cell, 66a ... one end 66b ... the other end, 244a ... current collector, 204 ... fuel Electrode terminal, 206 ... Air electrode terminal, 214 ... Electrolyte protrusion

Claims (5)

燃料極と、
前記燃料極に配置される電解質と、
前記電解質に配置される空気極と、
を備える固体酸化物形燃料電池セルであって、
前記空気極に配置される集電部を備え、
前記集電部はAg/Pd合金であり、
前記Ag/PdのAg割合が前記集電部の表側の方が高いことを特徴とする固体酸化物形燃料電池セル。 An anode,
An electrolyte disposed in the fuel electrode;
An air electrode disposed in the electrolyte;
A solid oxide fuel cell comprising:
A current collector disposed on the air electrode;
The current collector is an Ag / Pd alloy,
A solid oxide fuel cell, wherein the Ag ratio of Ag / Pd is higher on the front side of the current collector. 燃料極と、
前記燃料極に配置される電解質と、
前記電解質に配置される空気極と、
を備える固体酸化物形燃料電池セルであって、
前記空気極に配置される集電部を備え、
前記集電部はAg/Pd合金であり、
また表側にはPdが露出せず、Agのみが露出していることを特徴とする固体酸化物形燃料電池セル。 An anode,
An electrolyte disposed in the fuel electrode;
An air electrode disposed in the electrolyte;
A solid oxide fuel cell comprising:
A current collector disposed on the air electrode;
The current collector is an Ag / Pd alloy,
Also, a solid oxide fuel cell characterized in that Pd is not exposed on the front side and only Ag is exposed. 請求項１又は２のいずれか1項に記載の固体酸化物形燃料電池セルと、
前記空気極に配置される集電部と、
前記集電部と電気的に接続され、
前記固体酸化物形燃料電池セルの軸方向から電流を取り出すための端子と、
を備えることを特徴とする固体酸化物形燃料電池セルユニット。 The solid oxide fuel cell according to any one of claims 1 and 2 ,
A current collector disposed in the air electrode;
Electrically connected to the current collector,
A terminal for extracting current from the axial direction of the solid oxide fuel cell;
A solid oxide fuel cell unit comprising: 請求項３に記載の固体酸化物形燃料電池セルユニットを備えた燃料電池モジュール。 A fuel cell module comprising the solid oxide fuel cell unit according to claim 3 . 請求項１又は２のいずれか1項に記載の固体酸化物形燃料電池セルを備えた燃料電池モジュール。 Fuel cell module comprising a solid oxide fuel cell according to any one of claims 1 or 2.
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