JP2006236820A - Solid oxide fuel cell and manufacturing method of solid oxide fuel cell - Google Patents

Solid oxide fuel cell and manufacturing method of solid oxide fuel cell Download PDF

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JP2006236820A
JP2006236820A JP2005050760A JP2005050760A JP2006236820A JP 2006236820 A JP2006236820 A JP 2006236820A JP 2005050760 A JP2005050760 A JP 2005050760A JP 2005050760 A JP2005050760 A JP 2005050760A JP 2006236820 A JP2006236820 A JP 2006236820A
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intermediate layer
air electrode
fuel cell
solid oxide
electrolyte layer
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JP4795701B2 (en
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Reiichi Chiba
玲一 千葉
Yoshitaka Tabata
嘉隆 田畑
Himeko Orui
姫子 大類
Takeshi Komatsu
武志 小松
Kazuhiko Nozawa
和彦 野沢
Masayasu Arakawa
正泰 荒川
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Nippon Telegraph and Telephone Corp
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid oxide fuel cell capable of preventing overvoltage of an air electrode from augmenting and a manufacturing method of a solid oxide fuel cell. <P>SOLUTION: Transition metal oxide contained in an intermediate layer 5 dissolves only slightly in a solid electrolyte in a solid state at an operating temperature of the SOFC in an oxidation atmosphere, but does not contain rare earth elements with large ionic radii such as La and Sr. Therefore, even if a high temperature heat treatment is applied to have it stably exist at an interface with zirconia, interdiffusion with the electrolyte 2 hardly occurs, and a non-conductive phase such as of pyrochroite is not generated. Thereby, it becomes possible to prevent increase of overvoltage of the air electrode 3 by providing the above intermediate layer 5. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、固体酸化物型燃料電池（ＳＯＦＣ：Solid Oxide Fuel Cell）に関するものである。   The present invention relates to a solid oxide fuel cell (SOFC).

近年、酸素イオン伝導体を用いたＳＯＦＣに関心が高まりつつある。このＳＯＦＣは、カルノー効率の制約を受けないために本質的に高いエネルギー変換効率を有するとともに、良好な環境保全が期待できるなどの優れた特徴を有する。このため、特に、エネルギーの有効利用という観点で各分野から期待されている。   In recent years, interest in SOFCs using oxygen ion conductors is increasing. This SOFC has excellent characteristics such as high energy conversion efficiency because it is not restricted by Carnot efficiency and good environmental conservation. For this reason, it is especially expected from each field from the viewpoint of effective use of energy.

従来のＳＯＦＣでは、動作温度が９００℃〜１０００℃と高いために全ての部材をセラミックで構成しなければならず、このためにセルスタックの製造コストを低減するのが困難であった。ＳＯＦＣの動作温度を８００℃以下、好ましくは７００℃程度まで低減することができれば、インターコネクタ等に耐熱合金材料を用いることが可能となるため、製造コストの低減が可能となる。ところが、動作温度を低下させると、空気極における電気化学的な抵抗が急激に増えるために過電圧が増大し、出力電圧の低下を招いてしまうという新たな問題を引き起こしてしまう。この空気極の過電圧の増大という問題を解決するために、空気極の微細化や新たな空気極材料の開発が行われている。中でも、空気極を構成している材料の粒径を小さくするという方法は、常に過電圧を低減することが可能となるため、最も有効な方法である。   In the conventional SOFC, since the operating temperature is as high as 900 ° C. to 1000 ° C., all members must be made of ceramic, and it is difficult to reduce the manufacturing cost of the cell stack. If the operating temperature of the SOFC can be reduced to 800 ° C. or less, preferably about 700 ° C., it becomes possible to use a heat-resistant alloy material for the interconnector and the like, so that the manufacturing cost can be reduced. However, when the operating temperature is lowered, the electrochemical resistance in the air electrode is rapidly increased, so that an overvoltage is increased, resulting in a new problem that the output voltage is lowered. In order to solve the problem of an increase in the overvoltage of the air electrode, miniaturization of the air electrode and development of a new air electrode material have been performed. Among them, the method of reducing the particle size of the material constituting the air electrode is the most effective method because it can always reduce the overvoltage.

なお、出願人は、本明細書に記載した先行技術文献情報で特定される先行技術文献以外には、本発明に関連する先行技術文献を出願時までに発見するには至らなかった。
W. A. Fischer and A. Hoffmann，Arch. Eisenhuettenwes.，vol.28[11]、P.739-743，1957年 The applicant has not yet found prior art documents related to the present invention by the time of filing other than the prior art documents specified by the prior art document information described in this specification.
WA Fischer and A. Hoffmann, Arch. Eisenhuettenwes., Vol.28 [11], P.739-743, 1957

ところで、一般に空気極は、電解質層上に空気極を構成する材料を塗布し焼成して電解質層上に焼き付けることにより形成されるが、このときの焼き付けを過度の高温で行うと、空気極内の粒子同士が合体して粒成長を起こすため、空気極の過電圧の増大を招いてしまう。特に、電解質としてジルコニア系の材料、空気極としてＬａ系の材料を用いる場合には、Ｌａなどイオン半径の大きな稀土類元素が電解質中へ拡散しやすいため、これによりＳｒＺｒＯ3やパイロクロア相（Ｌａ2Ｚｒ2Ｏ7）など電子伝導性やイオン導電性が極めて低い不活性な物質がジルコニアと空気極の界面に形成されるので、空気極の過電圧の増大を招いてしまう。一方、焼き付け温度が低すぎると、空気極の構成材料とジルコニアとの密着力が低下するため、空気極が電解質から剥がれやすくなる。結果として、熱サイクル特性の低下などを引き起こし、ＳＯＦＣの信頼性を低下させてしまう。このように従来では、空気極を構成している材料の粒径を小さくすることにより、過電圧を低減させることが困難であった。 By the way, the air electrode is generally formed by applying the material constituting the air electrode on the electrolyte layer, baking it, and baking it on the electrolyte layer. If baking at this time is performed at an excessively high temperature, Since these particles coalesce to cause grain growth, the overvoltage of the air electrode is increased. In particular, when a zirconia-based material is used as the electrolyte and a La-based material is used as the air electrode, a rare earth element having a large ionic radius such as La is likely to diffuse into the electrolyte, so that SrZrO 3 or a pyrochlore phase (La 2 Since an inert substance having extremely low electronic conductivity and ionic conductivity such as Zr 2 O 7 ) is formed at the interface between zirconia and the air electrode, the overvoltage of the air electrode is increased. On the other hand, when the baking temperature is too low, the adhesion between the constituent material of the air electrode and zirconia is reduced, and the air electrode is easily peeled off from the electrolyte. As a result, the thermal cycle characteristics are deteriorated and the reliability of the SOFC is lowered. Thus, conventionally, it has been difficult to reduce the overvoltage by reducing the particle size of the material constituting the air electrode.

そこで、本発明は上述したような課題を解決するためになされたものであり、空気極の過電圧が増大するのを防ぐことができる固体酸化物型燃料電池および固体酸化物型燃料電池の製造方法を提供することを目的とする。   Therefore, the present invention has been made to solve the above-described problems, and a solid oxide fuel cell and a method for manufacturing the solid oxide fuel cell that can prevent an overvoltage of the air electrode from increasing. The purpose is to provide.

上述したような課題を解決するために本発明にかかる固体酸化物型燃料電池は、電解質層の両面に空気極と燃料極が設けられ、電解質層と空気極との間に中間層を有する固体酸化物型燃料電池において、電解質層は、稀土類添加ジルコニアから構成され、空気極は、ＬａまたはＬａおよびＳｒからなる第１の金属と、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素からなる第２の金属とからなるペロブスカイト構造の金属酸化物から構成され、中間層は、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素を含む酸化物から構成されることを特徴とする。   In order to solve the above-described problems, a solid oxide fuel cell according to the present invention is a solid oxide in which an air electrode and a fuel electrode are provided on both surfaces of an electrolyte layer, and an intermediate layer is provided between the electrolyte layer and the air electrode. In the oxide fuel cell, the electrolyte layer is composed of rare earth-added zirconia, the air electrode is composed of a first metal composed of La or La and Sr, and at least one of Fe, Co, Mn, and Ni. It is composed of a metal oxide having a perovskite structure composed of a second metal composed of an element, and the intermediate layer is composed of an oxide containing at least one element of Fe, Co, Mn, and Ni. And

上記固体酸化物型燃料電池において、中間層の厚さは、０．０１μｍ以上１μｍ以下であるようにしてもよい。   In the solid oxide fuel cell, the thickness of the intermediate layer may be 0.01 μm or more and 1 μm or less.

また、上記固体酸化物型燃料電池において、中間層は、稀土類添加ジルコニアと、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち何れか１つ以上の元素とを含む混合体の酸化物から構成されるようにしてもよい。ここで、稀土類添加ジルコニアは、１〜８０ｗｔ％の割合で混合されるようにしてもよい。また、中間層の厚さは、０．０２μｍ以上２μｍ以下であるようにしてもよい。   In the solid oxide fuel cell, the intermediate layer is composed of a mixed oxide containing rare earth-added zirconia and any one or more elements of Fe, Co, Mn, and Ni. It may be. Here, the rare earth added zirconia may be mixed at a ratio of 1 to 80 wt%. Further, the thickness of the intermediate layer may be 0.02 μm or more and 2 μm or less.

また、本発明にかかる固体酸化物型燃料電池の製造方法は、電解質層の両面に空気極と燃料極が設けられ、電解質層と空気極との間に中間層が形成された固体酸化物型燃料電池の製造方法であって、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち何れか１つ以上の元素を含む溶液を、稀土類添加ジルコニアからなる電解質層上に塗布し、焼成して中間層を形成する中間層形成ステップと、中間層上に、ＬａまたはＬａおよびＳｒからなる第１の金属と、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素からなる第２の金属とからなるペロブスカイト構造の金属酸化物を含むスラリを塗布し、焼成して空気極を形成する空気極形成ステップとを有することを特徴とする。   The method for producing a solid oxide fuel cell according to the present invention is a solid oxide type in which an air electrode and a fuel electrode are provided on both surfaces of an electrolyte layer, and an intermediate layer is formed between the electrolyte layer and the air electrode. A method for manufacturing a fuel cell, in which a solution containing one or more elements of Fe, Co, Mn, and Ni is applied on an electrolyte layer made of rare earth-added zirconia and baked to form an intermediate layer A perovskite comprising: an intermediate layer forming step; a first metal composed of La or La and Sr; and a second metal composed of at least one element of Fe, Co, Mn, and Ni on the intermediate layer. And an air electrode forming step in which a slurry containing a metal oxide having a structure is applied and fired to form an air electrode.

また、本発明にかかる他の固体酸化物型燃料電池の製造方法は、電解質層の両面に空気極と燃料極が設けられ、電解質層と空気極との間に中間層が形成された固体酸化物型燃料電池の製造方法であって、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素を含む溶液を、稀土類添加ジルコニアからなる電解質層上に塗布し、乾燥して薄膜を形成する薄膜形成ステップと、薄膜上に、ＬａまたはＬａおよびＳｒからなる第１の金属と、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素からなる第２の金属とからなるペロブスカイト構造の金属酸化物を含むスラリを塗布し、焼成して空気極および中間層を形成する形成ステップとを有することを特徴とする。   Further, another method of manufacturing a solid oxide fuel cell according to the present invention includes a solid oxide in which an air electrode and a fuel electrode are provided on both surfaces of an electrolyte layer, and an intermediate layer is formed between the electrolyte layer and the air electrode. A method for manufacturing a physical fuel cell, wherein a solution containing at least one element of Fe, Co, Mn, and Ni is applied onto an electrolyte layer made of rare earth-added zirconia and dried to form a thin film A perovskite structure comprising a thin film forming step, a first metal composed of La or La and Sr, and a second metal composed of at least one element of Fe, Co, Mn, and Ni on the thin film. And a forming step of applying a slurry containing a metal oxide and firing to form an air electrode and an intermediate layer.

また、本発明にかかる他の固体酸化物型燃料電池の製造方法は、電解質層の両面に空気極と燃料極が設けられ、電解質層と空気極との間に中間層が形成された固体酸化物型燃料電池の製造方法であって、真空成膜法により、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素を含む酸化物からなる中間層を、稀土類添加ジルコニアからなる電解質層上に形成する中間層形成ステップと、中間層上に、ＬａまたはＬａおよびＳｒからなる第１の金属と、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素からなる第２の金属とからなるペロブスカイト構造の金属酸化物を含むスラリを塗布し、焼成して空気極を形成する空気極形成ステップとを有することを特徴とする。   Further, another method of manufacturing a solid oxide fuel cell according to the present invention includes a solid oxide in which an air electrode and a fuel electrode are provided on both surfaces of an electrolyte layer, and an intermediate layer is formed between the electrolyte layer and the air electrode. A method for manufacturing a physical fuel cell, wherein an intermediate layer made of an oxide containing at least one element of Fe, Co, Mn, and Ni is formed by an vacuum film forming method, and an electrolyte layer made of rare earth-added zirconia An intermediate layer forming step formed thereon, a first metal composed of La or La and Sr, and a second metal composed of at least one element of Fe, Co, Mn, and Ni on the intermediate layer; And an air electrode forming step in which a slurry containing a metal oxide having a perovskite structure is applied and fired to form an air electrode.

本発明によれば、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素を酸化物からなる中間層を、稀土類添加ジルコニアからなる電解質と、ＬａまたはＬａおよびＳｒからなる第１の金属と、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素からなる第２の金属とからなるペロブスカイト構造の金属酸化物との間に形成することにより、空気極の過電圧が増大するのを防ぐことができる。   According to the present invention, the intermediate layer made of an oxide of at least one element of Fe, Co, Mn, and Ni, the electrolyte made of rare earth-added zirconia, and the first metal made of La or La and Sr And the perovskite structure metal oxide composed of the second metal composed of at least one of Fe, Co, Mn, and Ni, the overvoltage of the air electrode is increased. Can be prevented.

［第１の実施の形態］
以下、図面を参照して本発明の第１の実施の形態について詳細に説明する。図１は、本実施の形態にかかる固体酸化物型燃料電池の単セルの構成を模式的に示す断面図である。図１において、単セル１は、電解質層２と、この電解質層２の一の面上に中間層５を介して形成された空気極３と、電解質層２の他の面上に形成された燃料極４とを備えている。 [First Embodiment]
Hereinafter, a first embodiment of the present invention will be described in detail with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing the configuration of a single cell of a solid oxide fuel cell according to the present embodiment. In FIG. 1, a single cell 1 is formed on an electrolyte layer 2, an air electrode 3 formed on one surface of the electrolyte layer 2 via an intermediate layer 5, and another surface of the electrolyte layer 2. A fuel electrode 4 is provided.

電解質層２は、稀土類添加ジルコニア系酸化物から構成される。   The electrolyte layer 2 is composed of a rare earth-added zirconia oxide.

空気極３は、ＡサイトをＬａ、または、ＬａおよびＳｒが占め、ＢサイトをＦｅ、Ｃｏ、Ｍｎ、Ｎｉなどの遷移金属元素のうち少なくとも何れか１つが占めるＬａ(Ｓｒ）ＭｎＯ3，Ｌａ（Ｓｒ）Ｆｅ0.8Ｃｏ0.2Ｏ3，ＬａＮｉ0.6Ｆｅ0.4Ｏ3などペロブスカイト型構造（ＡＢＯ3）を有する多孔質から構成される。 In the air electrode 3, La (Sr) MnO 3 , La (occupying the A site with La or La and Sr and the B site with at least one of transition metal elements such as Fe, Co, Mn, Ni, etc. It is composed of a porous material having a perovskite structure (ABO 3 ) such as Sr) Fe 0.8 Co 0.2 O 3 , LaNi 0.6 Fe 0.4 O 3 .

燃料極４は、例えばＮｉＯ−ＹＳＺなど固体酸化物型燃料電池の燃料極として用いられる材料から構成される。   The fuel electrode 4 is made of a material used as a fuel electrode of a solid oxide fuel cell such as NiO-YSZ.

中間層５は、Ｆｅ、Ｃｏ、Ｍｎ、Ｎｉなどの遷移金属元素のうち少なくとも何れか１つの元素からなる金属酸化物、または、この遷移金属酸化物と稀土類添加ジルコニア系酸化物の混合体から構成される。   The intermediate layer 5 is made of a metal oxide composed of at least one of transition metal elements such as Fe, Co, Mn, and Ni, or a mixture of the transition metal oxide and rare earth-added zirconia oxide. Composed.

このような単セル１は、次のように形成される。まず、例えばドクターブレード法などの公知の方法により、厚さ１０〜１０μｍ程度の電解質層２を形成する。   Such a single cell 1 is formed as follows. First, the electrolyte layer 2 having a thickness of about 10 to 10 μm is formed by a known method such as a doctor blade method.

次いで、電解質層２の一方の面に燃料極４を形成後、電解質層２の他方の面に有機金属塩溶液または無機金属溶液を塗布し、この溶液を熱処理により乾燥および焼成または乾燥させる。これにより、遷移金属酸化物からなる中間層５、または、稀土類添加ジルコニア系酸化物と遷移金属酸化物との混合体からなる薄膜を形成する。なお、ＲＦスパッタリング法などの公知の真空成膜法により中間層５を形成するようにしてもよい。   Next, after forming the fuel electrode 4 on one surface of the electrolyte layer 2, an organic metal salt solution or an inorganic metal solution is applied to the other surface of the electrolyte layer 2, and this solution is dried and fired or dried by heat treatment. Thereby, the intermediate layer 5 made of a transition metal oxide or a thin film made of a mixture of a rare earth-added zirconia-based oxide and a transition metal oxide is formed. The intermediate layer 5 may be formed by a known vacuum film forming method such as an RF sputtering method.

次いで、中間層５または上記薄膜上にスラリ状に上記空気極３の材料をスクリーン印刷等の公知の方法により塗布し、ＳＯＦＣの動作温度よりも高い温度で焼成することにより空気極３または空気極３および中間層５を形成する。これにより、図１に示すような単セル１が形成される。   Next, the material of the air electrode 3 is applied in a slurry form on the intermediate layer 5 or the thin film by a known method such as screen printing, and is fired at a temperature higher than the operating temperature of the SOFC, whereby the air electrode 3 or the air electrode 3 and the intermediate layer 5 are formed. Thereby, the single cell 1 as shown in FIG. 1 is formed.

このように形成された単セル１において、中間層５に含まれるＦｅ，Ｃｏ，Ｍｎ，Ｎｉなどの金属元素からなる遷移金属酸化物は、ジルコニア、セリアなど螢石型結晶格子を有する固体電解質に、酸化雰囲気中におけるＳＯＦＣの動作温度で極めてわずかに固溶する（例えば、非特許文献１参照。）。しかしながら、上記遷移金属酸化物は、ＬａやＳｒなどのイオン半径の大きな稀土類元素を含まないので、ジルコニアとの界面に安定に存在させるために高温の熱処理を行っても、電解質層２との間で相互拡散が殆ど生じず、パイロクロアなどの不導体相などが生成されない。このため、上述した中間層５を設けることにより、空気極３の過電圧の増大を防ぐことが可能となる。   In the single cell 1 formed in this way, the transition metal oxide composed of metal elements such as Fe, Co, Mn, and Ni contained in the intermediate layer 5 is converted into a solid electrolyte having a meteorite-type crystal lattice such as zirconia and ceria. The solid solution dissolves very slightly at the operating temperature of SOFC in an oxidizing atmosphere (see, for example, Non-Patent Document 1). However, since the transition metal oxide does not contain a rare earth element having a large ionic radius such as La or Sr, even if heat treatment is performed at a high temperature in order to stably exist at the interface with zirconia, Interdiffusion hardly occurs between them, and non-conductive phases such as pyrochlore are not generated. For this reason, by providing the intermediate layer 5 described above, it is possible to prevent an increase in overvoltage of the air electrode 3.

また、上述したように中間層５に含まれる遷移金属酸化物が電解質層２にわずかに固溶することにより、中間層５の遷移金属酸化物と電解質層２のジルコニアとの密着力が強くなる。上記遷移金属酸化物は、空気極３を構成するＬａ（Ｓｒ）ＭｎＯ3，Ｌａ（Ｓｒ）Ｆｅ0.8Ｃｏ0.2Ｏ3，ＬａＮｉ0.6Ｆｅ0.4Ｏ3などＡＢＯ3で表される組成のペロブスカイト系酸化物のＢサイトと同じ金属元素を有しているため、空気極３と容易に相互拡散する。中間層３は、ミクロンオーダーに十分薄く形成されるため、空気極３を中間層５上に焼き付けると、空気極３と中間層５との間の相互拡散領域が電解質層２のジルコニアとの界面まで到達する。このため、空気極３を中間層５の上に焼き付けると、空気極３の焼き付け温度が比較的低温であっても、中間層５を介して電解質層２と空気極３との間で十分な密着力が得られるので、空気極３が電解質層２から剥がれるのを防ぐことができる。また、中間層５の組成も空気極３の組成に近いため、電解質層２と空気極３との間の電気化学的な活性を損なわない。これにより、空気極３の過電圧の増大を防ぐこともできる。 Further, as described above, the transition metal oxide contained in the intermediate layer 5 is slightly dissolved in the electrolyte layer 2, whereby the adhesion between the transition metal oxide of the intermediate layer 5 and the zirconia of the electrolyte layer 2 is increased. . The transition metal oxide is a perovskite oxide having a composition represented by ABO 3 such as La (Sr) MnO 3 , La (Sr) Fe 0.8 Co 0.2 O 3 , LaNi 0.6 Fe 0.4 O 3 constituting the air electrode 3. Since it has the same metal element as the B site, it easily interdiffuses with the air electrode 3. Since the intermediate layer 3 is formed to be sufficiently thin on the order of microns, when the air electrode 3 is baked on the intermediate layer 5, the interdiffusion region between the air electrode 3 and the intermediate layer 5 is an interface between the electrolyte layer 2 and zirconia. To reach. For this reason, when the air electrode 3 is baked on the intermediate layer 5, it is sufficient between the electrolyte layer 2 and the air electrode 3 through the intermediate layer 5 even if the baking temperature of the air electrode 3 is relatively low. Since the adhesion is obtained, the air electrode 3 can be prevented from peeling off from the electrolyte layer 2. Further, since the composition of the intermediate layer 5 is also close to the composition of the air electrode 3, the electrochemical activity between the electrolyte layer 2 and the air electrode 3 is not impaired. Thereby, increase of the overvoltage of the air electrode 3 can also be prevented.

したがって、中間層５の厚さは、遷移金属酸化物から構成される場合、単セル１を作製する際の高温プロセスを経ても中間層５が溶けて消滅しないよう０．０１μｍ以上で、かつ、空気極３と中間層５との間の相互拡散領域が電解質層２のジルコニアとの界面まで到達するよう１μｍ以下に、望ましくは０．０５μｍ以上０．５μｍ以下に、より望ましくは０．０８μｍ以上０．２μｍ以下に形成する。   Therefore, when the intermediate layer 5 is made of a transition metal oxide, the thickness of the intermediate layer 5 is 0.01 μm or more so that the intermediate layer 5 does not melt and disappear even through a high-temperature process in manufacturing the single cell 1. 1 μm or less, preferably 0.05 μm or more and 0.5 μm or less, more preferably 0.08 μm or more so that the interdiffusion region between the air electrode 3 and the intermediate layer 5 reaches the interface with the zirconia of the electrolyte layer 2. It is formed to 0.2 μm or less.

一方、稀土類添加ジルコニア系酸化物と遷移金属酸化物との混合体から構成される場合、中間層５の厚さは、単セル１を作製する際の高温プロセスを経ても中間層５が溶けて消滅しない０．０２μｍ以上で、かつ、空気極３と中間層５との間の相互拡散領域が電解質層２のジルコニアとの界面まで到達するよう２μｍ以下に、望ましくは０．０４μｍ以上１μｍ以下に、より望ましくは０．０５μｍ以上０．５μｍ以下に形成する。このとき、中間層５に混合させる稀土類添加ジルコニア系酸化物の割合は、１〜８０ｗｔ％、望ましくは１０〜７０ｗｔ％、より望ましくは４０〜６０ｗｔ％に設定する。   On the other hand, when composed of a mixture of rare earth-added zirconia-based oxide and transition metal oxide, the thickness of the intermediate layer 5 is such that the intermediate layer 5 is melted even through a high-temperature process when the single cell 1 is manufactured. 0.02 μm or more which does not disappear, and 2 μm or less, preferably 0.04 μm or more and 1 μm or less so that the interdiffusion region between the air electrode 3 and the intermediate layer 5 reaches the interface with the zirconia of the electrolyte layer 2. More desirably, it is formed to be 0.05 μm or more and 0.5 μm or less. At this time, the ratio of the rare earth-added zirconia oxide mixed in the intermediate layer 5 is set to 1 to 80 wt%, desirably 10 to 70 wt%, and more desirably 40 to 60 wt%.

［第２の実施の形態］
次に、本発明にかかる第２の実施の形態について説明する。図２は、本実施の形態にかかる固体酸化物型燃料電池の単セルの構成を示す模式図、図３は、図２の単セルを組み込んだ燃料電池の構成を模式的に示す要部断面図、図４は、密着力試験用の単セルの構成を示す模式図である。なお、本実施の形態は、上述した第１の実施の形態をより具体的に表すものである。 [Second Embodiment]
Next, a second embodiment according to the present invention will be described. FIG. 2 is a schematic diagram showing the configuration of a single cell of the solid oxide fuel cell according to the present embodiment, and FIG. 3 is a cross-sectional view of the main part schematically showing the configuration of the fuel cell incorporating the single cell of FIG. FIG. 4 and FIG. 4 are schematic views showing the configuration of a single cell for adhesion test. The present embodiment more specifically represents the first embodiment described above.

本実施の形態では、後述する所定の条件の下で図２に示すような単セルを形成し、この単セルを図３に示すような燃料電池に組み込んで発電試験を行った。また、空気極の密着力試験を行うために、図４に示すような単セルを形成した。まず、単セルおよびこの単セルを組み込んだ燃料電池について説明する。   In the present embodiment, a single cell as shown in FIG. 2 is formed under a predetermined condition to be described later, and this single cell is incorporated into a fuel cell as shown in FIG. 3 to perform a power generation test. Moreover, in order to perform the adhesion test of an air electrode, the single cell as shown in FIG. 4 was formed. First, a single cell and a fuel cell incorporating the single cell will be described.

単セル１０は、図２に示すように、平面視略矩形の板状の形状を有する電解質層１１と、この電解質層１１の一方の面に形成された平面視略円形の燃料極１２と、電解質層１１の他方の面に形成された平面視略円形の空気極１３と、電解質層１１および空気極１３の間に形成された中間層１４と、空気極１３が形成された側の面の電解質層１１の縁部に形成された参照極１５とを有する。なお、燃料極１２および空気極１３の表面には、それぞれ集電効率を向上させるために白金メッシュ集電体１６，１７が形成されている。   As shown in FIG. 2, the unit cell 10 includes an electrolyte layer 11 having a plate-like shape having a substantially rectangular shape in plan view, and a fuel electrode 12 having a substantially circular shape in plan view formed on one surface of the electrolyte layer 11. A substantially circular air electrode 13 in plan view formed on the other surface of the electrolyte layer 11, an intermediate layer 14 formed between the electrolyte layer 11 and the air electrode 13, and a surface on the side where the air electrode 13 is formed. And a reference electrode 15 formed at the edge of the electrolyte layer 11. Platinum mesh current collectors 16 and 17 are formed on the surfaces of the fuel electrode 12 and the air electrode 13 in order to improve the current collection efficiency.

燃料電池２０は、図３に示すように、上述した単セル１０と、シール３１を介して単セル１０の電解質層１１の部分を狭持するとともに単セル１０を気密保持するセルカバー３０と、単セル１０の空気極１３側に配設され空気やＯ2を供給し余分な空気やＯ2を排気する空気供給部４０と、単セル１０の燃料極１２側に配設されＨ2、Ｈ2＋Ｈ2Ｏ、ＣＨ4＋Ｈ2Ｏ等の燃料ガスを供給し排気ガスを排気する燃料供給部５０と、単セル１０の両極の白金メッシュ集電体１６，１７に接続され生成された電力を取り出す白金からなる端子６０と、単セル１０の参照極１５から参照電力を取り出す参照端子７０とを有する。 As shown in FIG. 3, the fuel cell 20 includes the unit cell 10 described above, a cell cover 30 that holds the portion of the electrolyte layer 11 of the unit cell 10 through the seal 31 and holds the unit cell 10 in an airtight manner, an air supply unit 40 which is disposed on the air electrode 13 side to exhaust the excess air or O 2 supply air or O 2 of the single cell 10 is disposed in the fuel electrode 12 side of the unit cell 10 H 2, H The generated power connected to the fuel supply unit 50 for supplying fuel gas such as 2 + H 2 O, CH 4 + H 2 O and the like and exhausting the exhaust gas, and the platinum mesh current collectors 16, 17 of the bipolar electrode of the single cell 10 is generated. A terminal 60 made of platinum to be taken out and a reference terminal 70 to take out reference power from the reference electrode 15 of the single cell 10 are provided.

次に、単セル１０の製造方法について説明する。まず、ドクターブレード法で焼成した厚さ０．２ｍｍのＹ2Ｏ3添加ジルコニア（ＹＳＺまたは０．９ＺｒＯ2−０．１Ｙ2Ｏ3）からなる電解質層１１の一方の面にＮｉＯ−ＹＳＺのスラリをスクリーン印刷法で塗布し、この上に白金メッシュ集電体１６を載せて１４００℃で８時間焼成を行い、厚さ６０μｍの燃料極１２を形成した。ここで、上記ＮｉＯ−ＹＳＺのスラリは、平均粒径が約０．６μｍのＹ2Ｏ3添加ジルコニアが４０ｗｔ％、平均粒径が約０．２μｍのＮｉＯ粉末が６０ｗｔ％含まれたものからなる。 Next, a method for manufacturing the single cell 10 will be described. First, a NiO—YSZ slurry is formed on one surface of an electrolyte layer 11 made of Y 2 O 3 -added zirconia (YSZ or 0.9ZrO 2 -0.1Y 2 O 3 ) having a thickness of 0.2 mm fired by a doctor blade method. Was applied by screen printing, and a platinum mesh current collector 16 was placed thereon and baked at 1400 ° C. for 8 hours to form a fuel electrode 12 having a thickness of 60 μm. The NiO—YSZ slurry is composed of 40 wt% of Y 2 O 3 added zirconia having an average particle diameter of about 0.6 μm and 60 wt% of NiO powder having an average particle diameter of about 0.2 μm. .

次いで、電解質層１１の他方の面に、トルエンで希釈したＣｏを含んだアルコキシド溶液をスピンコート法により塗布し、４００℃で乾燥させた後に１０００℃で４時間焼成し、厚さ０．０１μｍ〜０．１μｍのコバルト酸化物からなる中間層１４を形成した。なお、厚さ０．１μｍ以上の中間層１４については、４００℃の乾燥後と上記アルコキシド溶液のスピンコートを繰り返し行うことにより形成した。   Next, an alkoxide solution containing Co diluted with toluene is applied to the other surface of the electrolyte layer 11 by a spin coating method, dried at 400 ° C., and then baked at 1000 ° C. for 4 hours. An intermediate layer 14 made of 0.1 μm cobalt oxide was formed. The intermediate layer 14 having a thickness of 0.1 μm or more was formed by drying at 400 ° C. and repeated spin coating of the alkoxide solution.

次いで、所定の厚さに形成された中間層１４上に、ＡサイトがＬａおよびＳｒ、ＢサイトがＭｎから構成される粒径約０．８μｍのＬａ0.8Ｓｒ0.2ＭｎＯ3（ＬＳＭ）のスラリを塗布し、この上に白金メッシュ集電体１７を載せて１０００℃で２時間焼成し、厚さ６０μｍの空気極１３を形成した。なお、燃料極１２および空気極１３は何れも直径６ｍｍに形成した。 Next, a slurry of La 0.8 Sr 0.2 MnO 3 (LSM) having a particle size of about 0.8 μm composed of La and Sr at the A site and Mn at the B site is formed on the intermediate layer 14 having a predetermined thickness. The platinum mesh current collector 17 was placed thereon and baked at 1000 ° C. for 2 hours to form an air electrode 13 having a thickness of 60 μm. The fuel electrode 12 and the air electrode 13 were both formed to have a diameter of 6 mm.

このような方法により形成した中間層１４の厚さが異なる各セルを、それぞれセル＃１０１〜１０５とする。   Cells having different thicknesses of the intermediate layer 14 formed by such a method are designated as cells # 101 to 105, respectively.

また、上述したのと同様の方法で、Ｃｏ含有アルコキシド溶液に代えて、Ｆｅ含有アルコキシド溶液、Ｍｎ含有アルコキシド溶液、Ｎｉ含有アルコキシド溶液、または、Ｆｅ含有アルコキシド溶液とＣｏ含有アルコキシド溶液を用いて中間層１４を形成したセルを、それぞれセル＃１１１〜１４３とする。   Further, in the same manner as described above, instead of the Co-containing alkoxide solution, an intermediate layer using a Fe-containing alkoxide solution, a Mn-containing alkoxide solution, a Ni-containing alkoxide solution, or a Fe-containing alkoxide solution and a Co-containing alkoxide solution is used. The cells in which 14 is formed are referred to as cells # 111 to 143, respectively.

また、上述したのと同様の方法で、中間層１４を形成せず、電解質層１１上に粒径０．８μｍのＬＳＭ（Ｌａ0.78Ｓｒ0.2ＭｎＯ3）のスラリを塗布し、この上に白金メッシュ集電体１７を載せて１０００℃で４時間焼成し、厚さ６０μｍの空気極１３を形成したものを、参照用のセルとして作製した。このセルを＃１００とする。 Further, an intermediate layer 14 is not formed by the same method as described above, but an LSM (La 0.78 Sr 0.2 MnO 3 ) slurry having a particle size of 0.8 μm is applied on the electrolyte layer 11, and a platinum mesh is applied thereon. A current collector 17 was placed and baked at 1000 ° C. for 4 hours to form a 60 μm thick air electrode 13 as a reference cell. This cell is designated as # 100.

上記セル＃１００〜１４３を単セル１０として図３に示すような燃料電池２０に組み込み、８００℃において発電試験を行った。この発電試験では、電極性能の指標である界面抵抗を交流インピーダンス法で測定した。また、上記セル＃１００〜１４３において、図４に示すように、燃料極１２と参照極１５を設けず、電解質層１１を１ｃｍ角の矩形状に形成したセルも併せて作製し、密着力試験を行った。この密着力試験では、焼成後の空気極１３にテープを貼り付け、これを剥がした後の残留率を測定した。これらの試験結果を表１に示す。なお、発電試験において、空気供給部４０からはＯ2を供給し、燃料供給部５０からは室温加湿水素ガスを供給した。すると、開放起電力として１．１２Ｖ以上の値が得られた。 The cells # 100 to 143 were incorporated into a fuel cell 20 as shown in FIG. 3 as a single cell 10 and a power generation test was performed at 800 ° C. In this power generation test, the interfacial resistance, which is an index of electrode performance, was measured by the AC impedance method. Further, in the cells # 100 to 143, as shown in FIG. 4, a cell in which the fuel electrode 12 and the reference electrode 15 are not provided and the electrolyte layer 11 is formed in a rectangular shape of 1 cm square is also produced, and an adhesion test is performed. Went. In this adhesion test, a tape was attached to the air electrode 13 after firing, and the residual ratio after peeling the tape was measured. These test results are shown in Table 1. In the power generation test, O 2 was supplied from the air supply unit 40 and room temperature humidified hydrogen gas was supplied from the fuel supply unit 50. Then, a value of 1.12 V or more was obtained as the open electromotive force.

Figure 2006236820
Figure 2006236820

表１に示すように、中間層１４を形成したセル＃１０１〜１４３は、中間層１４を形成していないセル＃１００よりも密着力が向上している。また、セル＃１０１〜１４３は、セル＃１００よりも低い界面抵抗、すなわちより優れた電極特定が得られた。これは、空気極１３の密着力が向上したために空気極１３のミクロな剥がれが抑制され、電解質層１１のジルコニアとの界面をより強固に密着させることができ、この界面に設けた中間層１４の組成が活性の高い空気極１３に近いものとなったためと考えられる。以上のように、本実施の形態によれば、中間層１４を形成することにより、従来よりも空気極１３をジルコニア系の電解質層１１への密着力が向上するとともに、空気極界面抵抗を低い値に安定させることができた。   As shown in Table 1, cells # 101 to 143 in which the intermediate layer 14 is formed have improved adhesion than the cell # 100 in which the intermediate layer 14 is not formed. Moreover, cell # 101-143 obtained the interface resistance lower than cell # 100, ie, the more superior electrode specification. This is because the adhesion of the air electrode 13 is improved, so that the micro peeling of the air electrode 13 is suppressed, and the interface between the electrolyte layer 11 and zirconia can be more firmly adhered, and the intermediate layer 14 provided at this interface. This is considered to be because the composition of is close to the highly active air electrode 13. As described above, according to the present embodiment, the formation of the intermediate layer 14 improves the adhesion of the air electrode 13 to the zirconia-based electrolyte layer 11 and lowers the air electrode interface resistance. The value could be stabilized.

［第３の実施の形態］
次に、本発明の第３の実施の形態について説明する。なお、本実施の形態において、第２の実施の形態と同等の構成要素には、同じ名称および符号を付し、適宜説明を省略する。 [Third Embodiment]
Next, a third embodiment of the present invention will be described. In the present embodiment, the same components as those in the second embodiment are denoted by the same names and reference numerals, and description thereof will be omitted as appropriate.

本実施の形態は、上述した第２の実施の形態のセル＃１００〜１４３において、電解質層１１の材料をＹＳＺからＳＳＺ（０．９ＺｒＯ2−０．１Ｓｃ2Ｏ3）に、空気極１３の材料をＬＳＭからＡサイトがＬａおよびＳｒ、ＢサイトがＦｅから構成されるＬＳＦ（Ｌａ0.8Ｓｒ0.2ＦｅＯ3）に代えたものを、それぞれセル＃２００〜２４３としたものである。このようなセル＃２００〜２４３を用いて、第２の実施の形態と同様の試験を行った。この試験結果を表２に示す。 In this embodiment, in the cells # 100 to 143 of the second embodiment described above, the material of the electrolyte layer 11 is changed from YSZ to SSZ (0.9ZrO 2 −0.1Sc 2 O 3 ), and the air electrode 13 Cells # 200 to 243 were used in which the material was changed from LSM to LSF (La 0.8 Sr 0.2 FeO 3 ) composed of La and Sr at the A site and Fe at the B site. Using the cells # 200 to 243, the same test as in the second embodiment was performed. The test results are shown in Table 2.

Figure 2006236820
Figure 2006236820

表２に示すように本実施の形態においても、中間層１４を設けたセル＃２０１〜＃２４３は、中間層１４を形成していないセル＃２００と比較して、密着力が向上するとともに、界面抵抗においても同等または良好な特性が得られた。   As shown in Table 2, also in the present embodiment, the cells # 201 to # 243 provided with the intermediate layer 14 have improved adhesion as compared to the cell # 200 where the intermediate layer 14 is not formed. The same or good characteristics were obtained in the interface resistance.

［第４の実施の形態］
次に、本発明の第４の実施の形態について説明する。なお、本実施の形態において、第１，２の実施の形態と同等の構成要素には、同じ名称および符号を付し、適宜説明を省略する。 [Fourth Embodiment]
Next, a fourth embodiment of the present invention will be described. In the present embodiment, the same components as those in the first and second embodiments are denoted by the same names and reference numerals, and description thereof will be omitted as appropriate.

本実施の形態は、上述した第２の実施の形態のセル＃１００〜１４３において、電解質層１１の材料をＹＳＺからＳＡＳＺ（０．８９ＺｒＯ2−０．１Ｓｃ2Ｏ3−０．０１Ｓｃ2Ｏ3）に、空気極１３の材料をＬＳＭからＡサイトがＬａ、ＢサイトがＮｉおよびＦｅから構成されるＬＮＦ（ＬａＮｉ0.6Ｆｅ0.4Ｏ3）に代えたものを、それぞれセル＃３００〜３４３としたものである。このようなセル＃３００〜３４３を用いて、第２の実施の形態と同様の試験を行った。この試験結果を表３に示す。 This embodiment, in the cell # 100-143 of the second embodiment described above, SASZ material of the electrolyte layer 11 from YSZ (0.89ZrO 2 -0.1Sc 2 O 3 -0.01Sc 2 O 3 ), The material of the air electrode 13 is changed from LSM to LNF (LaNi 0.6 Fe 0.4 O 3 ) composed of A site La and B site Ni and Fe, respectively, to cells # 300 to 343 It is. Using the cells # 300 to 343, the same test as in the second embodiment was performed. The test results are shown in Table 3.

Figure 2006236820
Figure 2006236820

表３に示すように本実施の形態においても、中間層１４を設けたセル＃３０１〜＃３４３は、中間層１４を形成していないセル＃３００と比較して、密着力が向上するとともに、界面抵抗においても同等または良好な特性が得られた。   As shown in Table 3, also in the present embodiment, the cells # 301 to # 343 provided with the intermediate layer 14 have improved adhesion as compared to the cell # 300 where the intermediate layer 14 is not formed. The same or good characteristics were obtained in the interface resistance.

［第５の実施の形態］
次に、本発明の第５の実施の形態について説明する。なお、本実施の形態において、第２の実施の形態と同等の構成要素には、同じ名称および符号を付し、適宜説明を省略する。 [Fifth Embodiment]
Next, a fifth embodiment of the present invention will be described. In the present embodiment, the same components as those in the second embodiment are denoted by the same names and reference numerals, and description thereof will be omitted as appropriate.

本実施の形態は、上述した第２の実施の形態のセル＃１００〜１４３において、電解質層１１の材料をＹＳＺからＹＳＺ−ＹＤＣ（０．９｛０．９ＺｒＯ2−０．１Ｙ2Ｏ3｝＋０．１｛Ｃｅ0.8Ｙ0.2Ｏ2｝）に、空気極１３の材料をＬＳＭからＡサイトがＬａおよびＳｒ、ＢサイトがＦｅおよびＣｏから構成されるＬＳＣＦ（Ｌａ0.8Ｓｒ0.2Ｆｅ0.8Ｃｏ0.2Ｏ3）に代えたものを、それぞれセル＃４００〜４４３としたものである。ここで、中間層１４は、４００℃で乾燥のみを行い、空気極１３を塗布後に空気極１３と中間層１４とを同時に１０００℃で２時間焼成を行った。このようなセル＃４００〜４４３を用いて、第２の実施の形態と同様の試験を行った。この試験結果を表４に示す。 In this embodiment, in the cells # 100 to 143 of the second embodiment described above, the material of the electrolyte layer 11 is changed from YSZ to YSZ-YDC (0.9 {0.9ZrO 2 -0.1Y 2 O 3 }). +0.1 {Ce 0.8 Y 0.2 O 2 }), and the material of the air electrode 13 is made of LSCF (La 0.8 Sr 0.2 Fe 0.8 Co 0.2 O made of LSM, A site is La and Sr, and B site is Fe and Co). The cells replaced with 3 ) are cells # 400 to 443, respectively. Here, the intermediate layer 14 was only dried at 400 ° C., and after the air electrode 13 was applied, the air electrode 13 and the intermediate layer 14 were simultaneously fired at 1000 ° C. for 2 hours. Using the cells # 400 to 443, the same test as in the second embodiment was performed. The test results are shown in Table 4.

Figure 2006236820
Figure 2006236820

表４に示すように本実施の形態においても、中間層１４を設けたセル＃４０１〜＃４４３は、中間層１４を形成していないセル＃４００と比較して、密着力が向上するとともに、界面抵抗においても同等または良好な特性が得られた。   As shown in Table 4, also in the present embodiment, the cells # 401 to # 443 provided with the intermediate layer 14 have improved adhesion as compared to the cell # 400 where the intermediate layer 14 is not formed. The same or good characteristics were obtained in the interface resistance.

［第６の実施の形態］
次に、本発明の第６の実施の形態について説明する。なお、本実施の形態において、第２の実施の形態と同等の構成要素には、同じ名称および符号を付し、適宜説明を省略する。 [Sixth Embodiment]
Next, a sixth embodiment of the present invention will be described. In the present embodiment, the same components as those in the second embodiment are denoted by the same names and reference numerals, and description thereof will be omitted as appropriate.

本実施の形態では、上述した第２の実施の形態において、Ｃｏ，Ｆｅ，Ｍｎ，Ｎｉの何れかからなる遷移金属と、電解質層１１と同じＹＳＺの組成に対応する金属元素と所定の混合比で混合した溶液をスピンコート法により電解質層１１上に塗布し、４００℃で乾燥させた後に１０００℃で４時間焼成することにより、厚さ０．３μｍの中間層１４を形成した。このような方法により形成した中間層１４の各成分または混合比が異なる各セルを、それぞれセル＃５０１〜５３１とする。このようなセル＃５０１〜５３１を用いて、第２の実施の形態と同様の試験を行った。この試験結果を表５に示す。なお、表５において、中間層の組成は、モル混合比（ＭＯXと（Ｚｒ＋Ｙ）Ｏ2の比）を意味する。また、比較のため、表５には、第２の実施の形態で参照用のセルとして用いたセル＃１００を併記している。 In the present embodiment, in the second embodiment described above, a transition metal composed of any one of Co, Fe, Mn, and Ni, a metal element corresponding to the same YSZ composition as the electrolyte layer 11, and a predetermined mixing ratio are used. The solution mixed in (1) was applied onto the electrolyte layer 11 by spin coating, dried at 400 ° C., and then baked at 1000 ° C. for 4 hours, thereby forming an intermediate layer 14 having a thickness of 0.3 μm. Cells with different components or mixing ratios of the intermediate layer 14 formed by such a method are designated as cells # 501 to 531, respectively. Using the cells # 501 to 531, a test similar to that of the second embodiment was performed. The test results are shown in Table 5. In Table 5, the composition of the intermediate layer means a molar mixing ratio (ratio of MO X and (Zr + Y) O 2 ). For comparison, Table 5 also shows cell # 100 used as a reference cell in the second embodiment.

Figure 2006236820
Figure 2006236820

表５に示すように本実施の形態においても、中間層１４を設けたセル＃５０１〜＃５３１は、中間層１４を形成していないセル＃１００と比較して、密着力が向上するとともに、界面抵抗においても同等または良好な特性が得られた。   As shown in Table 5, also in the present embodiment, the cells # 501 to # 531 provided with the intermediate layer 14 have improved adhesion as compared to the cell # 100 where the intermediate layer 14 is not formed. The same or good characteristics were obtained in the interface resistance.

［第７の実施の形態］
次に、本発明の第７の実施の形態について説明する。なお、本実施の形態において、第２，３の実施の形態と同等の構成要素には、同じ名称および符号を付し、適宜説明を省略する。 [Seventh Embodiment]
Next, a seventh embodiment of the present invention will be described. In the present embodiment, the same components as those in the second and third embodiments are denoted by the same names and reference numerals, and description thereof will be omitted as appropriate.

本実施の形態では、上述した第３の実施の形態において、Ｃｏ，Ｆｅ，Ｍｎ，Ｎｉの何れかからなる遷移金属と、電解質層１１と同じＳＳＺの組成に対応する金属元素と所定の混合比で混合した溶液をスピンコート法により電解質層１１上に塗布し、４００℃で乾燥させた後に１０００℃で４時間焼成することにより、厚さ０．３μｍの中間層１４を形成した。このような方法により形成した中間層１４の各成分または混合比が異なる各セルを、それぞれセル＃６０１〜６３１とする。このようなセル＃６０１〜６３１を用いて、第２の実施の形態と同様の試験を行った。この試験結果を表６に示す。なお、表６において、中間層の組成は、モル混合比（ＭＯXと（Ｚｒ＋Ｓｃ＋Ａｌ）Ｏ2の比）を意味する。また、比較のため、表６には、第３の実施の形態で参照用のセルとして用いたセル＃２００を併記している。 In the present embodiment, in the third embodiment described above, a transition metal composed of any one of Co, Fe, Mn, and Ni, a metal element corresponding to the same SSZ composition as the electrolyte layer 11, and a predetermined mixing ratio. The solution mixed in (1) was applied onto the electrolyte layer 11 by spin coating, dried at 400 ° C., and then baked at 1000 ° C. for 4 hours, thereby forming an intermediate layer 14 having a thickness of 0.3 μm. Cells having different components or mixing ratios of the intermediate layer 14 formed by such a method are referred to as cells # 601 to 631, respectively. Using the cells # 601 to 631, tests similar to those in the second embodiment were performed. The test results are shown in Table 6. In Table 6, the composition of the intermediate layer means a molar mixing ratio (ratio of MO X and (Zr + Sc + Al) O 2 ). For comparison, Table 6 also shows cell # 200 used as a reference cell in the third embodiment.

Figure 2006236820
Figure 2006236820

表６に示すように本実施の形態においても、中間層１４を設けたセル＃６０１〜＃６３１は、中間層１４を形成していないセル＃２００と比較して、密着力が向上するとともに、界面抵抗においても同等または良好な特性が得られた。   As shown in Table 6, also in the present embodiment, the cells # 601 to # 631 provided with the intermediate layer 14 have improved adhesion as compared to the cell # 200 where the intermediate layer 14 is not formed. The same or good characteristics were obtained in the interface resistance.

［第８の実施の形態］
次に、本発明の第８の実施の形態について説明する。なお、本実施の形態において、第２，４の実施の形態と同等の構成要素には、同じ名称および符号を付し、適宜説明を省略する。 [Eighth Embodiment]
Next, an eighth embodiment of the present invention will be described. In the present embodiment, the same components as those in the second and fourth embodiments are denoted by the same names and reference numerals, and description thereof will be omitted as appropriate.

本実施の形態では、上述した第４の実施の形態において、Ｃｏ，Ｆｅ，Ｍｎ，Ｎｉの何れかからなる遷移金属と、電解質層１１と同じＳＡＳＺの組成に対応する金属元素と所定の混合比で混合した溶液をスピンコート法により電解質層１１上に塗布し、４００℃で乾燥させた後に１０００℃で４時間焼成することにより、厚さ０．３μｍの中間層１４を形成した。このような方法により形成した中間層１４の各成分または混合比が異なる各セルを、それぞれセル＃７０１〜７３１とする。このようなセル＃７０１〜７３１を用いて、第２の実施の形態と同様の試験を行った。この試験結果を表７に示す。なお、表７において、中間層の組成は、モル混合比（ＭＯXと（Ｚｒ＋Ｓｃ＋Ａｌ）Ｏ2の比）を意味する。また、比較のため、表７には、第４の実施の形態で参照用のセルとして用いたセル＃３００を併記している。 In the present embodiment, in the above-described fourth embodiment, a transition metal made of any one of Co, Fe, Mn, and Ni, a metal element corresponding to the same composition of SASZ as the electrolyte layer 11, and a predetermined mixing ratio are used. The solution mixed in (1) was applied onto the electrolyte layer 11 by spin coating, dried at 400 ° C., and then baked at 1000 ° C. for 4 hours, thereby forming an intermediate layer 14 having a thickness of 0.3 μm. Cells having different components or mixing ratios of the intermediate layer 14 formed by such a method are referred to as cells # 701 to 731, respectively. A test similar to that of the second embodiment was performed using such cells # 701 to 731. The test results are shown in Table 7. In Table 7, the composition of the intermediate layer means a molar mixing ratio (ratio of MO X and (Zr + Sc + Al) O 2 ). For comparison, Table 7 also shows cell # 300 used as a reference cell in the fourth embodiment.

Figure 2006236820
Figure 2006236820

表７に示すように本実施の形態においても、中間層１４を設けたセル＃７０１〜＃７３１は、中間層１４を形成していないセル＃３００と比較して、密着力が向上するとともに、界面抵抗においても同等または良好な特性が得られた。   As shown in Table 7, also in the present embodiment, the cells # 701 to # 731 provided with the intermediate layer 14 have improved adhesion as compared to the cell # 300 where the intermediate layer 14 is not formed. The same or good characteristics were obtained in the interface resistance.

［第９の実施の形態］
次に、本発明の第９の実施の形態について説明する。なお、本実施の形態において、第２，５の実施の形態と同等の構成要素には、同じ名称および符号を付し、適宜説明を省略する。 [Ninth Embodiment]
Next, a ninth embodiment of the present invention will be described. In the present embodiment, the same components as those in the second and fifth embodiments are denoted by the same names and reference numerals, and description thereof will be omitted as appropriate.

本実施の形態では、上述した第５の実施の形態において、Ｃｏ，Ｆｅ，Ｍｎ，Ｎｉの何れかからなる遷移金属と、電解質層１１と同じＹＳＺ−ＹＤＣ（０．９｛０．９ＺｒＯ2−０．１Ｙ2Ｏ3｝＋０．１｛Ｃｅ0.8Ｙ0.2Ｏ2｝）の組成に対応する金属元素と所定の混合比で混合した溶液をスピンコート法により電解質層１１上に塗布し、４００℃で乾燥のみを行い、空気極１３を塗布後に空気極１３と中間層１４とを同時に１０００℃で２時間焼成することにより、厚さ０．３μｍの中間層１４を形成した。このような方法により形成した中間層１４の各成分または混合比が異なる各セルを、それぞれセル＃８０１〜８３１とする。このようなセル＃８０１〜８３１を用いて、第２の実施の形態と同様の試験を行った。この試験結果を表８に示す。なお、表８において、中間層の組成は、モル混合比（ＭＯXと（Ｚｒ＋Ｃｅ＋Ｙ＋Ａｌ）Ｏ2の比）を意味する。また、比較のため、表８には、第５の実施の形態で参照用のセルとして用いたセル＃４００を併記している。 In the present embodiment, in the fifth embodiment described above, the transition metal composed of any one of Co, Fe, Mn, and Ni and the same YSZ-YDC (0.9 {0.9ZrO 2 − 0.1Y 2 O 3 } +0.1 {Ce 0.8 Y 0.2 O 2 }) and a solution mixed with a metal element corresponding to the composition at a predetermined mixing ratio are applied onto the electrolyte layer 11 by a spin coating method, and 400 ° C. The air electrode 13 and the intermediate layer 14 were simultaneously baked at 1000 ° C. for 2 hours after application of the air electrode 13 to form an intermediate layer 14 having a thickness of 0.3 μm. Cells having different components or mixing ratios of the intermediate layer 14 formed by such a method are referred to as cells # 801 to 831, respectively. Using the cells # 801 to 831, the same test as in the second embodiment was performed. The test results are shown in Table 8. In Table 8, the composition of the intermediate layer means a molar mixing ratio (a ratio of MO X to (Zr + Ce + Y + Al) O 2 ). For comparison, Table 8 also shows cell # 400 used as a reference cell in the fifth embodiment.

Figure 2006236820
Figure 2006236820

表８に示すように本実施の形態においても、中間層１４を設けたセル＃８０１〜＃８３１は、中間層１４を形成していないセル＃４００と比較して、密着力が向上するとともに、界面抵抗においても同等または良好な特性が得られた。   As shown in Table 8, also in the present embodiment, the cells # 801 to # 831 provided with the intermediate layer 14 have improved adhesion as compared to the cell # 400 where the intermediate layer 14 is not formed. The same or good characteristics were obtained in the interface resistance.

［第１０の実施の形態］
次に、本発明の第１０の実施の形態について説明する。なお、本実施の形態において、第２，４，８の実施の形態と同等の構成要素には、同じ名称および符号を付し、適宜説明を省略する。 [Tenth embodiment]
Next, a tenth embodiment of the present invention will be described. In the present embodiment, the same components as those in the second, fourth, and eighth embodiments are denoted by the same names and reference numerals, and description thereof will be omitted as appropriate.

本実施の形態では、上述した第８の実施の形態において、セル＃７０４の中間層の厚さを０．０５〜２μｍまで変化させたものをセル＃９０１〜９０５とした。また、セル＃７１４の中間層の厚さを０．０５〜２μｍまで変化させたものをセル＃９１１〜９１５とした。このようなセル＃９０１〜９１５を用いて、第２の実施の形態と同様の試験を行った。この試験結果を表９に示す。なお、比較のため、表９には、第４の実施の形態で参照用のセルとして用いたセル＃３００を併記している。   In the present embodiment, in the eighth embodiment, the cell # 901 to 905 is obtained by changing the thickness of the intermediate layer of the cell # 704 from 0.05 to 2 μm. Cell # 911-915 was obtained by changing the thickness of the intermediate layer of cell # 714 to 0.05-2 μm. Using the cells # 901 to 915, the same test as in the second embodiment was performed. The test results are shown in Table 9. For comparison, Table 9 also shows cell # 300 used as a reference cell in the fourth embodiment.

Figure 2006236820
Figure 2006236820

表９に示すように本実施の形態においても、中間層１４を設けたセル＃９０１〜＃９１５は、中間層１４を形成していないセル＃３００と比較して、密着力が向上するとともに、界面抵抗においても同等または良好な特性が得られた。   As shown in Table 9, also in the present embodiment, the cells # 901 to # 915 provided with the intermediate layer 14 have improved adhesion as compared to the cell # 300 where the intermediate layer 14 is not formed. The same or good characteristics were obtained in the interface resistance.

［第１１の実施の形態］
次に、本発明の第１１の実施の形態について説明する。なお、本実施の形態において、第４の実施の形態と同等の構成要素には、同じ名称および符号を付し、適宜説明を省略する。 [Eleventh embodiment]
Next, an eleventh embodiment of the present invention will be described. In the present embodiment, the same components as those in the fourth embodiment are denoted by the same names and reference numerals, and description thereof will be omitted as appropriate.

本実施の形態では、上述した第４の実施のセル＃３０２〜３０４，３１２〜３１４において、Ｃｏ3Ｏ4またはＦｅ2Ｏ3をターゲットとしたＲＦスパッタ法により中間層１４を形成したセルを、それぞれセル＃１００１〜１０１３としたものである。このようなセル＃１００１〜１０１３を用いて、第４の実施の形態と同様の試験を行った。この試験結果を表１０に示す。なお、比較のため、表１０には、第４の実施の形態で参照用のセルとして用いたセル＃３００を併記している。 In the present embodiment, a cell in which the intermediate layer 14 is formed by the RF sputtering method using Co 3 O 4 or Fe 2 O 3 as a target in the above-described fourth embodiment cells # 302 to 304, 312 to 314, These are cells # 1001 to 1013, respectively. Using the cells # 1001 to 1013, the same test as in the fourth embodiment was performed. The test results are shown in Table 10. For comparison, Table 10 also shows the cell # 300 used as a reference cell in the fourth embodiment.

Figure 2006236820
Figure 2006236820

表１０に示すように本実施の形態においても、中間層１４を設けたセル＃１００１〜＃１０１３は、中間層１４を形成していないセル＃３００と比較して、密着力が向上するとともに、界面抵抗においても同等または良好な特性が得られた。   As shown in Table 10, also in the present embodiment, the cells # 1001 to # 1013 provided with the intermediate layer 14 have improved adhesion as compared to the cell # 300 where the intermediate layer 14 is not formed. The same or good characteristics were obtained in the interface resistance.

［第１２の実施の形態］
次に、本発明の第１２の実施の形態について説明する。なお、本実施の形態において、第１１の実施の形態と同等の構成要素には、同じ名称および符号を付し、適宜説明を省略する。 [Twelfth embodiment]
Next, a twelfth embodiment of the present invention will be described. In the present embodiment, the same components as those in the eleventh embodiment are denoted by the same names and reference numerals, and description thereof will be omitted as appropriate.

本実施の形態では、上述した第１１の実施の形態において、ＳＡＳＺターゲットとＣｏ3Ｏ4、または、ＳＡＳＺターゲットとＦｅ2Ｏ3とを用いた２次元同時ＲＦスパッタにより、所定の組成を有する厚さ０．２μｍの中間層１４を形成した。このような方法により形成した中間層１４の各成分または混合比が異なる各セルを、それぞれセル＃１１０１〜１１１４とする。このようなセル＃１１０１〜１１１４を用いて第１１の実施の形態と同等の試験を行った。この試験結果を表１１に示す。なお、表１１において、中間層の組成は、ＳＡＳＺとＭｏX（Ｍ＝Ｃｏ，Ｆｅ）の混合比を（Ｚｒ＋Ｓｃ＋Ａｌ）：Ｍとして変化させたものである。また、比較のため、表１１には、第４の実施の形態で参照用のセルとして用いたセル＃３００を併記している。 In this embodiment, in the eleventh embodiment described above, a thickness having a predetermined composition is obtained by two-dimensional simultaneous RF sputtering using a SASZ target and Co 3 O 4 or a SASZ target and Fe 2 O 3. An intermediate layer 14 having a thickness of 0.2 μm was formed. Cells having different components or mixing ratios of the intermediate layer 14 formed by such a method are designated as cells # 1101 to 1114, respectively. A test equivalent to that of the eleventh embodiment was performed using such cells # 1101 to 1114. The test results are shown in Table 11. In Table 11, the composition of the intermediate layer is obtained by changing the mixing ratio of SASZ and Mo x (M = Co, Fe) as (Zr + Sc + Al): M. For comparison, Table 11 also shows cell # 300 used as a reference cell in the fourth embodiment.

Figure 2006236820
Figure 2006236820

表１１に示すように本実施の形態においても、中間層１４を設けたセル＃１１０１〜＃１１１４は、中間層１４を形成していないセル＃３００と比較して、密着力が向上するとともに、界面抵抗においても同等または良好な特性が得られた。   As shown in Table 11, also in the present embodiment, the cells # 1101 to # 1114 provided with the intermediate layer 14 have improved adhesion as compared to the cell # 300 where the intermediate layer 14 is not formed. The same or good characteristics were obtained in the interface resistance.

本発明の固体酸化物型燃料電池の単セルの構成を示す断面図である。It is sectional drawing which shows the structure of the single cell of the solid oxide fuel cell of this invention. （ａ）本発明の固体酸化物型燃料電池の単セルの構成を示す平面図、（ｂ）本発明の固体酸化物型燃料電池の単セルの構成を示す断面図である。(A) The top view which shows the structure of the single cell of the solid oxide fuel cell of this invention, (b) It is sectional drawing which shows the structure of the single cell of the solid oxide fuel cell of this invention. 図２の単セルを組み込んだ燃料電池の構成を示す要部断面図である。It is principal part sectional drawing which shows the structure of the fuel cell incorporating the single cell of FIG. 密着力試験用の単セルの構成を示す模式図である。It is a schematic diagram which shows the structure of the single cell for an adhesive force test.

符号の説明Explanation of symbols

１…単セル、２…電解質層、３…空気極、４…燃料極、５…中間層、１０…単セル、１１…電解質層、１２…燃料極、１３…空気極、１４…中間層、１５…参照極、１６…白金メッシュ集電体、２０…燃料電池、３０…セルカバー、３１…シール、４０…空気供給部、５０…燃料供給部、６０…端子、７０…参照端子。
DESCRIPTION OF SYMBOLS 1 ... Single cell, 2 ... Electrolyte layer, 3 ... Air electrode, 4 ... Fuel electrode, 5 ... Intermediate layer, 10 ... Single cell, 11 ... Electrolyte layer, 12 ... Fuel electrode, 13 ... Air electrode, 14 ... Intermediate layer, DESCRIPTION OF SYMBOLS 15 ... Reference electrode, 16 ... Platinum mesh current collector, 20 ... Fuel cell, 30 ... Cell cover, 31 ... Seal, 40 ... Air supply part, 50 ... Fuel supply part, 60 ... Terminal, 70 ... Reference terminal.

Claims (8)

電解質層の両面に空気極と燃料極が設けられ、前記電解質層と前記空気極との間に中間層を有する固体酸化物型燃料電池において、
前記電解質層は、稀土類添加ジルコニアから構成され、
前記空気極は、ＬａまたはＬａおよびＳｒからなる第１の金属と、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素からなる第２の金属とからなるペロブスカイト構造の金属酸化物から構成され、
前記中間層は、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素を含む酸化物から構成される
ことを特徴とする固体酸化物型燃料電池。 In a solid oxide fuel cell in which an air electrode and a fuel electrode are provided on both surfaces of an electrolyte layer, and an intermediate layer is provided between the electrolyte layer and the air electrode,
The electrolyte layer is composed of rare earth added zirconia,
The air electrode is composed of a metal oxide having a perovskite structure composed of a first metal composed of La or La and Sr, and a second metal composed of at least one element of Fe, Co, Mn, and Ni. And
The intermediate layer is composed of an oxide containing at least one element of Fe, Co, Mn, and Ni. A solid oxide fuel cell, wherein: 前記中間層の厚さは、０．０１μｍ以上１μｍ以下である
ことを特徴とする請求項１記載の固体酸化物型燃料電池。 2. The solid oxide fuel cell according to claim 1, wherein a thickness of the intermediate layer is not less than 0.01 μm and not more than 1 μm. 前記中間層は、稀土類添加ジルコニアと、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素とを含む混合体の酸化物から構成される
ことを特徴とする請求項１記載の固体酸化物型燃料電池。 2. The solid oxide according to claim 1, wherein the intermediate layer is composed of a mixed oxide containing rare earth-added zirconia and at least one element of Fe, Co, Mn, and Ni. Physical fuel cell. 前記稀土類添加ジルコニアは、１〜８０ｗｔ％の割合で混合される
ことを特徴とする請求項３記載の固体酸化物型燃料電池。 The solid oxide fuel cell according to claim 3, wherein the rare earth-added zirconia is mixed at a ratio of 1 to 80 wt%. 前記中間層の厚さは、０．０２μｍ以上２μｍ以下である
ことを特徴とする請求項３または４記載の固体酸化物型燃料電池。 5. The solid oxide fuel cell according to claim 3, wherein the intermediate layer has a thickness of 0.02 μm to 2 μm. 電解質層の両面に空気極と燃料極が設けられ、前記電解質層と前記空気極との間に中間層が形成された固体酸化物型燃料電池の製造方法であって、
Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち何れか１つ以上の元素を含む溶液を、稀土類添加ジルコニアからなる前記電解質層上に塗布し、焼成して前記中間層を形成する中間層形成ステップと、
前記中間層上に、ＬａまたはＬａおよびＳｒからなる第１の金属と、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素からなる第２の金属とからなるペロブスカイト構造の金属酸化物を含むスラリを塗布し、焼成して前記空気極を形成する空気極形成ステップと
を有することを特徴とする固体酸化物型燃料電池の製造方法。 A method for producing a solid oxide fuel cell in which an air electrode and a fuel electrode are provided on both surfaces of an electrolyte layer, and an intermediate layer is formed between the electrolyte layer and the air electrode,
An intermediate layer forming step of applying a solution containing any one or more elements of Fe, Co, Mn, and Ni onto the electrolyte layer made of rare earth-added zirconia and firing to form the intermediate layer;
A metal oxide having a perovskite structure made of a first metal made of La or La and Sr and a second metal made of at least one element of Fe, Co, Mn, and Ni is formed on the intermediate layer. And an air electrode forming step of forming an air electrode by applying and baking a slurry containing the solid oxide fuel cell. 電解質層の両面に空気極と燃料極が設けられ、前記電解質層と前記空気極との間に中間層が形成された固体酸化物型燃料電池の製造方法であって、
Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素を含む溶液を、稀土類添加ジルコニアからなる前記電解質層上に塗布し、乾燥して薄膜を形成する薄膜形成ステップと、
前記薄膜上に、ＬａまたはＬａおよびＳｒからなる第１の金属と、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素からなる第２の金属とからなるペロブスカイト構造の金属酸化物を含むスラリを塗布し、焼成して前記空気極および前記中間層を形成する形成ステップと
を有することを特徴とする固体酸化物型燃料電池の製造方法。 A method for producing a solid oxide fuel cell in which an air electrode and a fuel electrode are provided on both surfaces of an electrolyte layer, and an intermediate layer is formed between the electrolyte layer and the air electrode,
Applying a solution containing at least one element of Fe, Co, Mn, and Ni onto the electrolyte layer made of rare earth-added zirconia and drying to form a thin film; and
A metal oxide having a perovskite structure including a first metal composed of La or La and Sr and a second metal composed of at least one element of Fe, Co, Mn, and Ni is included on the thin film. And a formation step of forming the air electrode and the intermediate layer by applying a slurry and firing the slurry. A method for producing a solid oxide fuel cell, comprising: 電解質層の両面に空気極と燃料極が設けられ、前記電解質層と前記空気極との間に中間層が形成された固体酸化物型燃料電池の製造方法であって、
真空成膜法により、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素を含む酸化物からなる前記中間層を、稀土類添加ジルコニアからなる前記電解質層上に形成する中間層形成ステップと、
前記中間層上に、ＬａまたはＬａおよびＳｒからなる第１の金属と、Ｆｅ，Ｃｏ，Ｍｎ，Ｎｉのうち少なくとも何れか１つの元素からなる第２の金属とからなるペロブスカイト構造の金属酸化物を含むスラリを塗布し、焼成して前記空気極を形成する空気極形成ステップと
を有することを特徴とする固体酸化物型燃料電池の製造方法。
A method for producing a solid oxide fuel cell in which an air electrode and a fuel electrode are provided on both surfaces of an electrolyte layer, and an intermediate layer is formed between the electrolyte layer and the air electrode,
An intermediate layer forming step of forming the intermediate layer made of an oxide containing at least one element of Fe, Co, Mn, and Ni on the electrolyte layer made of rare earth-added zirconia by a vacuum film forming method; ,
A metal oxide having a perovskite structure made of a first metal made of La or La and Sr and a second metal made of at least one element of Fe, Co, Mn, and Ni is formed on the intermediate layer. And an air electrode forming step of forming an air electrode by applying and baking a slurry containing the solid oxide fuel cell.
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