JP2011249186A - Unit cell for solid oxide fuel battery - Google Patents

Unit cell for solid oxide fuel battery Download PDF

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JP2011249186A
JP2011249186A JP2010122425A JP2010122425A JP2011249186A JP 2011249186 A JP2011249186 A JP 2011249186A JP 2010122425 A JP2010122425 A JP 2010122425A JP 2010122425 A JP2010122425 A JP 2010122425A JP 2011249186 A JP2011249186 A JP 2011249186A
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electrolyte
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intermediate layer
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JP5517297B2 (en
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Himeko Orui
姫子 大類
Reiichi Chiba
玲一 千葉
Takeshi Komatsu
武志 小松
Hiroaki Taguchi
博章 田口
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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
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Abstract

PROBLEM TO BE SOLVED: To improve power generation efficiency of a unit cell for a solid oxide fuel battery.SOLUTION: Between a fuel electrode 1 and an electrolyte 3, a fuel electrode intermediate layer 2 is provided of which the porosity is lower and the thickness is less than the fuel electrode 1. Furthermore, between the electrolyte 3 and an air electrode 5, an air electrode intermediate layer 4 is provided of which the porosity is lower and the thickness is less than the air electrode. Thus, fuel utilization efficiency can be improved by excellent gas supply and battery voltage efficiency can be improved by enlarging a three-phase interface compatibly, thereby improving power generation efficiency as a result.

Description

本発明は、固体酸化物形燃料電池に関するものである。   The present invention relates to a solid oxide fuel cell.

近年、規模の大小にかかわらず高い効率が得られることから、燃料電池が注目されている。燃料電池は、酸素などの酸化剤ガスと水素などの燃料ガスとの化学反応を利用した電池であり、空気極と呼ばれる陽極と、燃料極と呼ばれる陰極とで電解質の層を挟んだ単セルを、並列または直列に複数重ね合わせたスタック構造を用いている。一組のセル（単セル）で得られる電気の電圧は、約１Ｖであるが、複数の単セルを重ね合わせて用いることで、所望とする電圧の供給が可能である。   In recent years, fuel cells have attracted attention because of their high efficiency regardless of the size. A fuel cell is a battery that uses a chemical reaction between an oxidant gas such as oxygen and a fuel gas such as hydrogen. A fuel cell is composed of a single cell with an electrolyte layer sandwiched between an anode called an air electrode and a cathode called a fuel electrode. A stack structure in which a plurality of layers are stacked in parallel or in series is used. The electric voltage obtained in one set of cells (single cells) is about 1 V, but a desired voltage can be supplied by using a plurality of single cells in an overlapping manner.

このような燃料電池には、高分子材料を電解質層に用いる固体高分子型や、セラミックスなどの酸化物を電解質層に用いる固体酸化物形がある。この固体酸化物形燃料電池（ＳＯＦＣ：Solid Oxide Fuel Cells）は、他の燃料電池より高い電気変換効率や出力密度を有するため、分散電源として積極的に開発が進められている。   Such fuel cells include a solid polymer type using a polymer material for the electrolyte layer, and a solid oxide type using an oxide such as ceramics for the electrolyte layer. This solid oxide fuel cell (SOFC) has a higher electric conversion efficiency and output density than other fuel cells, and is therefore actively being developed as a distributed power source.

固体酸化物形燃料電池の単セルの一般的な構成材料は、電解質として安定化ジルコニア、空気極として希土類をドープしたランタンマンガンナイト、燃料極としてニッケル−ジルコニアサーメットが用いられている。このように、固体酸化物形燃料電池用単セルの構成材料は、全てセラミックス材料であり、異なる材料の積層構造となっている。   As a general constituent material of a single cell of a solid oxide fuel cell, stabilized zirconia is used as an electrolyte, rare earth-doped lanthanum manganite is used as an air electrode, and nickel-zirconia cermet is used as a fuel electrode. Thus, the constituent materials of the single cell for a solid oxide fuel cell are all ceramic materials and have a laminated structure of different materials.

また、固体酸化物形燃料電池用単セルの構造は、大きく円筒型と平板型に分類されるが、性能の点から燃料極を支持体として薄膜電解質を形成した平板型セルの開発が活発に行われている（例えば、非特許文献１参照。）。この燃料極支持型の単セルを図５に示す。   In addition, the structure of single cells for solid oxide fuel cells is roughly classified into a cylindrical type and a flat plate type. From the viewpoint of performance, development of a flat plate cell in which a thin film electrolyte is formed using a fuel electrode as a support is active. (For example, refer nonpatent literature 1.). FIG. 5 shows this fuel electrode support type single cell.

図５に示す固体酸化物形燃料電池における燃料極支持型の単セル１００は、板状の燃料極１０１と、この燃料極１０１の上面に形成された薄膜からなる電解質１０２と、この電解質１０２上に形成された薄膜からなる空気極１０３とから構成されている。ここで、電解質１０２と空気極１０３の厚さは数十μｍ程度であるのに対して、支持体となる燃料極１０１の厚さは１〜２μｍである。このように、燃料極１０１は、単セルの体積の大部分を占めるために、燃料極１０１の特性が単セルの特性に大きく影響することとなる。   A fuel cell-supported unit cell 100 in the solid oxide fuel cell shown in FIG. 5 includes a plate-shaped fuel electrode 101, an electrolyte 102 made of a thin film formed on the upper surface of the fuel electrode 101, and the electrolyte 102. And an air electrode 103 made of a thin film. Here, the thickness of the electrolyte 102 and the air electrode 103 is about several tens of μm, whereas the thickness of the fuel electrode 101 serving as a support is 1 to 2 μm. Thus, since the fuel electrode 101 occupies most of the volume of the single cell, the characteristics of the fuel electrode 101 greatly affect the characteristics of the single cell.

このような燃料電池の発電効率ηは、簡略化すると下式（１）に示すように、理論上得られる電圧に対する実際の運転で得られた電圧の割合を示す電池電圧効率と、供給した燃料量のうち実際の発電反応に利用された燃料量の割合を示す燃料利用率Ｕfとの積で表すことができる。この式（１）を踏まえると、発電効率ηを向上させるには、電池電圧効率と燃料利用率を向上させることが必要である。なお、下式（１）において、Ｖは運転電圧、Ｖ0は理論電圧を表している。 The power generation efficiency η of such a fuel cell can be simplified as shown in the following formula (1): the cell voltage efficiency indicating the ratio of the voltage obtained in the actual operation to the theoretically obtained voltage, and the supplied fuel It can be expressed by the product of the fuel utilization rate U f indicating the ratio of the amount of fuel used for the actual power generation reaction. Considering this equation (1), it is necessary to improve the cell voltage efficiency and the fuel utilization rate in order to improve the power generation efficiency η. In the following formula (1), V represents an operating voltage and V 0 represents a theoretical voltage.

η＝Ｖ／Ｖ0・Ｕf ・・・（１） η = V / V 0 · U f (1)

電池電圧効率を高くするには、単セルの自身の内部抵抗を低くする必要がある。これを実現するには、単セルの材料に反応活性の高い材料を用いるとともに、三相界面（反応場）の多い電極構造、言い換えると、電解質と、燃料極または空気極の構成粒子と、燃料ガスまたは酸化剤ガスとの三相が接する部分の多い電極構造を実現することが望ましい。   In order to increase the battery voltage efficiency, it is necessary to reduce the internal resistance of the single cell. To achieve this, a highly reactive material is used as the material of the single cell, and an electrode structure with many three-phase interfaces (reaction fields), in other words, an electrolyte, constituent particles of the fuel electrode or the air electrode, and fuel It is desirable to realize an electrode structure having many portions in contact with the three phases with gas or oxidant gas.

一方、燃料利用率を高くするには、電極反応場、すなわち電解質と燃料極または空気極との界面への良好なガス供給が必要である。特に、燃料極支持型の単セルでは、燃料極が電解質や空気極より厚く形成されているために燃料極内での燃料ガスの移動距離が大きいので、電極反応場への良好なガス供給を実現するには燃料極内部におけるガス透過性を高くすることが必要である。通常、ガス透過性を高くするには、燃料極における気孔率を高くしたり、細孔径を大きくしたりすることが必要である。   On the other hand, in order to increase the fuel utilization rate, a good gas supply to the electrode reaction field, that is, the interface between the electrolyte and the fuel electrode or the air electrode is necessary. In particular, in a fuel cell-supported single cell, the fuel electrode is formed thicker than the electrolyte and air electrodes, so the distance of movement of the fuel gas in the fuel electrode is large, so that good gas supply to the electrode reaction field is achieved. To achieve this, it is necessary to increase the gas permeability inside the fuel electrode. Usually, in order to increase gas permeability, it is necessary to increase the porosity of the fuel electrode or increase the pore diameter.

D. Ghosh, E. Tang, M. Perry, D. Prediger, M. Pastula and R. Boersma, in SOFC VII, H. Yokokawa and S. C. Singhal, Editors, PV 2001-16, p.100, The Electrochemical Society Proceedings Series, Pennington, NJ, (2001)D. Ghosh, E. Tang, M. Perry, D. Prediger, M. Pastula and R. Boersma, in SOFC VII, H. Yokokawa and SC Singhal, Editors, PV 2001-16, p.100, The Electrochemical Society Proceedings Series, Pennington, NJ, (2001)

しかしながら、ガス透過性を高くするために燃料極や空気極の気孔率を高くしたり細孔径を大きくしたりすると、燃料極および空気極と電解質の界面部分に大きな気孔が存在することになるので、三相界面が減少してしまい、電池電圧効率が低下してしまう。このように、良好なガス供給による燃料利用率の向上と、三相界面を多くすることによる電池電圧効率の向上とは、両立することが困難であったので、結果として発電効率を向上させることが困難となっていた。   However, if the porosity of the fuel electrode or the air electrode is increased or the pore diameter is increased in order to increase the gas permeability, there will be large pores at the interface between the fuel electrode, the air electrode and the electrolyte. The three-phase interface is reduced, and the battery voltage efficiency is lowered. As described above, it has been difficult to achieve both improvement in fuel utilization by good gas supply and improvement in battery voltage efficiency by increasing the number of three-phase interfaces. Has become difficult.

そこで、本発明は、固体酸化物形燃料電池用単セルの発電効率を向上させることを目的とする。   Then, an object of this invention is to improve the electric power generation efficiency of the single cell for solid oxide fuel cells.

上述したような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用単セルは、電解質と、この電解質の一方の面に形成された燃料極と、電解質の他方の面に形成された空気極とを備えた固体酸化物形燃料電池用単セルにおいて、燃料極と電解質との間および空気極と電解質の間の少なくとも一方に設けられ、隣接する燃料極または空気極よりも低い気孔率を有しかつ厚さが薄い中間層を備えることを特徴とするものである。   In order to solve the problems as described above, a unit cell for a solid oxide fuel cell according to the present invention is formed on an electrolyte, a fuel electrode formed on one surface of the electrolyte, and the other surface of the electrolyte. A solid oxide fuel cell unit cell provided with a formed air electrode, provided at least one between the fuel electrode and the electrolyte and between the air electrode and the electrolyte, and lower than the adjacent fuel electrode or air electrode An intermediate layer having a porosity and a small thickness is provided.

上記固体酸化物形燃料電池用単セルにおいて、電解質は、スカンジア安定化ジルコニアからなり、燃料極は、酸化ニッケルと、スカンジア安定化ジルコニアまたはイットリア安定化ジルコニアとの混合体からなり、中間層は、燃料極と電解質との間に設けられ、酸化ニッケルと金属酸化物をドープしたスカンジア安定化ジルコニアの混合体からなるようにしてもよい。   In the single cell for a solid oxide fuel cell, the electrolyte is composed of scandia-stabilized zirconia, the fuel electrode is composed of nickel oxide and a mixture of scandia-stabilized zirconia or yttria-stabilized zirconia, and the intermediate layer is It may be made of a mixture of scandia-stabilized zirconia provided between the fuel electrode and the electrolyte and doped with nickel oxide and metal oxide.

また、上記固体酸化物形燃料電池用単セルにおいて、空気極は、ランタン系複合酸化物からなり、電解質は、スカンジア安定化ジルコニアからなり、中間層は、空気極と電解質の間に設けられ、ランタンニッケル鉄酸化物とセリア系電解質の混合体からなるようにしてもよい。   In the solid oxide fuel cell unit cell, the air electrode is made of a lanthanum-based composite oxide, the electrolyte is made of scandia-stabilized zirconia, and the intermediate layer is provided between the air electrode and the electrolyte, You may make it consist of a mixture of a lanthanum nickel iron oxide and a ceria type electrolyte.

また、上記固体酸化物形燃料電池用単セルにおいて、電解質は、スカンジア安定化ジルコニアからなり、燃料極は、酸化ニッケルとスカンジア安定化ジルコニアまたはイットリア安定化ジルコニアとの混合体からなり、空気極は、ランタン系複合酸化物からなり、中間層は、燃料極と電解質との間および空気極と電解質との間に設けられ、燃料極と電解質との間に設けられた中間層は、酸化ニッケルと金属酸化物をドープしたスカンジア安定化ジルコニアの混合体からなり、空気極と電解質の間に設けられた中間層は、ランタンニッケル鉄酸化物とセリア系電解質の混合体からなるようにしてもよい。   In the above solid oxide fuel cell unit cell, the electrolyte is composed of scandia-stabilized zirconia, the fuel electrode is composed of a mixture of nickel oxide and scandia-stabilized zirconia or yttria-stabilized zirconia, and the air electrode is The intermediate layer is provided between the fuel electrode and the electrolyte and between the air electrode and the electrolyte, and the intermediate layer provided between the fuel electrode and the electrolyte is made of nickel oxide. It may be made of a mixture of scandia-stabilized zirconia doped with a metal oxide, and the intermediate layer provided between the air electrode and the electrolyte may be made of a mixture of lanthanum nickel iron oxide and a ceria-based electrolyte.

上記固体酸化物形燃料電池用単セルにおいて、燃料極と電解質との間に設けられた中間層は、厚さが７μｍ以上２５μｍ以下であるようにしてもよい。   In the single cell for a solid oxide fuel cell, the intermediate layer provided between the fuel electrode and the electrolyte may have a thickness of 7 μm or more and 25 μm or less.

また、上記固体酸化物形燃料電池用単セルにおいて、空気極と電解質との間に設けられた中間層は、厚さが１μｍ以上２．２μｍ以下であるようにしてもよい。   In the solid oxide fuel cell unit cell, the intermediate layer provided between the air electrode and the electrolyte may have a thickness of 1 μm or more and 2.2 μm or less.

本発明によれば、燃料極と電解質との間および空気極と電解質の間の少なくとも一方に設けられ、隣接する燃料極または空気極よりも低い気孔率を有しかつ厚さが薄い中間層を備えることにより、良好なガス供給による燃料利用率の向上と、三相界面を多くすることによる電池電圧効率の向上を両立できるので、結果として発電効率を向上させることができる。   According to the present invention, the intermediate layer provided between at least one of the fuel electrode and the electrolyte and between the air electrode and the electrolyte and having a porosity lower than that of the adjacent fuel electrode or air electrode and having a small thickness. By providing it, it is possible to improve both the fuel utilization rate by good gas supply and the cell voltage efficiency by increasing the number of three-phase interfaces. As a result, the power generation efficiency can be improved.

図１は、本発明に係る固体酸化物形燃料電池用単セルの構成を模式的に示す断面図である。FIG. 1 is a cross-sectional view schematically showing the configuration of a single cell for a solid oxide fuel cell according to the present invention. 図２は、発電試験の測定系を模式的に示す図である。FIG. 2 is a diagram schematically showing a measurement system for a power generation test. 図３は、燃料極中間層の厚さと出力密度との関係を示す図である。FIG. 3 is a diagram showing the relationship between the thickness of the fuel electrode intermediate layer and the power density. 図４は、空気極中間層の厚さと出力密度との関係を示す図である。FIG. 4 is a diagram showing the relationship between the thickness of the air electrode intermediate layer and the power density. 図５は、従来の固体酸化物形燃料電池用単セルの構成を模式的に示す断面図である。FIG. 5 is a cross-sectional view schematically showing the structure of a conventional single cell for a solid oxide fuel cell.

以下、図面を参照して、本発明の実施の形態について詳細に説明する。   Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

＜単セルの構成＞
図１に示すように、本実施の形態に係る固体酸化物形燃料電池用単セルは、板状の燃料極１と、この燃料極１上に設けられた燃料極中間層２と、この燃料極中間層２上に設けられた電解質３と、この電解質３上に設けられた空気極中間層４と、この空気極中間層４上に設けられた空気極５とから構成される。 <Single cell configuration>
As shown in FIG. 1, a single cell for a solid oxide fuel cell according to the present embodiment includes a plate-shaped fuel electrode 1, a fuel electrode intermediate layer 2 provided on the fuel electrode 1, and this fuel. An electrolyte 3 provided on the electrode intermediate layer 2, an air electrode intermediate layer 4 provided on the electrolyte 3, and an air electrode 5 provided on the air electrode intermediate layer 4.

燃料極１は、ＮｉＯ粉末と電解質３の材料またはイットリア安定化ジルコニア（Ｚｒ（Ｙ）Ｏ2）との混合物から構成される。 The fuel electrode 1 is composed of a mixture of NiO powder and an electrolyte 3 material or yttria-stabilized zirconia (Zr (Y) O 2 ).

燃料極中間層２は、ＮｉＯ粉末と金属酸化物をドープしたスカンジア安定化ジルコニアの混合体から構成される。この燃料極中間層２は、全体積中に占める空隙の割合を示す気孔率が、燃料極１よりも低くなるように形成されている。本実施の形態において、燃料極１の気孔率は２８〜３３％、燃料極中間層２の気孔率は６〜２０％に形成されている。また、細孔径は、燃料極１が０．６２〜０．７５μｍ、燃料極中間層２が０．１５〜０．２５μｍに形成されている。また、燃料極中間層２は、燃料極１よりも厚さが薄くなるように形成されている。本実施の形態において、燃料極１の厚さを１．２ｍｍ程度、燃料極中間層２の厚さを７〜７０μｍに形成したが、この燃料極中間層２の厚さについては、後述するように、７〜２５μｍが望ましく、７〜１４μｍがより望ましい。   The fuel electrode intermediate layer 2 is composed of a mixture of scandia-stabilized zirconia doped with NiO powder and metal oxide. The fuel electrode intermediate layer 2 is formed so that the porosity indicating the ratio of voids in the entire volume is lower than that of the fuel electrode 1. In the present embodiment, the porosity of the fuel electrode 1 is 28 to 33%, and the porosity of the fuel electrode intermediate layer 2 is 6 to 20%. The pore diameters of the fuel electrode 1 are 0.62 to 0.75 μm, and the fuel electrode intermediate layer 2 is 0.15 to 0.25 μm. The fuel electrode intermediate layer 2 is formed so as to be thinner than the fuel electrode 1. In this embodiment, the thickness of the fuel electrode 1 is about 1.2 mm and the thickness of the fuel electrode intermediate layer 2 is 7 to 70 μm. The thickness of the fuel electrode intermediate layer 2 will be described later. Furthermore, 7-25 micrometers is desirable and 7-14 micrometers is more desirable.

電解質３は、スカンジア安定化ジルコニア（Ｚｒ（Ｓｃ）Ｏ2）、または、金属酸化物をドープしたスカンジア安定化ジルコニア（Ｚｒ（Ｓｃ，Ａ）Ｏ2でＡがＡｌ2Ｏ3，ＣｅＯ2，Ｙ2Ｏ3のいずれか１つ）から構成される。 The electrolyte 3 is scandia-stabilized zirconia (Zr (Sc) O 2 ) or scandia-stabilized zirconia doped with metal oxide (Zr (Sc, A) O 2, where A is Al 2 O 3 , CeO 2 , Y Any one of 2 O 3 ).

空気極中間層４は、ランタンニッケル鉄酸化物（ＬＮＦ：ＬａＮｉ（Ｆｅ）Ｏ3）とセリア系電解質（ＧＤＣ：Gadolinium doped Ceria）の混合物から構成される。この空気極中間層４の気孔率は２５〜３５％に形成されており、後述する空気極５の気孔率よりも低くされている。また、空気極中間層４は、空気極５よりも厚さが薄くなるように形成されている。本実施の形態において、空気極中間層４の厚さを１〜３μｍ、空気極５の厚さを４０μｍに形成したが、後述するように、空気極中間層４の厚さは、１μｍ〜２．２μｍが望ましく、１μｍ〜１．５μｍがより望ましい。 The air electrode intermediate layer 4 is composed of a mixture of lanthanum nickel iron oxide (LNF: LaNi (Fe) O 3 ) and a ceria-based electrolyte (GDC: Gadolinium doped Ceria). The porosity of the air electrode intermediate layer 4 is 25 to 35%, and is lower than the porosity of the air electrode 5 described later. The air electrode intermediate layer 4 is formed so as to be thinner than the air electrode 5. In the present embodiment, the thickness of the air electrode intermediate layer 4 is 1 to 3 μm and the thickness of the air electrode 5 is 40 μm. However, as will be described later, the thickness of the air electrode intermediate layer 4 is 1 μm to 2 μm. 2 μm is desirable, and 1 μm to 1.5 μm is more desirable.

空気極５は、ランタン系複合酸化物（Ｌａ（Ｍ，Ｎ）Ｏ3で、ＭがＳｒ，Ｎｉ，Ｃａのいずれか１つ、ＮがＭｎ，Ｆｅ，Ｃｏのいずれか１つ）から構成される。この空気極５の気孔率は、３５〜５０％の範囲内で空気極中間層４の気孔率よりも大きく形成されている。 The air electrode 5 is composed of a lanthanum-based complex oxide (La (M, N) O 3 , where M is any one of Sr, Ni, and Ca, and N is any one of Mn, Fe, and Co). The The porosity of the air electrode 5 is formed to be larger than the porosity of the air electrode intermediate layer 4 within a range of 35 to 50%.

＜単セルの製造方法＞
次に、上述した本実施の形態に係る固体酸化物形燃料電池用単セルの製造方法について説明する。 <Manufacturing method of single cell>
Next, the manufacturing method of the single cell for solid oxide fuel cells which concerns on this Embodiment mentioned above is demonstrated.

まず、燃料極１の材料および燃料極中間層２の材料を用意し、それぞれにバインダー、可塑剤、分散剤等を添加してスラリーとし、これをドクターブレード法により燃料極１は厚さ３００〜６００μｍ、燃料極中間層２は厚さ３０〜７０μｍのシート状に成形した。   First, a material for the fuel electrode 1 and a material for the fuel electrode intermediate layer 2 are prepared, and a binder, a plasticizer, a dispersant, and the like are added to each to form a slurry. The fuel electrode intermediate layer 2 was molded into a sheet shape having a thickness of 600 to 300 μm.

ここで、燃料極１の材料としては、ＮｉＯ粉末と、後述する電解質３に使用するいずれかのジルコニア粉末を６：４の重量比で混合したものに、造孔剤としてカーボン粉末を添加したものを用いた。ＮｉＯ粉末は、平均粒径３〜５μｍ、比表面積０．８〜１．５ｍ2／ｇであり、カーボン粉末は、平均粒径８〜１２μｍであり、カーボン添加量は１０〜２０ｗｔ％である。ここで、平均粒径については、レーザ回折／散乱法（堀場製作所、レーザ回折／散乱方式粒度分布測定装置）、比表面積については、ＢＥＴ他点法（ユアサイオニクス、高速比表面積・細孔径分布測定装置）により測定した。なお、以下においては、燃料極１の材料としてＮｉＯ粉末と電解質３の混合物を使用する場合を例に説明するが、電解質３の材料の替わりにイットリア安定化ジルコニア（Ｚｒ（Ｙ）Ｏ2）を用いても同等の作用効果を得ることができる。 Here, the material of the fuel electrode 1 is a mixture of NiO powder and any zirconia powder used in the electrolyte 3 described later in a weight ratio of 6: 4, with carbon powder added as a pore forming agent. Was used. The NiO powder has an average particle size of 3 to 5 μm and a specific surface area of 0.8 to 1.5 m 2 / g, the carbon powder has an average particle size of 8 to 12 μm, and the amount of carbon added is 10 to 20 wt%. Here, the average particle size is measured by the laser diffraction / scattering method (Horiba, laser diffraction / scattering type particle size distribution measuring device), and the specific surface area is measured by the BET other point method (your sonics, high-speed specific surface area / pore size distribution measurement). Apparatus). In the following description, a case where a mixture of NiO powder and electrolyte 3 is used as the material of the fuel electrode 1 will be described as an example, but yttria stabilized zirconia (Zr (Y) O 2 ) is used instead of the material of the electrolyte 3. Even if it uses, an equivalent effect can be obtained.

また、燃料極中間層２の材料としては、ＮｉＯ粉末と、造孔剤として機能するカーボン粉末とを混合したものを用いた。ＮｉＯ粉末は、平均粒径１〜２μｍ、比表面積６〜８ｍ2／ｇである。また、カーボン粉末は、平均粒径２〜５μｍ、添加量が７〜１０ｗｔ％である。ここで、平均粒径および比表面積については、上述した燃料極１の材料の場合と同等の方法を用いて測定した。 As the material for the fuel electrode intermediate layer 2, a mixture of NiO powder and carbon powder functioning as a pore-forming agent was used. The NiO powder has an average particle size of 1 to 2 μm and a specific surface area of 6 to 8 m 2 / g. The carbon powder has an average particle diameter of 2 to 5 μm and an addition amount of 7 to 10 wt%. Here, the average particle diameter and the specific surface area were measured using the same method as that for the material of the fuel electrode 1 described above.

また、スラリーについては、上述したような燃料極１および燃料極中間層２の材料に、ポリビニル系のバインダーおよび界面活性剤を加え、これらを２−プロパノールなどの有機溶媒からなる分散材に分散させることにより生成した。   As for the slurry, a polyvinyl binder and a surfactant are added to the materials of the fuel electrode 1 and the fuel intermediate layer 2 as described above, and these are dispersed in a dispersion material made of an organic solvent such as 2-propanol. Was generated by

このように、燃料極１と燃料極中間層２の材料に添加する造孔剤として機能するカーボン粉末の粒径および添加量を制御することにより、燃料極１と燃料極中間層２の気孔率を制御することができる。すなわち、燃料極中間層２の材料に添加する造孔剤は、燃料極１に添加する造孔剤よりも、粒径を小さくかつ添加量を少なくする。これにより、燃料極中間層２は、燃料極１よりも気孔率を低くすることができる。   In this way, the porosity of the fuel electrode 1 and the fuel electrode intermediate layer 2 is controlled by controlling the particle size and amount of carbon powder that functions as a pore forming agent added to the material of the fuel electrode 1 and the fuel electrode intermediate layer 2. Can be controlled. That is, the pore forming agent added to the material of the fuel electrode intermediate layer 2 has a smaller particle size and a smaller addition amount than the pore forming agent added to the fuel electrode 1. As a result, the fuel electrode intermediate layer 2 can have a lower porosity than the fuel electrode 1.

燃料極１および燃料極中間層２のシートを成形し、各シートを乾燥させた後、燃料極１のシートを１．２ｍｍ程度の厚さに積層し、この上に燃料極中間層２のシートを１枚だけ積層して熱圧着する。   After the sheets of the fuel electrode 1 and the fuel electrode intermediate layer 2 are formed and each sheet is dried, the sheet of the fuel electrode 1 is laminated to a thickness of about 1.2 mm, and the sheet of the fuel electrode intermediate layer 2 is formed thereon. Only one sheet is laminated and thermocompression bonded.

燃料極１と燃料極中間層２のシートを熱圧着した後、電解質３の材料にバインダーおよび溶剤を添加してスラリーとし、これをスクリーン印刷法により燃料極中間層２のシート上に厚さ７〜２０μｍ程度に印刷し、乾燥させる。   After the sheets of the fuel electrode 1 and the fuel electrode intermediate layer 2 are thermocompression bonded, a binder and a solvent are added to the material of the electrolyte 3 to form a slurry, which is formed on the sheet of the fuel electrode intermediate layer 2 by a screen printing method to a thickness of 7 Print to about 20 μm and dry.

ここで、電解質３の材料としては、８ｍｏｌ％Ｙ2Ｏ3安定化ＺｒＯ2（ＹＳＺ）またはＡｌ2Ｏ3を少量ドープしたスカンジア安定化ジルコニア（Ｚｒ（Ｓｃ，Ａｌ2Ｏ3）Ｏ2：ＳＡＳＺ）を用いた。 Here, the material of the electrolyte 3 is 8 mol% Y 2 O 3 stabilized ZrO 2 (YSZ) or scandia stabilized zirconia doped with a small amount of Al 2 O 3 (Zr (Sc, Al 2 O 3 ) O 2 : SASZ. ) Was used.

電解質３の材料を含むスラリーを乾燥させると、この積層体を適宜切り出して１３００℃で焼結することにより、燃料極１、燃料極中間層２および電解質３からなるハーフセルを作製した。このハーフセルにおいて、水銀圧入法により測定した燃料極１の気孔率は２８〜３３％、燃料極中間層２の気孔率は６〜２０％であった。また、水銀圧入法により測定した細孔径は、燃料極１が０．６２〜０．７５μｍ、燃料極中間層２が０．１５〜０．２５μｍであった。   When the slurry containing the material of the electrolyte 3 was dried, the laminate was appropriately cut out and sintered at 1300 ° C., so that a half cell composed of the fuel electrode 1, the fuel electrode intermediate layer 2, and the electrolyte 3 was produced. In this half cell, the porosity of the fuel electrode 1 measured by mercury porosimetry was 28 to 33%, and the porosity of the fuel electrode intermediate layer 2 was 6 to 20%. The pore diameters measured by mercury porosimetry were 0.62 to 0.75 μm for the fuel electrode 1 and 0.15 to 0.25 μm for the fuel electrode intermediate layer 2.

なお、燃料極中間層２は、上述したようなドクターブレード法のみならず、スクリーン印刷法を用いて形成するようにしてもよい。この場合、まず、上述した燃料極１の材料を含むスラリーをドクターブレード法により厚さ３００〜６００μｍのシート状に形成し、このシートを乾燥させた後に厚さが１．２ｍｍ程度になるまで積層し、ホットプレスする。このシートの積層体上に、燃料極中間層２の材料を含むスラリーをスクリーン印刷法により厚さ７〜３０μｍ程度に印刷して乾燥させる。この上に、電解質３の材料を含むスラリーをスクリーン印刷法により厚さ７〜２０μｍ程度に印刷して乾燥させる。このようにして形成された積層体を一体焼結することにより、燃料極１、燃料極中間層２および電解質３からなるハーフセルを作製することができる。このように、スクリーン印刷法を用いた場合には、ドクターブレード法を用いた場合よりも燃料極中間層２をより薄く形成することができる。   The fuel electrode intermediate layer 2 may be formed not only by the doctor blade method as described above but also by a screen printing method. In this case, first, the slurry containing the material of the fuel electrode 1 described above is formed into a sheet shape having a thickness of 300 to 600 μm by the doctor blade method, and the sheet is dried until the thickness becomes about 1.2 mm. And hot press. On this laminate of sheets, a slurry containing the material of the fuel electrode intermediate layer 2 is printed to a thickness of about 7 to 30 μm by a screen printing method and dried. On this, the slurry containing the material of the electrolyte 3 is printed to a thickness of about 7 to 20 μm by a screen printing method and dried. A half cell composed of the fuel electrode 1, the fuel electrode intermediate layer 2, and the electrolyte 3 can be produced by integrally sintering the thus formed laminate. Thus, when the screen printing method is used, the fuel electrode intermediate layer 2 can be formed thinner than when the doctor blade method is used.

このようにして燃料極中間層２の厚さを７〜７０μｍの範囲で変えて作製したハーフセルの電解質３上に、空気極中間層４と空気極５を形成する。具体的には、ハーフセルの電解質３上に空気極中間層４となるＬＮＦ（粒径１μｍ）とＧＤＣ（粒径０．３μｍ）の混合体のスラリーをスクリーン印刷法により厚さ２〜３μｍに印刷して乾燥させ、この上に空気極５となるＬＮＦ（粒径１μｍ）のスラリーをスクリーン印刷法により厚さ５０μｍ程度に印刷して乾燥させ、１０００℃で焼結させる。これにより、図１に示すような単セルを作製した。なお、空気極中間層４の厚さを１〜３μｍの範囲で変えた単セルも併せて作製した。このときの燃料極中間層２の厚さは４０μｍとした。また、水銀圧入法により測定した空気極中間層４の気孔率は２５〜３５％、細孔径は０．１５〜０．２５μｍであった。   The air electrode intermediate layer 4 and the air electrode 5 are formed on the electrolyte 3 of the half cell manufactured by changing the thickness of the fuel electrode intermediate layer 2 in the range of 7 to 70 μm. Specifically, a slurry of a mixture of LNF (particle size: 1 μm) and GDC (particle size: 0.3 μm) to be the air electrode intermediate layer 4 is printed on the half-cell electrolyte 3 to a thickness of 2 to 3 μm by screen printing. Then, a slurry of LNF (particle size: 1 μm) that becomes the air electrode 5 is printed thereon by a screen printing method to a thickness of about 50 μm, dried, and sintered at 1000 ° C. Thereby, a single cell as shown in FIG. 1 was produced. In addition, the single cell which changed the thickness of the air electrode intermediate | middle layer 4 in the range of 1-3 micrometers was also produced collectively. At this time, the thickness of the fuel electrode intermediate layer 2 was set to 40 μm. Moreover, the porosity of the air electrode intermediate layer 4 measured by mercury porosimetry was 25 to 35%, and the pore diameter was 0.15 to 0.25 μm.

このように、空気極中間層４と空気極５の材料の粒径を制御することにより、空気極中間層４と空気極５の気孔率を制御することができる。すなわち、空気極中間層４の材料は、空気極５の材料よりも粒径を小さくする。これにより、空気極中間層４は、空気極５よりも気孔率を低くすることができる。   Thus, the porosity of the air electrode intermediate layer 4 and the air electrode 5 can be controlled by controlling the particle size of the material of the air electrode intermediate layer 4 and the air electrode 5. That is, the material of the air electrode intermediate layer 4 has a smaller particle diameter than the material of the air electrode 5. As a result, the air electrode intermediate layer 4 can have a lower porosity than the air electrode 5.

＜発電試験＞
このようにして作製した単セルについて発電試験を行った。この発電試験に用いた測定系を図２に示す。この図２に示す測定系は、上面に単セルを固定する凹部１１ａを備えた耐熱性合金からなる下部マニホールド１１と、このセルホルダ１１と単セルとの隙間を塞ぐガラスシール１２と、単セル上に載置される耐熱性合金からなる上部マニホールド１３と、この上部マニホールド１３上に載置された重り１４とから構成されている。ここで、単セルは、凹部１１ａの底面に燃料極１が当接した状態で下部マニホールド１１に固定されている。また、下部マニホールド１１には、外部から供給される燃料ガスを単セルに導く燃料ガス流路１１ｂと、未反応の燃料ガスを外部に排出する排ガス流路１１ｃとが設けられている。また、上部マニホールド１３には、外部から供給される酸化剤ガスを空気極５に導く酸化剤ガス流路１３ａが設けられている。 <Power generation test>
A power generation test was performed on the single cell thus produced. The measurement system used for this power generation test is shown in FIG. The measurement system shown in FIG. 2 includes a lower manifold 11 made of a heat-resistant alloy having a concave portion 11a for fixing a single cell on the upper surface, a glass seal 12 that closes a gap between the cell holder 11 and the single cell, And an upper manifold 13 made of a heat resistant alloy and a weight 14 placed on the upper manifold 13. Here, the single cell is fixed to the lower manifold 11 with the fuel electrode 1 in contact with the bottom surface of the recess 11a. Further, the lower manifold 11 is provided with a fuel gas passage 11b for guiding fuel gas supplied from the outside to a single cell, and an exhaust gas passage 11c for discharging unreacted fuel gas to the outside. The upper manifold 13 is provided with an oxidant gas flow path 13 a that guides an oxidant gas supplied from the outside to the air electrode 5.

このような測定系を電気炉にセットし、燃料ガスとして窒素ガス、酸化剤ガスとして空気を供給しながら昇温させ、８００℃に到達したときに燃料ガスを純水素に切り替えることにより発電を行った。生成された電力は、下部マニホールド１１と上部マニホールド１３とに接続された負荷回路により取り出した。このような測定を、上述したように燃料極中間層２（７〜７０μｍ）および空気極中間層４（１〜３μｍ）の厚さを単セルそれぞれについて変えて行った。この測定による燃料極中間層２の厚さと出力密度との関係を図３、空気極中間層４の厚さと出力密度との関係を図４に示す。   Such a measurement system is set in an electric furnace, and the temperature is raised while supplying nitrogen gas as fuel gas and air as oxidant gas. When the temperature reaches 800 ° C., power is generated by switching the fuel gas to pure hydrogen. It was. The generated electric power was taken out by a load circuit connected to the lower manifold 11 and the upper manifold 13. Such measurement was performed by changing the thicknesses of the fuel electrode intermediate layer 2 (7 to 70 μm) and the air electrode intermediate layer 4 (1 to 3 μm) for each single cell as described above. FIG. 3 shows the relationship between the thickness of the fuel electrode intermediate layer 2 and the power density, and FIG. 4 shows the relationship between the thickness of the air electrode intermediate layer 4 and the power density.

図３に示すように、燃料極中間層２を設けることにより約０．３［Ｗ／ｃｍ2］以上の出力密度を実現できることがわかる。また、燃料極中間層２の厚さを７μｍ〜２５μｍとすると、さらに出力密度が向上することがわかる。特に、燃料極中間層２がより薄くなるほど、単セルの出力密度が高くなる傾向にあり、７μｍ〜１４μｍの領域で出力密度が最も大きくなっている。これは、燃料極中間層２が燃料極１よりも気孔率が低いので、厚さが小さくなることにより燃料ガスの拡散が良好になったためと考える。また、燃料極中間層２がＮｉＯとジルコニアの混合体からなり、電極反応がＮｉと電解質３との界面のみならず燃料極中間層２内部のＮｉとジルコニアとの界面でも進行するので、電極反応場である三相界面が平面方向だけでなく燃料極中間層２の厚さ方向にも延びて形成されたものとも考える。燃料極中間層２の厚さについては、図３からわかるように、７μｍ〜２５μｍが望ましく、７μｍ〜１４μｍがより望ましい。 As shown in FIG. 3, it can be seen that the power density of about 0.3 [W / cm 2 ] or more can be realized by providing the fuel electrode intermediate layer 2. It can also be seen that when the thickness of the fuel electrode intermediate layer 2 is 7 μm to 25 μm, the output density is further improved. In particular, as the fuel electrode intermediate layer 2 becomes thinner, the power density of the single cell tends to increase, and the power density is the highest in the region of 7 μm to 14 μm. This is thought to be because the fuel electrode intermediate layer 2 has a lower porosity than the fuel electrode 1, and thus the diffusion of the fuel gas is improved due to the reduced thickness. Further, since the fuel electrode intermediate layer 2 is made of a mixture of NiO and zirconia, the electrode reaction proceeds not only at the interface between Ni and the electrolyte 3, but also at the interface between Ni and zirconia inside the fuel electrode intermediate layer 2, so that the electrode reaction It is considered that the three-phase interface as a field is formed not only in the planar direction but also in the thickness direction of the fuel electrode intermediate layer 2. As can be seen from FIG. 3, the thickness of the fuel electrode intermediate layer 2 is preferably 7 μm to 25 μm, and more preferably 7 μm to 14 μm.

図４に示すように、空気極中間層４を設けることにより、約０．３［Ｗ／ｃｍ2］以上の出力密度を実現できることがわかる。また、空気極中間層４の厚さを１μｍ〜２．２μｍとすることで出力密度が向上することがわかる。この領域で空気極中間層４の厚さを薄くするほど出力密度が向上し、厚さが１μｍ〜１．５μｍの領域が最も顕著に出力密度が向上することが確認できた。このように出力密度が向上したのは、空気極中間層４がＬＮＦとＧＤＣの混合体からなり、電極反応がＬＮＦと電解質３の界面のみならずＬＮＦとＧＤＣの界面においても進行するためと考えられる。すなわち、電極反応場である三相界面が、単に平面上だけでなく空気極中間層４の厚さ方向にも伸びて形成されたためと思料する。空気極中間層４の厚さについては、図４からわかるように、１μｍ〜２．２μｍが望ましく、１μｍ〜１．５μｍがより望ましい。 As shown in FIG. 4, it can be seen that by providing the air electrode intermediate layer 4, a power density of about 0.3 [W / cm 2 ] or more can be realized. It can also be seen that the output density is improved by setting the thickness of the air electrode intermediate layer 4 to 1 μm to 2.2 μm. It was confirmed that the power density was improved as the thickness of the air electrode intermediate layer 4 was reduced in this region, and the power density was most significantly improved in the region having a thickness of 1 μm to 1.5 μm. The power density is thus improved because the air electrode intermediate layer 4 is made of a mixture of LNF and GDC, and the electrode reaction proceeds not only at the interface between LNF and electrolyte 3, but also at the interface between LNF and GDC. It is done. That is, it is considered that the three-phase interface as an electrode reaction field is formed not only on a plane but also extending in the thickness direction of the air electrode intermediate layer 4. As can be seen from FIG. 4, the thickness of the air electrode intermediate layer 4 is preferably 1 μm to 2.2 μm, and more preferably 1 μm to 1.5 μm.

以上説明したように、本実施の形態によれば、燃料極１よりも気孔率が低くかつ厚さが薄い燃料極中間層２、および、空気極５よりも気孔率が低くかつ厚さが薄い空気極中間層４を設けることにより、良好なガス供給による燃料利用率の向上と、三相界面を多くすることによる電池電圧効率の向上を両立できるので、結果として発電効率を向上させることができる。   As described above, according to the present embodiment, the fuel electrode intermediate layer 2 having a lower porosity and a thinner thickness than the fuel electrode 1 and the porosity and a thinner thickness than the air electrode 5. By providing the air electrode intermediate layer 4, it is possible to improve both the fuel utilization rate by good gas supply and the battery voltage efficiency by increasing the three-phase interface, and as a result, the power generation efficiency can be improved. .

すなわち、燃料電池の発電効率の向上のためには、高い電池電圧、高い燃料利用率での発電の実現が必要であるが、これらの両立のために、電極（燃料極および空気極）の大部分はガス透過性に優れる多孔質な構造の電極で、電解質との界面は電極活性の高い微細な構造を有する電極中間層（燃料極中間層２、空気極中間層４）を形成する２層構造の電極構成とした。また、この電極中間層の薄膜化により電極反応場の三相界面へのガス供給がスムーズに進行し、セル出力が向上した。電極中間層では、三相界面を三次元的に増加するため２種材料の混合体を用いているが、電極中間層の最適化により三相界面を減少させることなく出力を向上することができる。これらの結果、固体酸化物形燃料電池の出力密度が向上するため、小型で高出力な燃料電池システムを実現できる。   That is, in order to improve the power generation efficiency of the fuel cell, it is necessary to realize power generation with a high cell voltage and a high fuel utilization rate. To achieve both of these, the electrodes (fuel electrode and air electrode) are large. The part is an electrode having a porous structure excellent in gas permeability, and the interface with the electrolyte is two layers forming an electrode intermediate layer (fuel electrode intermediate layer 2, air electrode intermediate layer 4) having a fine structure with high electrode activity. The electrode configuration was structured. In addition, the thinning of the electrode intermediate layer facilitated the gas supply to the three-phase interface of the electrode reaction field, improving the cell output. In the electrode intermediate layer, a mixture of two kinds of materials is used to increase the three-phase interface three-dimensionally, but the output can be improved without reducing the three-phase interface by optimizing the electrode intermediate layer. . As a result, since the output density of the solid oxide fuel cell is improved, a small and high output fuel cell system can be realized.

なお、本実施の形態では、造孔材としてカーボン粉末を使用する場合を例に説明するが、造孔剤はカーボン粉末に限定されず、セラミックスの焼結の際に燃焼して空孔を形成するような材料であれば各種材料を適宜自由に用いることができる。   In this embodiment, the case where carbon powder is used as the pore forming material will be described as an example. However, the pore forming agent is not limited to carbon powder, and burns during ceramic sintering to form pores. Any material can be used as appropriate as long as it is such a material.

また、本実施の形態では、単セルに燃料極中間層２および空気極中間層４を設ける場合を例に説明したが、燃料極中間層２および空気極中間層４のうち少なくとも一方を設けるようにしてもよい。このようにしても、本実施の形態と同等の作用効果を得ることができる。   In the present embodiment, the case where the fuel electrode intermediate layer 2 and the air electrode intermediate layer 4 are provided in the single cell has been described as an example. However, at least one of the fuel electrode intermediate layer 2 and the air electrode intermediate layer 4 is provided. It may be. Even if it does in this way, the effect equivalent to this Embodiment can be acquired.

本発明は、固体酸化物形燃料電池に適用することができる。   The present invention can be applied to a solid oxide fuel cell.

１…燃料極、２…燃料極中間層、３…電解質、４…空気極中間層、５…空気極、１１…下部マニホールド、１１ａ…凹部、１１ｂ…燃料流路、１１ｃ…排ガス流路、１２…ガラスシール、１３…上部マニホールド、１３ａ…酸化剤ガス流路、１４…重り。   DESCRIPTION OF SYMBOLS 1 ... Fuel electrode, 2 ... Fuel electrode intermediate | middle layer, 3 ... Electrolyte, 4 ... Air electrode intermediate | middle layer, 5 ... Air electrode, 11 ... Lower manifold, 11a ... Recessed part, 11b ... Fuel flow path, 11c ... Exhaust gas flow path, 12 ... Glass seal, 13 ... Upper manifold, 13a ... Oxidant gas flow path, 14 ... Weight.

Claims (6)

電解質と、この電解質の一方の面に形成された燃料極と、前記電解質の他方の面に形成された空気極とを備えた固体酸化物形燃料電池用単セルにおいて、
前記燃料極と前記電解質との間および前記空気極と前記電解質の間の少なくとも一方に設けられ、隣接する前記燃料極または前記空気極よりも低い気孔率を有しかつ厚さが薄い中間層を備える
ことを特徴とする固体酸化物形燃料電池用単セル。 In a solid oxide fuel cell single cell comprising an electrolyte, a fuel electrode formed on one surface of the electrolyte, and an air electrode formed on the other surface of the electrolyte,
An intermediate layer provided between at least one of the fuel electrode and the electrolyte and between the air electrode and the electrolyte and having a porosity lower than that of the adjacent fuel electrode or the air electrode and having a small thickness. A single cell for a solid oxide fuel cell. 前記電解質は、スカンジア安定化ジルコニアからなり、
前記燃料極は、酸化ニッケルと、前記スカンジア安定化ジルコニアまたはイットリア安定化ジルコニアとの混合体からなり、
前記中間層は、前記燃料極と前記電解質との間に設けられ、酸化ニッケルと金属酸化物をドープしたスカンジア安定化ジルコニアの混合体からなる
ことを特徴とする請求項１記載の固体酸化物形燃料電池用単セル。 The electrolyte is composed of scandia-stabilized zirconia,
The fuel electrode comprises a mixture of nickel oxide and the scandia-stabilized zirconia or yttria-stabilized zirconia,
2. The solid oxide form according to claim 1, wherein the intermediate layer is provided between the fuel electrode and the electrolyte, and is composed of a mixture of scandia-stabilized zirconia doped with nickel oxide and metal oxide. Single cell for fuel cells. 前記空気極は、ランタン系複合酸化物からなり、
前記電解質は、スカンジア安定化ジルコニアからなり、
前記中間層は、前記空気極と前記電解質の間に設けられ、ランタンニッケル鉄酸化物とセリア系電解質の混合体からなる
ことを特徴とする請求項１記載の固体酸化物形燃料電池用単セル。 The air electrode is made of a lanthanum complex oxide,
The electrolyte is composed of scandia-stabilized zirconia,
2. The single cell for a solid oxide fuel cell according to claim 1, wherein the intermediate layer is provided between the air electrode and the electrolyte, and is made of a mixture of lanthanum nickel iron oxide and a ceria-based electrolyte. . 前記電解質は、スカンジア安定化ジルコニアからなり、
前記燃料極は、酸化ニッケルと、前記スカンジア安定化ジルコニアまたはイットリア安定化ジルコニアとの混合体からなり、
前記空気極は、ランタン系複合酸化物からなり、
前記中間層は、前記燃料極と前記電解質との間および前記空気極と前記電解質との間に設けられ、
前記燃料極と前記電解質との間に設けられた中間層は、酸化ニッケルと金属酸化物をドープしたスカンジア安定化ジルコニアの混合体からなり、
前記空気極と前記電解質の間に設けられた中間層は、ランタンニッケル鉄酸化物とセリア系電解質の混合体からなる
ことを特徴とする請求項１記載の固体酸化物形燃料電池用単セル。 The electrolyte is composed of scandia-stabilized zirconia,
The fuel electrode comprises a mixture of nickel oxide and the scandia-stabilized zirconia or yttria-stabilized zirconia,
The air electrode is made of a lanthanum complex oxide,
The intermediate layer is provided between the fuel electrode and the electrolyte and between the air electrode and the electrolyte,
The intermediate layer provided between the fuel electrode and the electrolyte is composed of a mixture of scandia-stabilized zirconia doped with nickel oxide and metal oxide,
The single layer for a solid oxide fuel cell according to claim 1, wherein the intermediate layer provided between the air electrode and the electrolyte is composed of a mixture of lanthanum nickel iron oxide and a ceria-based electrolyte. 前記燃料極と前記電解質との間に設けられた前記中間層は、厚さが７μｍ以上２５μｍ以下である
ことを特徴とする請求項２または４記載の固体酸化物形燃料電池用単セル。 5. The single cell for a solid oxide fuel cell according to claim 2, wherein the intermediate layer provided between the fuel electrode and the electrolyte has a thickness of 7 μm or more and 25 μm or less. 前記空気極と前記電解質との間に設けられた前記中間層は、厚さが１μｍ以上２．２μｍ以下である
ことを特徴とする請求項３または４記載の固体酸化物形燃料電池用単セル。
5. The single cell for a solid oxide fuel cell according to claim 3, wherein the intermediate layer provided between the air electrode and the electrolyte has a thickness of 1 μm to 2.2 μm. .
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013115255A1 (en) * 2012-01-30 2013-08-08 京セラ株式会社 Solid oxide fuel battery cell, fuel battery module, and fuel battery device
JP2016529663A (en) * 2013-10-02 2016-09-23 エルジー・ケム・リミテッド Method for producing anode support for solid oxide fuel cell and anode support for solid oxide fuel cell
JP2017059504A (en) * 2015-09-18 2017-03-23 大阪瓦斯株式会社 Metal support electrochemical element, solid oxide fuel cell, and manufacturing method of metal support electrochemical element
JP2019515462A (en) * 2016-09-30 2019-06-06 エルジー・ケム・リミテッド Solid oxide fuel cell

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006236820A (en) * 2005-02-25 2006-09-07 Nippon Telegr & Teleph Corp <Ntt> Solid oxide fuel cell and manufacturing method of solid oxide fuel cell
JP2007073336A (en) * 2005-09-07 2007-03-22 Toto Ltd Solid oxide fuel cell
JP2007149431A (en) * 2005-11-25 2007-06-14 Nippon Telegr & Teleph Corp <Ntt> Solid oxide fuel cell and its formation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006236820A (en) * 2005-02-25 2006-09-07 Nippon Telegr & Teleph Corp <Ntt> Solid oxide fuel cell and manufacturing method of solid oxide fuel cell
JP2007073336A (en) * 2005-09-07 2007-03-22 Toto Ltd Solid oxide fuel cell
JP2007149431A (en) * 2005-11-25 2007-06-14 Nippon Telegr & Teleph Corp <Ntt> Solid oxide fuel cell and its formation method

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013115255A1 (en) * 2012-01-30 2013-08-08 京セラ株式会社 Solid oxide fuel battery cell, fuel battery module, and fuel battery device
JP5404973B1 (en) * 2012-01-30 2014-02-05 京セラ株式会社 Solid oxide fuel cell, fuel cell module, and fuel cell device
US9812726B2 (en) 2012-01-30 2017-11-07 Kyocera Corporation Solid oxide fuel cell, fuel cell module, and fuel cell device
JP2016529663A (en) * 2013-10-02 2016-09-23 エルジー・ケム・リミテッド Method for producing anode support for solid oxide fuel cell and anode support for solid oxide fuel cell
US10483578B2 (en) 2013-10-02 2019-11-19 Lg Chem, Ltd. Method for manufacturing anode support of solid oxide fuel cell, and anode support of solid oxide fuel cell
JP2017059504A (en) * 2015-09-18 2017-03-23 大阪瓦斯株式会社 Metal support electrochemical element, solid oxide fuel cell, and manufacturing method of metal support electrochemical element
WO2017047656A1 (en) * 2015-09-18 2017-03-23 大阪瓦斯株式会社 Metal support type electrochemical element, and method for manufacturing solid oxide type fuel cell and metal support type electrochemical element
US10892493B2 (en) 2015-09-18 2021-01-12 Osaka Gas Co., Ltd. Metal-supported electrochemical element, solid oxide fuel cell and method of manufacturing such metal-supported electrochemical element
US11189839B2 (en) 2015-09-18 2021-11-30 Osaka Gas Co., Ltd. Metal-supported electrochemical element, solid oxide fuel cell and method of manufacturing such metal-supported electrochemical element
US11189838B2 (en) 2015-09-18 2021-11-30 Osaka Gas Co., Ltd. Metal-supported electrochemical element, solid oxide fuel cell and method of manufacturing such metal-supported electrochemical element
JP2019515462A (en) * 2016-09-30 2019-06-06 エルジー・ケム・リミテッド Solid oxide fuel cell

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