JP5132104B2 - Heat-resistant alloy member, current collecting member for fuel cell, fuel cell stack, fuel cell - Google Patents

Heat-resistant alloy member, current collecting member for fuel cell, fuel cell stack, fuel cell Download PDF

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JP5132104B2
JP5132104B2 JP2006232483A JP2006232483A JP5132104B2 JP 5132104 B2 JP5132104 B2 JP 5132104B2 JP 2006232483 A JP2006232483 A JP 2006232483A JP 2006232483 A JP2006232483 A JP 2006232483A JP 5132104 B2 JP5132104 B2 JP 5132104B2
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昌彦 東
則光 深水
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Kyocera 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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Description

本発明は、Ｃｒを含有する合金板の表面をＣｒ拡散防止層により被覆してなる耐熱性合金部材及び燃料電池用集電部材並びに燃料電池セルスタック、燃料電池に関する。   The present invention relates to a heat-resistant alloy member, a current collecting member for a fuel cell, a fuel cell stack, and a fuel cell formed by coating the surface of an alloy plate containing Cr with a Cr diffusion preventing layer.

次世代エネルギーとして、近年、例えば、燃料電池セルのスタックを収納容器内に収容した燃料電池が種々提案されている。固体電解質形燃料電池は、複数の燃料電池セルを電気的に接続した燃料電池セルスタックを収納容器内に収容して構成され、燃料電池セルの燃料極側に燃料ガス（水素）を流し、空気極（酸素極ともいう）側に空気（酸素）を流して６００〜９００℃の高温で発電する。燃料電池セル間を電気的に接続するためには、従来からフェルト状や板状の燃料電池用集電部材（以下、特に断らない限り集電部材ともいう）が用いられている。   In recent years, for example, various fuel cells in which a stack of fuel cells is accommodated in a storage container have been proposed as next-generation energy. A solid oxide fuel cell is configured by storing a fuel cell stack in which a plurality of fuel cells are electrically connected in a storage container, and flowing a fuel gas (hydrogen) to the fuel electrode side of the fuel cell, and air Electric power is generated at a high temperature of 600 to 900 ° C. by flowing air (oxygen) to the electrode (also referred to as oxygen electrode) side. In order to electrically connect the fuel cells, a felt-shaped or plate-shaped current collecting member for a fuel cell (hereinafter also referred to as a current collecting member unless otherwise specified) has been used.

このような集電部材としては導電率の高い合金が採用され、さらに高温下で使用されることから、耐熱性合金が望ましく採用され、このような導電率の高い耐熱性合金として、Ｃｒを１０〜３０質量％含有する合金が一般的に用いられる。しかしながら、Ｃｒを含有する合金からなる集電部材を燃料電池セル間に介装し、複数の燃料電池セルを電気的に接続した場合、燃料電池を長期間発電させると、集電部材中のＣｒが集電部材の外部に拡散してしまい、拡散したＣｒは空気極と固体電解質との界面に達し、活性を劣化させてしまう。この現象は、いわゆるＣｒ被毒といわれ、燃料電池セルの発電能力の低下をまねくこととなる。   As such a current collecting member, an alloy having a high conductivity is adopted, and since it is used at a high temperature, a heat-resistant alloy is preferably adopted. As such a heat-resistant alloy having a high conductivity, 10% of Cr is used. An alloy containing -30% by mass is generally used. However, when a current collecting member made of an alloy containing Cr is interposed between the fuel cells and a plurality of fuel cells are electrically connected, if the fuel cell generates power for a long time, Cr in the current collecting member Diffuses to the outside of the current collector, and the diffused Cr reaches the interface between the air electrode and the solid electrolyte and degrades the activity. This phenomenon is referred to as so-called Cr poisoning and leads to a decrease in the power generation capacity of the fuel cell.

このようなＣｒ被毒を防止するため、従来、Ｃｒを含有する合金板の表面をＭｎ、Ｆｅ、Ｃｏ、Ｎｉで被覆することが行われている（特許文献１参照）。
特表平１１−５０１７６４号公報 In order to prevent such Cr poisoning, conventionally, the surface of an alloy plate containing Cr is coated with Mn, Fe, Co, and Ni (see Patent Document 1).
Japanese National Patent Publication No. 11-501764

しかしながら、Ｃｒの拡散を防止するため、上記特許文献１に記載されているようにＣｒ含有の合金板の表面をＭｎ、Ｆｅ、Ｃｏ、ＮｉからなるＣｒ拡散防止層で隙間なく被覆して集電部材を構成した場合、合金板中のＣｒが外部に拡散することをある程度抑制することができるものの、Ｃｒは特に大気に接する割合の高い集電部材の角部から拡散し、完全には防止できなかった。   However, in order to prevent the diffusion of Cr, as described in Patent Document 1, the surface of the Cr-containing alloy plate is covered with a Cr diffusion prevention layer made of Mn, Fe, Co, and Ni without any gap, thereby collecting current. When the member is configured, it is possible to prevent the Cr in the alloy plate from diffusing to the outside to some extent, but Cr diffuses from the corner of the current collecting member that is particularly in contact with the atmosphere and can be completely prevented. There wasn't.

即ち、合金板をＭｎ、Ｆｅ、Ｃｏ、Ｎｉを含有する浸漬溶液中に浸漬し、焼き付けてＣｒ拡散防止層を形成した場合、通常、Ｃｒ拡散防止層の厚みは角部が平坦部よりも薄くなり、この角部に電流集中が生じ、高温となってＣｒ拡散防止層が破損し易く、これによりＣｒが拡散し易いという問題があった。また、スパッタ法により被覆することも可能ではあるが、角部を十分に被覆することができず、角部から拡散し易いという問題があった。   That is, when an alloy plate is immersed in an immersion solution containing Mn, Fe, Co, Ni and baked to form a Cr diffusion prevention layer, the corner of the Cr diffusion prevention layer is usually thinner than the flat part. As a result, current concentration occurs in the corner portion, and the Cr diffusion preventing layer is easily damaged at a high temperature, thereby causing a problem that Cr is easily diffused. Further, although it is possible to cover by the sputtering method, there is a problem that the corner portion cannot be sufficiently covered and is easily diffused from the corner portion.

さらに、集電部材の作製上、必然的に角部が存在し、この角部にはバリが残り易く、その角部における被覆が不十分となり、そこからＣｒが拡散し易いという問題もある。   Further, in the production of the current collecting member, there is a problem that corners are inevitably present, and burrs are likely to remain at the corners, so that the coating at the corners is insufficient, and Cr easily diffuses therefrom.

本発明は、角部からのＣｒの拡散を防止できる耐熱性合金部材及び燃料電池用集電部材並びに燃料電池セルスタック、燃料電池を提供することを目的とする。   It is an object of the present invention to provide a heat-resistant alloy member, a fuel cell current collecting member, a fuel cell stack, and a fuel cell that can prevent Cr from diffusing from corners.

本発明の耐熱性合金部材は、Ｃｒを含有する合金板の表面をＭｎとＺｎとを含有する酸
化物からなる緻密なＣｒ拡散防止層で被覆し、該Ｃｒ拡散防止層の表面を酸化物からなり５５０〜９００℃で１Ｓｃｍ −１ 以上の導電率を有する被覆層で被覆してなるとともに、該被覆層の厚みが前記合金板の平面部よりも角部の方で厚いことを特徴とする。本発明の耐熱性合金部材では、Ｃｒ拡散防止層によりＣｒの拡散を防止できるとともに、Ｃｒ拡散が発生しやすい角部の被覆層の厚みを他の平面部の厚みより厚くしたので、角部の被覆層に電流集中が生じることがなくなり、これにより角部の異常発熱を防止し、Ｃｒ拡散防止層の破損を防止でき、角部からのＣｒの拡散を防止できる。
The heat resistant alloy member of the present invention covers the surface of an alloy plate containing Cr with a dense Cr diffusion prevention layer made of an oxide containing Mn and Zn, and the surface of the Cr diffusion prevention layer. together with formed by coating with a coating layer having a 1Scm -1 or more conductivity at 550 to 900 ° C. Do Ri oxide, the thickness of the coating layer is thicker than towards the corner than the planar portion of the alloy plate It is characterized by. In the heat resistant alloy member of the present invention, the Cr diffusion preventing layer can prevent the diffusion of Cr, and the thickness of the covering layer at the corner where Cr diffusion is likely to occur is made thicker than the thickness of the other flat portion. Current concentration does not occur in the coating layer, thereby preventing abnormal heat generation at the corners, preventing damage to the Cr diffusion preventing layer, and preventing diffusion of Cr from the corners.

また、本発明の耐熱性合金部材は、前記合金板の表面に、メッキ法又は静電塗装法により形成された金属層を熱処理して前記合金板の表面に前記Ｃｒ拡散防止層が形成され、該Ｃｒ拡散防止層の表面に被覆層が形成されていることを特徴とする。このような耐熱性合金部材では、合金板の角部における導電性の被覆層の厚みを平面部よりも厚く形成することができ、これにより、合金板の角部での異常発熱を防止でき、角部からのＣｒの拡散を防止できる。   Further, the heat resistant alloy member of the present invention, the Cr diffusion prevention layer is formed on the surface of the alloy plate by heat-treating a metal layer formed by plating or electrostatic coating method on the surface of the alloy plate, A coating layer is formed on the surface of the Cr diffusion preventing layer. In such a heat-resistant alloy member, the thickness of the conductive coating layer at the corner of the alloy plate can be formed thicker than the plane portion, thereby preventing abnormal heat generation at the corner of the alloy plate, The diffusion of Cr from the corner can be prevented.

さらに、本発明の耐熱性合金部材は、前記合金板の表面に、下地層をメッキ法で形成し、その上面に金属層をメッキ法で形成し、これを熱処理して、前記合金板の表面に酸化物からなる下地層を介して前記Ｃｒ拡散防止層が形成され、該Ｃｒ拡散防止層の表面に被覆層が形成されていることを特徴とする。   Furthermore, the heat-resistant alloy member of the present invention is formed by forming a base layer on the surface of the alloy plate by a plating method, forming a metal layer on the upper surface thereof by a plating method, and heat-treating the surface to the surface of the alloy plate. The Cr diffusion prevention layer is formed through an underlayer made of oxide, and a coating layer is formed on the surface of the Cr diffusion prevention layer.

このような耐熱性合金部材では、合金板に、濡れ性の良好な下地層をメッキ法で形成し、この上にＣｒ拡散防止層となる金属層をメッキ法で形成し、熱処理したので、合金板に酸化された下地層が形成され、この下地層の表面に、メッキ法でＣｒ拡散防止層、平面部よりも角部が厚い被覆層を確実に形成できる。下地層は、Ｆｅ、Ｃｏ、Ｎｉ及びＣｕのうち少なくとも一種から形成することが望ましい。   In such a heat-resistant alloy member, a base layer having good wettability is formed on the alloy plate by a plating method, and a metal layer serving as a Cr diffusion preventing layer is formed on the alloy plate by a plating method and heat-treated. An oxidized base layer is formed on the plate, and on the surface of the base layer, a Cr diffusion preventing layer and a coating layer whose corners are thicker than the flat part can be reliably formed by plating. The underlayer is preferably formed from at least one of Fe, Co, Ni, and Cu.

また、本発明の耐熱性合金部材は、前記合金板中にＭｎを含有するとともに、前記被覆層がＺｎを含有することを特徴とする。このような耐熱性合金部材では、被覆層がＺｎを含有することにより、高温での導電性が良好となる。
Further, the heat resistant alloy member of the present invention is to contain Mn in the alloy plate in front Symbol coating layer is characterized by containing Zn. In such a heat-resistant alloy member, by which the covering layer contains Zn, the conductivity of the high temperature becomes good.

本発明の燃料電池用集電部材は、燃料電池セルからの集電を行う集電部材が、上記耐熱性合金部材からなることを特徴とする。また、本発明の燃料電池セルスタックは、複数の燃料電池セルの間に、上記燃料電池用集電部材を介装してなる燃料電池セルスタックであって、前記燃料電池セルと前記燃料電池用集電部材とが、導電性接着材により接合されていることを特徴とする。本発明の燃料電池は、上記燃料電池セルスタックを、収納容器内に収納してなることを特徴とする。   The current collecting member for a fuel cell according to the present invention is characterized in that the current collecting member for collecting current from the fuel cell is composed of the above heat-resistant alloy member. The fuel cell stack of the present invention is a fuel cell stack in which the fuel cell current collecting member is interposed between a plurality of fuel cells, and the fuel cell and the fuel cell The current collecting member is joined by a conductive adhesive. The fuel cell of the present invention is characterized in that the fuel cell stack is stored in a storage container.

このような燃料電池用集電部材では、Ｃｒの拡散を十分に防止できるため、燃料電池セルの、いわゆるＣｒ被毒を防止でき、燃料電池セルの発電能力を高く維持できる。このような燃料電池用集電部材を用いた燃料電池セルスタック、燃料電池では、発電性能を高く維持できる。   In such a fuel cell current collector, Cr diffusion can be sufficiently prevented, so-called Cr poisoning of the fuel cell can be prevented, and the power generation capacity of the fuel cell can be maintained high. In the fuel cell stack and the fuel cell using such a current collecting member for a fuel cell, the power generation performance can be maintained high.

本発明の耐熱性合金部材は、合金板に、平面部よりも角部の方が厚い導電性の被覆層を形成したので、角部における電流集中が防止され、異常発熱によるＣｒ拡散防止層の破損を防止でき、これにより合金板角部からのＣｒの拡散を防止できる。   In the heat resistant alloy member of the present invention, a conductive coating layer having a thicker corner than a flat surface is formed on the alloy plate, so that current concentration at the corner is prevented and the Cr diffusion preventing layer due to abnormal heat generation is prevented. Breakage can be prevented, thereby preventing diffusion of Cr from the corners of the alloy plate.

図１は本発明の燃料電池用集電部材を示す斜視図であり、図２及び図３は図１に示す燃料電池用集電部材２０のＣｒ拡散防止層２０２、被覆層２０３の被覆状態を示す説明図である。図２は図１に示すＡ−Ａ線断面図であり、図３は図１に示すＢ−Ｂ線断面図である。燃料電池用集電部材２０は、図１に示すように、例えば耐熱性合金板を櫛刃状に加工し、隣り合う刃を交互に反対側に折り曲げて構成される。   FIG. 1 is a perspective view showing a fuel cell current collecting member according to the present invention. FIGS. 2 and 3 show the covering state of the Cr diffusion preventing layer 202 and the coating layer 203 of the fuel cell current collecting member 20 shown in FIG. It is explanatory drawing shown. 2 is a cross-sectional view taken along line AA shown in FIG. 1, and FIG. 3 is a cross-sectional view taken along line BB shown in FIG. As shown in FIG. 1, the fuel cell current collecting member 20 is formed, for example, by processing a heat-resistant alloy plate into a comb blade shape and alternately bending adjacent blades to the opposite side.

この集電部材２０は、Ｃｒを含有する合金からなる耐熱性合金板（以下、集電基材という。）２０１の表面を、酸化物（例えばセラミックス等、以下同じ）からなる緻密なＣｒ拡散防止層２０２、導電性の被覆層２０３が被覆している。尚、図２，図３においては、Ｃｒ拡散防止層２０２を太線で記載した。Ｃｒ拡散防止層２０２は、集電基材２０１の全周面を隙間なく被覆している。なお、本発明の燃料電池用集電部材２０は、図１に示すような形状のものに限定されるものではなく、例えば、円筒状、メッシュ状のものであってもよい。   This current collecting member 20 has a dense Cr diffusion prevention made of an oxide (for example, ceramic, etc., hereinafter the same) on the surface of a heat resistant alloy plate (hereinafter referred to as current collecting base material) 201 made of an alloy containing Cr. The layer 202 and the conductive coating layer 203 are covered. 2 and 3, the Cr diffusion preventing layer 202 is indicated by a bold line. The Cr diffusion preventing layer 202 covers the entire circumferential surface of the current collecting base material 201 without any gaps. The fuel cell current collecting member 20 of the present invention is not limited to the shape shown in FIG. 1, and may be, for example, a cylindrical shape or a mesh shape.

ここで集電基材２０１の材料としては、導電性および耐熱性の高いＣｒを１０〜３０質量％含有する合金、例えばＦｅ−Ｃｒ系合金、Ｎｉ−Ｃｒ系合金等を用いることができる。   Here, as a material of the current collecting base material 201, an alloy containing 10 to 30% by mass of Cr having high conductivity and heat resistance, for example, Fe—Cr alloy, Ni—Cr alloy, or the like can be used.

そして、この集電基材２０１の表面には、酸化物からなるＣｒ拡散防止層２０２、酸化物からなる導電性の被覆層２０３が被覆されている。Ｃｒ拡散防止層２０２は、ＭｎとＺｎを含有する酸化物からなることが好ましい。 The surface of the current collecting base 201 is covered with a Cr diffusion preventing layer 202 made of an oxide and a conductive coating layer 203 made of an oxide. The Cr diffusion preventing layer 202 is preferably made of an oxide containing Mn and Zn.

上述したように、Ｃｒ拡散防止層２０２は、集電基材２０１に含有されるＣｒが拡散することを有効に防止するため、例えば、スピネル構造を有する金属酸化物により形成される。ここで、Ｃｒの拡散を防止する上で、Ｃｒ拡散防止層２０２は、特に、Ｚｎ系スピネルからなるものであるのが好ましく、例えばＺｎ−Ｍｎ系スピネルからなるのがより好ましい。Ｚｎ−Ｍｎ系スピネルにおいては、Ｆｅ、Ｃｒ等の元素を含有してもよい。具体的には、Ｚｎ−Ｍｎ系スピネル、例えば、（Ｚｎ，Ｍｎ）Ｍｎ２Ｏ４からなる、ＺｎとＭｎを含む金属酸化物は、Ｃｒを固溶しにくいために、Ｃｒの拡散を抑制する効果を有している。 As described above, the Cr diffusion preventing layer 202 is formed of, for example, a metal oxide having a spinel structure in order to effectively prevent Cr contained in the current collector base material 201 from diffusing. Here, in order to prevent Cr from diffusing, the Cr diffusion preventing layer 202 is particularly preferably made of Zn-based spinel, and more preferably made of, for example, Zn-Mn spinel. The Zn—Mn spinel may contain elements such as Fe and Cr. Specifically, a metal oxide containing Zn and Mn made of a Zn—Mn-based spinel, for example, (Zn, Mn) Mn 2 O 4 , suppresses Cr diffusion because it is difficult to dissolve Cr. Has an effect.

このＺｎ−Ｍｎ系スピネルは、例えば、Ｍｎを含有する集電基材２０１に、Ｚｎをメッキし、熱処理することにより、Ｍｎが集電基材２０１から拡散し、集電基材２０１表面をＺｎ−Ｍｎ系スピネルからなるＣｒ拡散防止層２０２で被覆される。さらに、このＣｒ拡散防止層２０２の表面には、Ｍｎが拡散していない、ＺｎＯからなる被覆層２０３が形成されることになる。   In this Zn—Mn-based spinel, for example, Zn is plated on a current collecting base material 201 containing Mn and heat-treated, so that Mn diffuses from the current collecting base material 201, and the surface of the current collecting base material 201 becomes Zn. Covered with a Cr diffusion preventing layer 202 made of -Mn spinel. Furthermore, a coating layer 203 made of ZnO in which Mn is not diffused is formed on the surface of the Cr diffusion preventing layer 202.

Ｃｒ拡散防止層２０２の厚みは、２μｍ以下、特には１μｍ以下であれば、ある程度絶縁性であっても集電部材としての導電性に影響を与えることがない。   If the thickness of the Cr diffusion preventing layer 202 is 2 μm or less, particularly 1 μm or less, the conductivity as a current collecting member is not affected even if it is insulative to some extent.

そして、導電性の被覆層２０３の厚みは、図４（ａ）に示すように、集電基材２０１の平面部の被覆層２０３ｂよりも角部の被覆層２０３ａの方が厚く形成されている。   As shown in FIG. 4A, the conductive coating layer 203 is formed such that the corner coating layer 203 a is thicker than the planar coating layer 203 b of the current collecting base material 201. .

このような被覆層２０３は、集電基材２０１に、メッキ法又は静電塗装法により形成された金属層を熱処理することにより、集電基材２０１の表面にＣｒ拡散防止層２０２を形成し、該Ｃｒ拡散防止層２０２の表面に被覆層２０３を形成することができる。   Such a covering layer 203 forms a Cr diffusion preventing layer 202 on the surface of the current collecting base material 201 by heat-treating a metal layer formed on the current collecting base material 201 by a plating method or an electrostatic coating method. The coating layer 203 can be formed on the surface of the Cr diffusion preventing layer 202.

Ｃｒ拡散防止層２０２、被覆層２０３を形成するための金属層は、例えば、電解メッキにより、容易に形成することができる。電解メッキでは集電基材２０１と電解液との電位差により被覆するものであるが、特に角部は外部に晒されている割合が大きいため、電解液中では平面部より厚く被覆することができる。同じ理由で、静電塗装法による被覆でも、角部の被覆層２０３ａを厚く被覆することができる。   The metal layer for forming the Cr diffusion preventing layer 202 and the covering layer 203 can be easily formed by, for example, electrolytic plating. In electrolytic plating, coating is performed by the potential difference between the current collecting base material 201 and the electrolytic solution. However, since the corner portion is exposed to the outside in particular, the electrolytic solution can be coated thicker than the flat portion. . For the same reason, the coating layer 203a at the corners can be thickly coated by the electrostatic coating method.

従来、ディップ法などにより角部の被覆層２０３ａの厚みを十分に厚くしようとすると、それ以上に平面部の被覆層２０３ｂが厚くなり、集電基材２０１との熱膨張差の違いにより被覆層にクラックなどが発生し、このクラックに沿って、Ｃｒが拡散しやすくなるが、本発明では、平面部の被覆層２０３ｂの厚みを必要以上に厚くすることなく、角部の被覆層２０３ａの厚みを十分に厚くできるため、熱膨張差によるクラックの発生も防ぐことができる。   Conventionally, when it is attempted to sufficiently increase the thickness of the covering layer 203a at the corners by the dipping method or the like, the covering layer 203b at the flat portion becomes thicker than that, and the coating layer is different due to a difference in thermal expansion from the current collector base 201. In the present invention, the thickness of the corner coating layer 203a is increased without increasing the thickness of the planar coating layer 203b more than necessary. Can be made sufficiently thick to prevent cracking due to thermal expansion differences.

被覆層２０３の厚みは、ＺｎＯからなる場合には、導電性を有するという点から、３μｍ以下であることが望ましい。また、後述するように、ＺｎＯにＦｅが固溶した導電性の被覆層の場合には、集電基材２０１との熱膨張係数差を小さくするという点から、５０μｍ以下であることが望ましい。   The thickness of the coating layer 203 is desirably 3 μm or less from the viewpoint of having conductivity when made of ZnO. As will be described later, in the case of a conductive coating layer in which Fe is dissolved in ZnO, the thickness is preferably 50 μm or less from the viewpoint of reducing the difference in thermal expansion coefficient from the current collecting base material 201.

電解メッキで、Ｚｎ−Ｍｎ系スピネルからなるＣｒ拡散防止層２０２を形成するには、亜鉛イオンを１０〜６００ｇ／ｌ含む浴に、Ｍｎを含有する集電基材２０１を陰極として挿入し、電流密度１５〜４００Ａ／ｍ２の電流を印加することにより、集電基材２０１にＺｎからなる金属層が形成され、この金属層を１０００〜１１００℃で熱処理することにより、集電基材２０１表面にＺｎ−Ｍｎ系スピネルからなるＣｒ拡散防止層２０２を形成し、その表面にＺｎＯからなる被覆層２０３を形成することができる。メッキ法の場合、急激に高温とするとＺｎが気化するという理由から、一度、例えば３５０℃で熱処理し、酸化亜鉛にした後、１０００〜１１００℃で再度、熱処理することが望ましい。 In order to form the Cr diffusion preventing layer 202 made of Zn—Mn spinel by electrolytic plating, a current collecting base material 201 containing Mn is inserted as a cathode into a bath containing 10 to 600 g / l of zinc ions, By applying a current having a density of 15 to 400 A / m 2, a metal layer made of Zn is formed on the current collecting base material 201, and by heat-treating this metal layer at 1000 to 1100 ° C., the surface of the current collecting base material 201 A Cr diffusion preventing layer 202 made of Zn-Mn spinel can be formed on the surface, and a coating layer 203 made of ZnO can be formed on the surface thereof. In the case of the plating method, it is desirable to heat-treat once at, for example, 350 ° C. to make zinc oxide, and then heat-treat again at 1000 to 1100 ° C. because Zn vaporizes when the temperature is rapidly increased.

集電基材２０１には直接Ｚｎメッキしにくいため、Ｆｅ、Ｃｏ、Ｎｉ及びＣｕのうち少なくとも一種の下地層をメッキ法で形成し、その上面にＺｎをメッキ法で形成し、これを大気中にて熱処理することが望ましい。尚、Ｆｅ、Ｃｏ、Ｎｉ及びＣｕは、Ｃｒの拡散を防止する機能も有するため、さらにＣｒの拡散が防止できる。さらに、Ｆｅを下地層として用いる場合には、このＦｅが被覆層２０３を形成するＺｎＯに固溶し、導電性を有することができるため、望ましい。   Since the current collecting base material 201 is difficult to be directly plated with Zn, at least one underlayer of Fe, Co, Ni, and Cu is formed by a plating method, and Zn is formed on the upper surface thereof by a plating method. It is desirable to heat-treat with. In addition, since Fe, Co, Ni, and Cu also have a function of preventing the diffusion of Cr, the diffusion of Cr can be further prevented. Further, when Fe is used as the underlayer, it is desirable because this Fe can be dissolved in ZnO forming the covering layer 203 and have conductivity.

尚、集電基材２０１にＦｅを含有する場合には、Ｆｅが熱処理時に拡散して、被覆層２０３を形成するＺｎＯに固溶し、導電性を有することができる。被覆層２０３は、高温中で導電性を有するものであるが、５５０〜９００℃で１Ｓｃｍ−１以上の導電率を有することが望ましい。この導電率は、５５０〜９００℃に加熱した被覆層２０３に、電流を印加し電圧を測定することにより測定することができる。 When Fe is contained in the current collecting base material 201, Fe diffuses during the heat treatment and can be dissolved in ZnO forming the coating layer 203 to have conductivity. The covering layer 203 has conductivity at a high temperature, but desirably has a conductivity of 1 Scm −1 or more at 550 to 900 ° C. This conductivity can be measured by applying a current to the coating layer 203 heated to 550 to 900 ° C. and measuring the voltage.

また、静電塗装法によりＣｒ拡散防止層を形成するには、集電基材２０１から０．１〜０．５ｍ離れた位置に帯電塗装ガンを設置し、塗装ガン印加電圧−４０〜−１００ｋＶ、吐出量５０〜１５０ｇ／分、吐出圧０．５〜２．５×１０５Ｎ／ｍ２、エアー流量３〜６ｍ３／ｈで、Ｚｎ粉末を吐出し、集電基材２０１表面に塗装し、１０００〜１１００℃で熱処理することにより、集電基材２０１表面にＺｎ−Ｍｎ系スピネルからなるＣｒ拡散防止層２０２を形成し、その表面にＺｎＯからなる被覆層２０３を形成することができる。静電塗装法の場合には、Ｚｎ粉末のみならず、Ｚｎ粉末とＦｅ粉末を吐出できる。 Further, in order to form the Cr diffusion preventing layer by the electrostatic coating method, a charged coating gun is installed at a position 0.1 to 0.5 m away from the current collecting base material 201, and a coating gun applied voltage of -40 to -100 kV. The Zn powder is discharged at a discharge amount of 50 to 150 g / min, a discharge pressure of 0.5 to 2.5 × 10 5 N / m 2 , and an air flow rate of 3 to 6 m 3 / h, and the surface of the current collecting substrate 201 is coated. Then, by performing heat treatment at 1000 to 1100 ° C., the Cr diffusion preventing layer 202 made of Zn—Mn spinel can be formed on the surface of the current collecting base material 201, and the coating layer 203 made of ZnO can be formed on the surface. . In the case of the electrostatic coating method, not only Zn powder but also Zn powder and Fe powder can be discharged.

尚、図４（ｂ）は、従来のディップ法によりＣｒ拡散防止層２０２、被覆層２０３を形成した場合であり、この場合には、被覆層２０３は角部の被覆層２０３ａが平面部の被覆層２０３ｂより薄く形成され、角部での電流集中により、異常発熱が生じ、Ｃｒ拡散防止層２０２が破損し易いことが判る。   FIG. 4B shows the case where the Cr diffusion preventing layer 202 and the covering layer 203 are formed by the conventional dipping method. In this case, the covering layer 203 is formed by covering the corner portion covering layer 203a with the flat portion. It can be seen that the layer 203b is thinner than the layer 203b, and abnormal heat generation occurs due to current concentration at the corners, and the Cr diffusion preventing layer 202 is easily damaged.

以上のように構成された燃料電池用集電部材では、Ｃｒ拡散防止層２０２によりＣｒの拡散を防止できるとともに、Ｃｒ拡散が発生しやすい角部の被覆層２０３ａの厚みを他の平面部の厚みより厚くしたので、角部の被覆層２０３ａに電流集中が生じることがなくなり、これにより角部の被覆層２０３ａの異常発熱を防止し、Ｃｒ拡散防止層２０２の破損を防止でき、角部からのＣｒの拡散を防止できる。   In the fuel cell current collector configured as described above, Cr diffusion can be prevented by the Cr diffusion prevention layer 202, and the thickness of the covering layer 203a at the corner portion where Cr diffusion is likely to occur is made the thickness of the other flat portion. Since it is thicker, current concentration does not occur in the corner covering layer 203a, thereby preventing abnormal heating of the corner covering layer 203a and preventing the Cr diffusion prevention layer 202 from being damaged. Cr diffusion can be prevented.

図５は本発明の燃料電池セルの斜視図であり、図６は燃料電池セルを集電部材により電気的に接続してなるセルスタックを示す断面図である。本発明によるセルスタックは、図６に示すように、燃料電池用集電部材２０が、図５に示す中空平板形の燃料電池セル１間に配置されて複数の燃料電池セル１を電気的に接続する構成を有する。   FIG. 5 is a perspective view of the fuel battery cell of the present invention, and FIG. 6 is a cross-sectional view showing a cell stack in which the fuel battery cells are electrically connected by a current collecting member. In the cell stack according to the present invention, as shown in FIG. 6, a fuel cell current collecting member 20 is disposed between the hollow flat plate fuel cells 1 shown in FIG. It has a configuration to connect.

燃料電池セル１は、図５に示すように、平板状の支持基板１０と、平板状の支持基板１０の周囲に設けられた多孔質の燃料極層２、緻密な固体電解質層３、多孔質の酸素極層４、緻密なインターコネクタ５、及び酸素極材料層１４とを備え、支持基板１０は、さらに内部に、燃料電池セル１の積層方向に交わる方向（セル長さ方向）に伸びた複数の燃料ガス通路１６を有している。   As shown in FIG. 5, the fuel battery cell 1 includes a flat support substrate 10, a porous fuel electrode layer 2 provided around the flat support substrate 10, a dense solid electrolyte layer 3, a porous The oxygen electrode layer 4, the dense interconnector 5, and the oxygen electrode material layer 14, and the support substrate 10 further extends in the direction intersecting the stacking direction of the fuel cells 1 (cell length direction). A plurality of fuel gas passages 16 are provided.

支持基板１０は、例えば、多孔質かつ導電性の材料からなり、図５に示すように横断面が平坦部と平坦部の両端の弧状部とからなっている。平坦部の対向する面の一方とその両端の弧状部を覆うように多孔質の燃料極層２が設けられており、この燃料極層２を覆うように、緻密質な固体電解質層３が積層されており、さらに、この固体電解質層３の上には、燃料極層２に対向するように、多孔質の導電性セラミックからなる酸素極層４が積層されている。また、支持基板１０の電極層２、４が設けられた面に対向する面には、緻密なインターコネクタ５が形成されている。このインターコネクタ５の表面には、酸素極材料からなる酸素極材料層１４が形成されている。ここで、酸素極材料は、例えばペロブスカイト構造のＬａＦｅＯ３系やＬａＭｎＯ３系等（例えば、Ｌａ（Ｆｅ，Ｍｎ）Ｏ３、（Ｌａ，Ｓｒ）（Ｃｏ，Ｆｅ）Ｏ３等）の酸化物（導電性セラミックス）からなる。ただし、この酸素極材料層１４については、必ずしも形成する必要はない。図５に示すように、燃料極層２及び固体電解質層３は、インターコネクタ５の両サイドまで延び、支持基板１０の表面が外部に露出しないように構成されている。 The support substrate 10 is made of, for example, a porous and conductive material, and has a flat cross section and arcuate portions at both ends of the flat portion as shown in FIG. A porous fuel electrode layer 2 is provided so as to cover one of the opposing surfaces of the flat portion and arc-shaped portions at both ends thereof, and a dense solid electrolyte layer 3 is laminated so as to cover the fuel electrode layer 2. Further, an oxygen electrode layer 4 made of a porous conductive ceramic is laminated on the solid electrolyte layer 3 so as to face the fuel electrode layer 2. A dense interconnector 5 is formed on the surface of the support substrate 10 that faces the surface on which the electrode layers 2 and 4 are provided. An oxygen electrode material layer 14 made of an oxygen electrode material is formed on the surface of the interconnector 5. Here, the oxygen electrode material is an oxide (for example, La (Fe, Mn) O 3 , (La, Sr) (Co, Fe) O 3, etc.) having a perovskite structure such as LaFeO 3 or LaMnO 3. Conductive ceramic). However, the oxygen electrode material layer 14 is not necessarily formed. As shown in FIG. 5, the fuel electrode layer 2 and the solid electrolyte layer 3 extend to both sides of the interconnector 5 and are configured so that the surface of the support substrate 10 is not exposed to the outside.

このような構造の燃料電池セル１は、燃料極層２の酸素極層４と対面している部分が燃料極として作動して発電する。即ち、酸素極層４の外側に空気等の酸素含有ガスを流し、且つ支持基板１０内のガス通路１６に燃料ガス（水素）を流し、所定の作動温度まで加熱することにより、酸素極層４で下記の式（１）の電極反応が生じ、また燃料極層２の燃料極となる部分では例えば下記の式（２）の電極反応が生じることによって発電する。   In the fuel cell 1 having such a structure, the portion of the fuel electrode layer 2 facing the oxygen electrode layer 4 operates as a fuel electrode to generate electric power. That is, an oxygen-containing gas such as air is allowed to flow outside the oxygen electrode layer 4 and a fuel gas (hydrogen) is supplied to the gas passage 16 in the support substrate 10 and heated to a predetermined operating temperature. Then, an electrode reaction of the following formula (1) occurs, and power is generated by, for example, an electrode reaction of the following formula (2) occurring in the portion that becomes the fuel electrode of the fuel electrode layer 2.

酸素極： １／２Ｏ２＋２ｅ− → Ｏ２ − （固体電解質） （１）
燃料極： Ｏ２ − （固体電解質）＋ Ｈ２ → Ｈ２Ｏ＋２ｅ− （２）
かかる電極反応によって発生した電流は、支持基板１０に取り付けられているインターコネクタ５を介して集電される。 Oxygen electrode: 1 / 2O 2 + 2e − → O 2 − (solid electrolyte) (1)
Fuel electrode: O 2 − (solid electrolyte) + H 2 → H 2 O + 2e − (2)
The current generated by the electrode reaction is collected through the interconnector 5 attached to the support substrate 10.

このような複数の燃料電池セルの間には、図６に示すように、集電部材２０が介装されて電気的に接続され、これによりセルスタックが構成されている。即ち、集電部材２０が、一方の燃料電池セル１の酸素極層４に多孔質の導電性セラミック等の導電性接着材２５により接合されると共に、隣設する他方の燃料電池セル１の酸素極材料層１４に導電性接着材２５により接合され、これにより、複数の燃料電池セル１が電気的に直列に接続され、セルスタックが構成されている。   As shown in FIG. 6, a current collecting member 20 is interposed and electrically connected between the plurality of fuel cells as described above, thereby forming a cell stack. That is, the current collecting member 20 is joined to the oxygen electrode layer 4 of one fuel battery cell 1 by a conductive adhesive 25 such as a porous conductive ceramic, and the oxygen of the other fuel battery cell 1 adjacent thereto is joined. The electrode material layer 14 is joined by a conductive adhesive 25, whereby the plurality of fuel cells 1 are electrically connected in series to form a cell stack.

セルスタックの製造は、燃料電池セル１と集電部材２０を交互に積層することによって行われる。   The cell stack is manufactured by alternately stacking the fuel cells 1 and the current collecting members 20.

初めに、導電性接着材２５をスクリーン印刷法により燃料電池セル１の電極部（酸素極層４、酸素極材料層１４）に塗布する。次に燃料電池セル１の電極部に燃料電池用集電部材２０を載置し、さらにその上に次の燃料電池セル１を載置する。これを必要数繰り返して、燃料電池セル１と燃料電池用集電部材２０の積層体を作製する。   First, the conductive adhesive 25 is applied to the electrode portions (the oxygen electrode layer 4 and the oxygen electrode material layer 14) of the fuel cell 1 by screen printing. Next, the fuel cell current collecting member 20 is placed on the electrode portion of the fuel cell 1, and the next fuel cell 1 is placed thereon. This is repeated as many times as necessary to produce a laminate of the fuel cell 1 and the fuel cell current collecting member 20.

次に、該積層体を９００℃〜１１００℃の温度に加熱して、導電性接着材２５を燃料電池セル１の電極部と燃料電池用集電部材２０に焼き付け、セルスタックを作製する。 Next, the laminated body is heated to a temperature of 900 ° C. to 1100 ° C., and the conductive adhesive 25 is baked on the electrode part of the fuel cell 1 and the current collecting member 20 for the fuel cell to produce a cell stack.

なお、導電性接着材２５としては、酸素極材料、又は酸素極材料とＣｒ拡散防止層２０２の材料を含有する材料が用いられる。尚、酸素極材料層１４を形成しない場合にはインターコネクタに接合される。   As the conductive adhesive 25, an oxygen electrode material or a material containing the oxygen electrode material and the material of the Cr diffusion preventing layer 202 is used. When the oxygen electrode material layer 14 is not formed, it is joined to the interconnector.

尚、図５において、燃料電池セル１は中空平板型の燃料電池セル１を示したが、例えば円筒形等の燃料電池セルを用いることもできる。ただし、本発明においては、燃料電池セル１と燃料電池用集電部材２０との剥離を防止するため、両者を面と面とで接合することが好ましい。なお、面と面とで接合するとは、燃料電池セル１と燃料電池用集電部材２０との対向する面同士が、導電性接着材等により接合される状態を意味する。これにより、燃料電池セル１と燃料電池用集電部材２０とが、十分な接合面積にて接合されることとなる。   In FIG. 5, the fuel battery cell 1 is a hollow plate type fuel battery cell 1. However, for example, a cylindrical fuel battery cell may be used. However, in the present invention, in order to prevent the fuel cell 1 and the fuel cell current collecting member 20 from being peeled off, it is preferable to join both of them face to face. In addition, joining with a surface means the state by which the surfaces where the fuel cell 1 and the current collecting member 20 for fuel cells oppose are joined by a conductive adhesive or the like. Thereby, the fuel cell 1 and the fuel cell current collecting member 20 are joined with a sufficient joining area.

本発明の燃料電池は、上記のセルスタックを収納容器内に収容し、この収納容器に、都市ガス等の燃料ガスを供給する燃料ガス導入管及び空気を供給するための空気導入管を配設することにより構成される。このようなセルスタック及び燃料電池により、電圧低下の少ない長期信頼性に優れた燃料電池を得ることができる。   The fuel cell of the present invention accommodates the cell stack in a storage container, and a fuel gas introduction pipe for supplying fuel gas such as city gas and an air introduction pipe for supplying air are disposed in the storage container. It is constituted by doing. With such a cell stack and fuel cell, it is possible to obtain a fuel cell with little voltage drop and excellent long-term reliability.

尚、上記形態では、本発明の耐熱性合金部材を燃料電池用集電部材２０として用いた場合について説明したが、収納容器内に収容される他の耐熱性合金からなる部品、例えば、マニホールド用として、また改質器用として、さらには収納容器を形成する壁部材として用いることができる。   In the above embodiment, the case where the heat-resistant alloy member of the present invention is used as the fuel cell current collecting member 20 has been described. However, for example, a component made of another heat-resistant alloy housed in the housing container, for example, for a manifold In addition, it can be used for a reformer, and further as a wall member for forming a storage container.

また、上記形態では、本発明の耐熱性合金部材を燃料電池用集電部材２０として用いた場合について説明したが、本発明の耐熱性合金部材を燃料電池以外のものに用いても良い。例えば、酸素センサのリード部等の高温雰囲気で導電性を有するもの、具体的には、従来高温雰囲気で導電性を示すものとして使用されていたＰｔの代用として使用することができる。因みに、酸素センサ等のリード部では、高温で導電性を確保するため、Ｐｔ等の貴金属を用いており、高価であったが、本発明の耐熱性導電部材を用いることにより、安価とすることができる。   Moreover, although the said form demonstrated the case where the heat resistant alloy member of this invention was used as the current collection member 20 for fuel cells, you may use the heat resistant alloy member of this invention for things other than a fuel cell. For example, it can be used as a substitute for Pt that has conductivity in a high temperature atmosphere such as a lead portion of an oxygen sensor, specifically, Pt that has been conventionally used to exhibit conductivity in a high temperature atmosphere. By the way, lead parts such as oxygen sensors use precious metals such as Pt in order to ensure conductivity at high temperatures, and are expensive. However, by using the heat-resistant conductive member of the present invention, the lead parts should be made inexpensive. Can do.

厚さ０．４ｍｍ、幅２０ｍｍ、長さ１２０ｍｍのＦｅ−Ｃｒ系耐熱性合金板（Ｆｅ７５質量％含有、残部Ｃｒ、Ｍｎ、Ｎｉ含有）からなる集電基材のアルカリ脱脂を行った後、水洗し、表面を活性化させるために、硝酸で酸洗いを行った。その後再度水洗し、下地にニッケルメッキを電界メッキにて１μｍ施し、その後水洗をした。   After performing alkaline degreasing of a current collecting base material comprising a Fe—Cr heat-resistant alloy plate (containing 75% by mass of Fe, containing the remaining Cr, Mn, and Ni) having a thickness of 0.4 mm, a width of 20 mm, and a length of 120 mm, then washing with water In order to activate the surface, pickling with nitric acid was performed. Thereafter, it was washed again with water, and nickel plating was applied to the base by 1 μm by electroplating, followed by washing with water.

次に亜鉛イオンを２００ｇ／ｌ含む亜鉛浴を用意し、その中に集電基材を浸漬した。この集電基材を陰極とするように、電流を電流密度が１５０Ａ／ｍ２となるように、印加した。印加時間は７分とした。この後、３５０℃の炉に１０時間入れ、酸化亜鉛を形成した。さらにその後に１０００℃の炉に２時間入れることで酸化亜鉛と集電基材とを反応させ、Ｚｎ−Ｍｎ系スピネルからなるＣｒ拡散防止層、ＺｎＯにＦｅが固溶した被覆層を形成した。Ｃｒ拡散防止層の厚みは１μｍであり、被覆層の厚みは平面部で３μｍ、角部で５μｍであった。 Next, a zinc bath containing 200 g / l of zinc ions was prepared, and the current collecting substrate was immersed therein. A current was applied so that the current density was 150 A / m 2 so that the current collecting substrate was a cathode. The application time was 7 minutes. Thereafter, it was placed in a furnace at 350 ° C. for 10 hours to form zinc oxide. Furthermore, after putting in a 1000 degreeC furnace for 2 hours, the zinc oxide and the current collection base material were made to react, and the Cr diffusion prevention layer which consists of Zn-Mn spinel, and the coating layer which Fe dissolved in ZnO were formed. The thickness of the Cr diffusion preventing layer was 1 μm, and the thickness of the coating layer was 3 μm at the flat portion and 5 μm at the corner.

次に、平均粒径０．５μｍのＬａ０．６Ｓｒ０．４Ｃｏ０．２Ｆｅ０．８Ｏ３粉末（ＬＳＣＦ）と、アクリル系バインダーと、グリコール系溶剤とを添加して得られたスラリー中に、被覆層が形成された集電部材を浸漬し、１０００℃で２時間の焼付け処理を行い、被覆層表面に厚さ２０μｍのＬＳＣＦ膜を形成し、テストピースとした。このテストピースを８５０℃の炉に３０００ｈｒ投入した後、断面を切り出しＥＰＭＡによる半定量分析を行った。ＥＰＭＡ分析には、日本電子製のＪＸＡ−８１００を用いた。測定条件として、加速電圧１５ｋＶ、プローブ電流２．０×１０−７Ａ、分析エリア５０μｍ×５０μｍ、分光結晶にＬＩＦを用いた。その結果、Ｃｒ拡散防止層の外側のＬＳＣＦではＣｒの拡散量が検出限界の０．５質量％以下であった。尚、ＬＳＣＦ膜はＣｒと容易に反応して反応生成物を形成するため、被覆層から外部にＣｒが拡散した場合でも、ＬＳＣＦ膜で必ずＣｒの反応生成物を形成し、外部に拡散することはない。 Next, it was obtained by adding La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 powder (LSCF) having an average particle size of 0.5 μm, an acrylic binder, and a glycol solvent. The current collecting member on which the coating layer was formed was immersed in the slurry and subjected to a baking treatment at 1000 ° C. for 2 hours to form a LSCF film having a thickness of 20 μm on the surface of the coating layer to obtain a test piece. After putting this test piece into a furnace at 850 ° C. for 3000 hours, a cross section was cut out and semi-quantitative analysis by EPMA was performed. For the EPMA analysis, JXA-8100 manufactured by JEOL Ltd. was used. As measurement conditions, an acceleration voltage of 15 kV, a probe current of 2.0 × 10 −7 A, an analysis area of 50 μm × 50 μm, and LIF were used for the spectroscopic crystal. As a result, in the LSCF outside the Cr diffusion preventing layer, the Cr diffusion amount was 0.5% by mass or less of the detection limit. Since the LSCF film easily reacts with Cr to form a reaction product, even when Cr diffuses from the coating layer to the outside, the LSCF film always forms a Cr reaction product and diffuses to the outside. There is no.

また、電流密度が２００Ａ／ｍ２とする以外は上記と同様にして、厚みが１μｍのＣｒ拡散防止層、平面部の厚みが５μｍ、角部の厚みが７μｍの被覆層を形成した。さらに、電流の印加時間を１４分とする以外は上記と同様にして、厚みが１μｍのＣｒ拡散防止層、平面部の厚みが５μｍ、角部の厚みが７μｍの被覆層を形成した。これらについても、上記と同様にして、被覆層表面に厚さ２０μｍのＬＳＣＦ膜を形成し、８５０℃の炉に３０００ｈｒ投入した後、断面を切り出しＥＰＭＡによる半定量分析を上記と同様にして行った結果、Ｃｒ拡散防止層の外側のＬＳＣＦではＣｒの拡散量が検出限界の０．５質量％以下であった。 In addition, a Cr diffusion preventing layer having a thickness of 1 μm, a covering layer having a thickness of 5 μm on a flat surface, and a thickness of 7 μm on a corner were formed in the same manner as described above except that the current density was 200 A / m 2 . Further, a Cr diffusion preventing layer having a thickness of 1 μm, a covering layer having a planar portion having a thickness of 5 μm, and a corner portion having a thickness of 7 μm were formed in the same manner as described above except that the current application time was 14 minutes. In these cases, a LSCF film having a thickness of 20 μm was formed on the surface of the coating layer in the same manner as described above, and after 3,000 hours of charging in a furnace at 850 ° C., a cross section was cut out and semiquantitative analysis by EPMA was performed in the same manner as described above. As a result, in the LSCF outside the Cr diffusion preventing layer, the Cr diffusion amount was 0.5% by mass or less of the detection limit.

上記実施例１と同様、集電基材の脱脂を行った後、乾燥を行った。その後集電基材を塗装ガンより３００ｍｍ離れた位置に配置し、塗装ガン印加電圧−７５ｋＶ、亜鉛の吐出量を１００ｇ／分、吐出圧１．１×１０５Ｎ／ｍ２、エアー流量４．３ｍ３／ｈの条件で被覆を行った。この後、３５０℃の炉に１０時間入れ、酸化亜鉛を形成した。さらにその後に１０００℃の炉に２時間入れることで酸化亜鉛と集電基材とを反応させ、Ｚｎ−Ｍｎ系スピネルからなるＣｒ拡散防止層、ＺｎＯにＦｅが固溶した被覆層を形成した。Ｃｒ拡散防止層の厚みは１μｍであり、被覆層の厚みは平面部で１４μｍ、角部で２０μｍであった。 Similar to Example 1, the current collecting base material was degreased and then dried. Thereafter, the current collecting base material is disposed at a position 300 mm away from the coating gun, the coating gun applied voltage is -75 kV, the discharge amount of zinc is 100 g / min, the discharge pressure is 1.1 × 10 5 N / m 2 , and the air flow rate is 4. The coating was performed under the condition of 3 m 3 / h. Thereafter, it was placed in a furnace at 350 ° C. for 10 hours to form zinc oxide. Furthermore, after putting in a 1000 degreeC furnace for 2 hours, the zinc oxide and the current collection base material were made to react, and the Cr diffusion prevention layer which consists of Zn-Mn type | system | group spinel, and the coating layer which Fe dissolved in ZnO were formed. The thickness of the Cr diffusion preventing layer was 1 μm, and the thickness of the coating layer was 14 μm at the flat part and 20 μm at the corner part.

次に、上記実施例１と同様にして、被覆層表面に厚さ２０μｍのＬＳＣＦ膜を形成し、テストピースとした。このテストピースを８５０℃の炉に３０００ｈｒ投入した後、断面を切り出しＥＰＭＡによる半定量分析を実施例１と同様にして行った。その結果、Ｃｒ拡散防止層の外側のＬＳＣＦではＣｒの拡散量が検出限界の０．５質量％以下であった。   Next, in the same manner as in Example 1, a LSCF film having a thickness of 20 μm was formed on the surface of the coating layer to obtain a test piece. After putting this test piece into a furnace at 850 ° C. for 3000 hr, a cross section was cut out and semi-quantitative analysis by EPMA was performed in the same manner as in Example 1. As a result, in the LSCF outside the Cr diffusion preventing layer, the Cr diffusion amount was 0.5% by mass or less of the detection limit.

比較例として、上記実施例１と同様、集電基材の脱脂を行った集電基材を亜鉛：溶剤：バインダー：分散剤が１００：７２：１５：２の重量割合のディップ液の中に浸漬した。その後１３０℃で乾燥させた後に３５０℃の炉に１０時間入れ、酸化亜鉛を形成した。さらにその後に１０００℃の炉に２時間入れることで酸化亜鉛と集電基材とを反応させ、Ｚｎ−Ｍｎ系スピネルからなるＣｒ拡散防止層、ＺｎＯにＦｅが固溶した被覆層を形成した。Ｃｒ拡散防止層の厚みは１μｍであり、被覆層の厚みは平面部で１４μｍ、角部で２μｍであった。   As a comparative example, in the same manner as in Example 1, the current collecting base material that had been degreased was placed in a dip solution having a weight ratio of zinc: solvent: binder: dispersant of 100: 72: 15: 2. Soaked. Then, after drying at 130 ° C., it was placed in a 350 ° C. oven for 10 hours to form zinc oxide. Furthermore, after putting in a 1000 degreeC furnace for 2 hours, the zinc oxide and the current collection base material were made to react, and the Cr diffusion prevention layer which consists of Zn-Mn type | system | group spinel, and the coating layer which Fe dissolved in ZnO were formed. The thickness of the Cr diffusion preventing layer was 1 μm, and the thickness of the coating layer was 14 μm at the flat portion and 2 μm at the corner portion.

次に、上記実施例１と同様にして、被覆層表面に厚さ２０μｍのＬＳＣＦ膜を形成し、テストピースとした。このテストピースを８５０℃の炉に３０００ｈｒ投入した後、断面を切り出しＥＰＭＡによる半定量分析を実施例１と同様にして行った。その結果、Ｃｒ拡散防止層の外側のＬＳＣＦでは、角部における被覆層でＣｒの拡散量が３．８質量％であった。   Next, in the same manner as in Example 1, a LSCF film having a thickness of 20 μm was formed on the surface of the coating layer to obtain a test piece. After putting this test piece into a furnace at 850 ° C. for 3000 hr, a cross section was cut out and semi-quantitative analysis by EPMA was performed in the same manner as in Example 1. As a result, in the LSCF outside the Cr diffusion preventing layer, the Cr diffusion amount in the coating layer at the corner was 3.8% by mass.

本発明の燃料電池用集電部材の一例を示す斜視図である。It is a perspective view which shows an example of the current collection member for fuel cells of this invention. 図１に示すＡ−Ａ線に沿った燃料電池用集電部材の断面図である。It is sectional drawing of the current collection member for fuel cells along the AA line shown in FIG. 図１に示すＢ−Ｂ線に沿った燃料電池用集電部材の断面図である。It is sectional drawing of the current collection member for fuel cells along the BB line shown in FIG. 集電部材の断面を拡大して示すもので、（ａ）は本発明の集電部材の断面図、（ｂ）は従来の集電部材の断面図である。The cross section of a current collection member is expanded and shown, (a) is a sectional view of the current collection member of the present invention, and (b) is a sectional view of the conventional current collection member. 燃料電池セルの断面斜視図である。It is a cross-sectional perspective view of a fuel battery cell. 本発明の燃料電池セルスタックの縦断面図である。It is a longitudinal cross-sectional view of the fuel cell stack of the present invention.

符号の説明Explanation of symbols

１ 燃料電池セル
２０ 燃料電池用集電部材
２０１ 集電基材
２０２ Ｃｒ拡散防止層
２０３ 被覆層
２０３ａ 角部の被覆層
２０３ｂ 平面部の被覆層 DESCRIPTION OF SYMBOLS 1 Fuel cell 20 Current collecting member 201 for fuel cells Current collecting base material 202 Cr diffusion preventing layer 203 Coating layer 203a Corner coating layer 203b Plane coating layer

Claims (7)

Ｃｒを含有する合金板の表面をＭｎとＺｎとを含有する酸化物からなる緻密なＣｒ拡散防止層で被覆し、該Ｃｒ拡散防止層の表面を酸化物からなり５５０〜９００℃で１Ｓｃｍ −１ 以上の導電率を有する被覆層で被覆してなるとともに、該被覆層の厚みが前記合金板の平面部よりも角部の方で厚いことを特徴とする耐熱性合金部材。 The surface of the alloy plate containing Cr was coated with a dense Cr diffusion preventing layer made of oxide containing Mn and Zn, 1Scm the surface of the Cr diffusion preventing layer at 550 to 900 ° C. Do Ri oxide - A heat-resistant alloy member, wherein the heat-resistant alloy member is coated with a coating layer having an electrical conductivity of 1 or more , and the thickness of the coating layer is thicker at the corner portion than at the flat portion of the alloy plate. 前記合金板の表面に、メッキ法又は静電塗装法により形成された金属層を大気中にて熱処理して形成されていることを特徴とする請求項１記載の耐熱性合金部材。   2. The heat resistant alloy member according to claim 1, wherein a metal layer formed by plating or electrostatic coating is heat-treated in the atmosphere on the surface of the alloy plate. 前記合金板の表面に、下地層をメッキ法で形成し、その上面に金属層をメッキ法で形成し、これを大気中にて熱処理して形成されていることを特徴とする請求項１記載の耐熱性合金部材。   2. A base layer is formed on the surface of the alloy plate by a plating method, and a metal layer is formed on the upper surface of the alloy plate by a plating method, which is formed by heat treatment in the atmosphere. Heat-resistant alloy member. 前記合金板中にＭｎを含有するとともに、前記被覆層がＺｎを含有することを特徴とする請求項１乃至３のうちいずれかに記載の耐熱性合金部材。 With containing Mn in the alloy plate during the heat-resistant alloy member according to any one of claims 1 to 3 before Symbol coating layer is characterized by containing Zn. 燃料電池セルからの集電を行う集電部材が、請求項１乃至４のうちいずれかに記載の耐熱性合金部材からなることを特徴とする燃料電池用集電部材。   A current collector for a fuel cell, wherein the current collector for collecting current from the fuel cell comprises the heat resistant alloy member according to any one of claims 1 to 4. 複数の燃料電池セルの間に、請求項５記載の燃料電池用集電部材を介装してなる燃料電池セルスタックであって、前記燃料電池セルと前記燃料電池用集電部材とが、導電性接着材により接合されていることを特徴とする燃料電池セルスタック。   6. A fuel cell stack comprising the fuel cell current collecting member according to claim 5 interposed between a plurality of fuel cells, wherein the fuel cell and the fuel cell current collecting member are electrically conductive. The fuel cell stack is characterized by being bonded by an adhesive material. 請求項６記載の燃料電池セルスタックを、収納容器内に収納してなることを特徴とする燃料電池。   7. A fuel cell comprising the fuel cell stack according to claim 6 housed in a housing container.
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