JPH0992307A - Molten carbonate type fuel cell - Google Patents

Molten carbonate type fuel cell

Info

Publication number
JPH0992307A
JPH0992307A JP7288684A JP28868495A JPH0992307A JP H0992307 A JPH0992307 A JP H0992307A JP 7288684 A JP7288684 A JP 7288684A JP 28868495 A JP28868495 A JP 28868495A JP H0992307 A JPH0992307 A JP H0992307A
Authority
JP
Japan
Prior art keywords
current collector
plate
fuel cell
collector plate
cathode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP7288684A
Other languages
Japanese (ja)
Inventor
Hiroshi Tateishi
浩史 立石
Hideyuki Ozu
秀行 大図
Yoshihiro Akasaka
芳浩 赤坂
Kazuaki Nakagawa
和明 中川
Morohiro Tomimatsu
師浩 富松
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toshiba Corp
Original Assignee
Toshiba Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toshiba Corp filed Critical Toshiba Corp
Priority to JP7288684A priority Critical patent/JPH0992307A/en
Publication of JPH0992307A publication Critical patent/JPH0992307A/en
Pending legal-status Critical Current

Links

Classifications

    • 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

Abstract

PROBLEM TO BE SOLVED: To provide a fuel cell with high performance and long life by providing an accumulating plate having a non-stoichiometric composite oxide layer excellent in current conductivity and corrosion resistance formed on the surface so that the peeling in the part adjacent to a cathode is prevented even when heat cycle of increasing and decreasing temperature is received. SOLUTION: Current collecting plates 4, 5 on corrugated fuel gas side and oxidizing agent side are arranged on the surfaces opposite to an electrolyte plate 1 of the anode 2 and cathode 3 of a cell unit, respectively. In the oxidizing agent side current collecting plate 5, at least the surface making contact with the cathode of a current collector body formed of austenite stainless steel is covered with a Fe-Cr-Ni alloy layer having a composition consisting of 23-45wt.% of Fe, 12-27wt.% of Cr, the remainder of Ni, and 1wt.% or less of obligatory impurities, and a nickel-ferrite non-stoichiometric composite oxide layer is formed on the alloy layer surface. A molten carbonate type fuel cell with high performance and long life can be provided by use of this accumulating plate 5.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、溶融炭酸塩型燃料
電池に関し、特に集電板を改良した溶融炭酸塩型燃料電
池に係わる。TECHNICAL FIELD The present invention relates to a molten carbonate fuel cell, and more particularly to a molten carbonate fuel cell having an improved current collector plate.

【０００２】[0002]

【従来の技術】従来より各種の燃料電池が提案および実
用化されている。中でも、溶融炭酸塩型燃料電池は高効
率で、かつ燃料ガスとして石炭ガスが利用できるため、
広く研究、開発がなされている。2. Description of the Related Art Various fuel cells have been proposed and put into practical use. Above all, molten carbonate fuel cells are highly efficient and can use coal gas as fuel gas.
Widely researched and developed.

【０００３】前記溶融炭酸塩型燃料電池は、例えばアノ
ード（燃料極）、カソード（空気極）および電解質板に
より構成された複数のユニットセルを積層し、これらセ
ル間に集電板をそれぞれ配置し、さらに前記集電板間に
インターコネクタをそれぞれ配置して仕切った構造を有
する。２枚のエッジシール板は、前記電解質板の周縁部
を挟むように配置されている。前記エッジシール板は、
前記電解質板の周縁部と接してウェットシールを形成
し、前記ユニットセルを外部雰囲気からシールドする役
目をなす。In the molten carbonate fuel cell, for example, a plurality of unit cells composed of an anode (fuel electrode), a cathode (air electrode) and an electrolyte plate are laminated, and a current collector plate is arranged between these cells. Further, it has a structure in which interconnectors are respectively arranged between the current collector plates and partitioned. The two edge seal plates are arranged so as to sandwich the peripheral edge of the electrolyte plate. The edge seal plate is
A wet seal is formed in contact with the peripheral portion of the electrolyte plate to serve to shield the unit cell from the external atmosphere.

【０００４】ところで、前記酸化剤側集電板は前記燃料
電池の稼働時において前記空気極から滲し出された腐食
性の高い溶融炭酸塩の液膜に覆われている。このため、
前記集電板は従来より耐食性に優れたステンレス鋼によ
り形成されている。前記ステンレス鋼は、主にＳＵＳ３
１０Ｓ、ＳＵＳ３１６Ｌが使用されている。By the way, the oxidant-side current collector plate is covered with a liquid film of highly corrosive molten carbonate exuded from the air electrode during operation of the fuel cell. For this reason,
The current collector plate is made of stainless steel, which has a higher corrosion resistance than before. The stainless steel is mainly SUS3
10S and SUS316L are used.

【０００５】しかしながら、ステンレス鋼からなる前記
集電板は前記燃料電池の稼働時にその表面に腐食された
鉄を含む腐食生成物が層状に形成される。特に、前記燃
料電池を１０００時間以上の長時間に亘って稼働させる
と、前記腐食生成物が成長して電気抵抗が増大するた
め、燃料電池の性能が著しく劣化する。つまり、前記腐
食生成物が前記集電板に形成されることにより燃料電池
の高性能化と長寿命化が妨げられる。However, the current collector plate made of stainless steel has a layered corrosion product containing iron which is corroded on the surface of the current collector plate during operation of the fuel cell. In particular, when the fuel cell is operated for a long time of 1000 hours or more, the corrosion product grows and the electric resistance increases, so that the performance of the fuel cell is significantly deteriorated. That is, since the corrosion product is formed on the current collector plate, it is difficult to improve the performance and extend the life of the fuel cell.

【０００６】特開平５−３２４４６０号公報には、前記
ステンレス鋼の表面に予めＮｉＯ層を形成した集電板が
開示されている。この集電体は、Ｎｉ層が燃料電池内部
で酸化してＮｉＯ層を形成し、電気抵抗の高い腐食層の
形成を防止するため、電気抵抗の増大を抑制することが
可能である。しかしながら、前記集電板のＮｉＯ層は多
孔質で電解質の引き込み量が多いためにセルユニット内
部の電解質保持量が不足し、電池性能が劣化する恐れが
あった。さらに、前記ステンレス鋼や前記ＮｉＯ層が被
覆されたステンレス鋼からなる集電板は発電後の降温時
に冷却速度の差から発生する温度分布の影響により変形
を生じ、カソードと接する集電板の表面部分において剥
離が生じてそれらの密着性が損なわれる。その結果、前
記ステンレス鋼や前記ＮｉＯ層が被覆されたステンレス
鋼からなる集電体が組み込まれた溶融炭酸塩型燃料電池
では、昇降温の熱サイクルを受けると電池性能が劣化す
る恐れがある。Japanese Unexamined Patent Publication (Kokai) No. 5-324460 discloses a current collector plate in which a NiO layer is previously formed on the surface of the stainless steel. In this current collector, the Ni layer oxidizes inside the fuel cell to form a NiO layer, which prevents the formation of a corrosive layer having a high electric resistance, so that an increase in electric resistance can be suppressed. However, since the NiO layer of the current collector plate is porous and has a large amount of electrolyte drawn therein, the amount of electrolyte retained inside the cell unit is insufficient, which may deteriorate battery performance. Further, the current collector plate made of the stainless steel or the stainless steel coated with the NiO layer is deformed by the influence of the temperature distribution generated from the difference in the cooling rate during the temperature decrease after the power generation, and the surface of the current collector plate in contact with the cathode. Peeling occurs at the parts, and their adhesion is impaired. As a result, in a molten carbonate fuel cell in which a current collector made of the stainless steel or the stainless steel coated with the NiO layer is incorporated, the cell performance may be deteriorated when the thermal cycle of temperature rising / falling is performed.

【０００７】[0007]

【発明が解決しようとする課題】本発明の目的は、優れ
た電気伝導性を有し、電解質の引き込みが少なく耐食性
の優れた不定比複合酸化物層が表面に形成され、さらに
昇降温の熱サイクルを受けてもカソードと接する部分で
剥離するのを防止した酸化剤ガス側集電板を備えた高性
能、長寿命の溶融炭酸塩型燃料電池を提供しようとする
ものである。An object of the present invention is to form a non-stoichiometric composite oxide layer having excellent electrical conductivity, less entrainment of electrolyte and excellent corrosion resistance on the surface, and further heat up / down heat. It is an object of the present invention to provide a high-performance, long-life molten carbonate fuel cell provided with an oxidant gas side current collector which prevents peeling at a portion in contact with the cathode even when subjected to a cycle.

【０００８】本発明の別の目的は、酸化剤ガス側集電板
とインターコネクタとの接触部の腐食を防止して、電気
抵抗の増大のない長寿命の溶融炭酸塩型燃料を提供しよ
うとするものである。Another object of the present invention is to prevent corrosion of the contact portion between the oxidant gas side current collector plate and the interconnector and to provide a long-life molten carbonate fuel without increase in electric resistance. To do.

【０００９】本発明のさらに別の目的は、１００００時
間以上の長時間に亘って稼働させても、カソート、アノ
ードの電極からの剥離を防止した集電板を備えた溶融炭
酸塩型燃料電池を提供しようとするものである。Still another object of the present invention is to provide a molten carbonate fuel cell provided with a current collector plate which prevents peeling of the castort and the anode from the electrode even when operated for a long time of 10,000 hours or more. It is the one we are trying to provide.

【００１０】[0010]

【課題を解決するための手段】本発明に係わる溶融炭酸
塩型燃料電池は、多孔質体に炭酸塩を含浸して形成され
た電解質板と、この電解質板の両面に配置されたカソー
ドおよびアノードとからなるセルユニット；前記セルユ
ニットの前記アノード表面および前記カソード表面にそ
れぞれ配置された波形状を有する集電板；および前記集
電板表面にそれぞれ配置されたインターコネクタ；を具
備し、前記カソード側の前記集電板は、オーステナイト
系ステンレス鋼からなる集電体本体と、少なくとも前記
カソードと接する前記集電体本体表面に被覆されたＦｅ
２３〜４５重量％、Ｃｒ１２〜２７重量％、残部Ｎｉお
よび不可避的不純物１重量％以下の組成を有するＦｅ−
Ｃｒ−Ｎｉ合金層と、前記合金層表面に形成されたニッ
ケルフェライト系の不定比複合酸化物層とからなること
を特徴とするものである。[MEANS FOR SOLVING THE PROBLEMS] A molten carbonate fuel cell according to the present invention comprises an electrolyte plate formed by impregnating a porous body with a carbonate, and a cathode and an anode arranged on both sides of the electrolyte plate. A cell unit comprising: a current collecting plate having a wave shape, which is arranged on each of the anode surface and the cathode surface of the cell unit; and an interconnector, which is arranged on each of the current collecting plate surfaces. The current collector plate on the side is a current collector body made of austenitic stainless steel, and Fe coated on at least the surface of the current collector body in contact with the cathode.
Fe- having a composition of 23 to 45% by weight, Cr 12 to 27% by weight, balance Ni and inevitable impurities of 1% by weight or less.
It is characterized by comprising a Cr-Ni alloy layer and a nickel ferrite-based non-stoichiometric composite oxide layer formed on the surface of the alloy layer.

【００１１】また本発明に係わる別の溶融炭酸塩型燃料
電池は、多孔質体に炭酸塩を含浸して形成された電解質
板と、この電解質板の両面に配置されたカソードおよび
アノードとからなるセルユニット；前記セルユニットの
前記カソードおよびアノードの表面にそれぞれ配置され
た波形状を有する集電板；および前記集電板表面にそれ
ぞれ配置されたインターコネクタ；を具備し、前記カソ
ード側の集電板は、前記インターコネクタの平面と所定
の部位で接触し、前記部位は両端に曲面を有し、かつバ
リア材は前記インターコネクタの平面と前記集電板の部
位の曲面との間で形成される空間に充填されていること
を特徴とするものである。Another molten carbonate fuel cell according to the present invention comprises an electrolyte plate formed by impregnating a porous body with carbonate, and a cathode and an anode arranged on both sides of the electrolyte plate. A cell unit; current collecting plates each having a wave shape and arranged on the surfaces of the cathode and the anode of the cell unit; and interconnectors respectively arranged on the surface of the current collecting plate; The plate is in contact with the flat surface of the interconnector at a predetermined portion, the portion has curved surfaces at both ends, and the barrier material is formed between the flat surface of the interconnector and the curved surface of the collector plate portion. It is characterized by being filled in the space.

【００１２】さらに本発明に係わる別の溶融炭酸塩型燃
料電池は、多孔質体に炭酸塩を含浸して形成された電解
質板と、この電解質板の両面に配置された一対の電極と
からなるセルユニット；前記セルユニットの前記各電極
表面にそれぞれ配置された波形状を有する集電板；およ
び前記集電板表面にそれぞれ配置されたインターコネク
タ；を具備し、前記波形状の集電板は、前記電極と接す
る第１面および前記インターコネクタと接する第２面を
有し、前記第１面の幅は前記第２面の幅より広く、かつ
前記第１面は複数のガス供給用貫通孔が開口され、さら
に前記第１面は前記電極に向かって円弧状に膨らんでい
ることを特徴とするものである。Further, another molten carbonate fuel cell according to the present invention comprises an electrolyte plate formed by impregnating a porous body with a carbonate, and a pair of electrodes arranged on both sides of the electrolyte plate. A cell unit; a corrugated current collector plate disposed on each of the electrode surfaces of the cell unit; and an interconnector disposed on each of the current collector plate surfaces; A first surface in contact with the electrode and a second surface in contact with the interconnector, the width of the first surface is wider than the width of the second surface, and the first surface has a plurality of through holes for gas supply. Is opened, and further, the first surface bulges in an arc shape toward the electrode.

【００１３】[0013]

【発明の実施の形態】以下、本発明を図１を参照して詳
細に説明する。図１は、複数のユニットセルを積層した
構造を有する積層電池の一部を示す断面図である。電解
質板１は、アノード（燃料極）２とカソード（空気極）
３の間に配置されている。前記電解質板１は、多孔質体
に少なくともリチウム炭酸塩等の炭酸塩を含む電解質を
含浸させることにより形成されている。前記電解質板
１、アノード２およびカソード３によりユニットセルを
構成している。波形の燃料ガス側、酸化剤側の集電板
４、５は、前記アノード２およびカソード３の前記電解
質板１と反対側の面にそれぞれ配置されている。前記各
集電板４、５は、前記アノード２およびカソード３と接
触する部分にガス供給用貫通孔（図示せず）がそれぞれ
開孔されている。燃料ガスは、前記アノード２と前記集
電板４とで形成された流路６を流通する。酸化剤ガス
は、前記カソード３と前記集電板５とで形成された流路
７を流通する。セパレータは、積層された複数の前記ユ
ニットセルの間に配置され、それらユニットセルの仕切
りとして機能する。前記セパレータは、前記各流路６、
７を分離するためのインターコネクタ８と、前記電解質
板１の周縁部を挟むように配置された２枚のエッジシー
ル板９、１０とから構成されている。前記エッジシール
板９、１０は、前記電解質板１の周縁部と接してウェッ
トシールを形成し、前記ユニットセルの発電部品を外部
雰囲気からシールドする役目をなしている。また、前記
エッジシール板９、１０はそれぞれ前記電解質板１の周
縁部の挟持部においてスプリング部材１１、１２により
通常５ｋｇ／ｃｍ2 以下の面圧が両側から加えられるこ
とにより、前記ウェットシール性が確保されている。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to FIG. FIG. 1 is a sectional view showing a part of a laminated battery having a structure in which a plurality of unit cells are laminated. The electrolyte plate 1 includes an anode (fuel electrode) 2 and a cathode (air electrode).
It is located between the three. The electrolyte plate 1 is formed by impregnating a porous body with an electrolyte containing at least a carbonate such as lithium carbonate. A unit cell is constituted by the electrolyte plate 1, the anode 2 and the cathode 3. The corrugated fuel gas side and oxidant side current collecting plates 4 and 5 are respectively arranged on the surfaces of the anode 2 and the cathode 3 opposite to the electrolyte plate 1. Each of the current collector plates 4 and 5 has a gas supply through hole (not shown) formed in a portion in contact with the anode 2 and the cathode 3. The fuel gas flows through the flow path 6 formed by the anode 2 and the current collector plate 4. The oxidant gas flows through the flow path 7 formed by the cathode 3 and the current collector plate 5. The separator is arranged between the plurality of stacked unit cells and functions as a partition of the unit cells. The separators are the flow paths 6,
It is composed of an interconnector 8 for separating 7 and two edge seal plates 9 and 10 arranged so as to sandwich the peripheral edge of the electrolyte plate 1. The edge seal plates 9 and 10 are in contact with the peripheral edge of the electrolyte plate 1 to form a wet seal, and serve to shield the power generation component of the unit cell from the external atmosphere. Further, the edge seal plates 9 and 10 are provided with a wet-sealing property by applying a surface pressure of usually 5 kg / cm 2 or less from both sides by the spring members 11 and 12 at the sandwiching portions of the peripheral edge of the electrolyte plate 1. Has been secured.

【００１４】前記電解質板１は、例えばリチウムアルミ
ネート（ＬｉＡｌＯ2 ）を主成分とする多孔質体に電解
質を溶融状態で含浸した構成を有する。前記電解液とし
ては、例えば炭酸リチウム（Ｌｉ2 ＣＯ3 ）と炭酸カリ
ウム（Ｋ2 ＣＯ3 ）の混合物、Ｌｉ2 ＣＯ3 と炭酸ナト
リウム（Ｎａ2 ＣＯ3 の混合物、Ｌｉ2 ＣＯ3 とＫ2Ｃ
Ｏ3 とＮａ2 ＣＯ3 の混合物等の混合アルカリ炭酸塩を
挙げることができる。前記電解液は、前記混合アルカリ
炭酸塩にさらにアルカリ土類炭酸塩を添加した組成を有
することを許容する。The electrolyte plate 1 has a structure in which, for example, a porous body containing lithium aluminate (LiAlO 2 ) as a main component is impregnated with an electrolyte in a molten state. Examples of the electrolytic solution include a mixture of lithium carbonate (Li 2 CO 3 ) and potassium carbonate (K 2 CO 3 ), a mixture of Li 2 CO 3 and sodium carbonate (Na 2 CO 3 ), Li 2 CO 3 and K 2 C
Mention may be made of mixed alkali carbonates such as a mixture of O 3 and Na 2 CO 3 . The electrolyte solution is allowed to have a composition in which an alkaline earth carbonate is further added to the mixed alkali carbonate.

【００１５】前記アノード２、カソード３は、例えばニ
ッケル基合金の焼結体のような多孔質体から形成され
る。前記インターコネクタ８およびエッジシ―ル９、１
０は、例えばステンレス鋼から形成される。The anode 2 and the cathode 3 are formed of a porous material such as a sintered body of nickel-based alloy. The interconnector 8 and the edge seals 9, 1
0 is formed of stainless steel, for example.

【００１６】前記燃料ガスとしては、例えば水素（Ｈ
2 ）と二酸化炭素（ＣＯ2 ）との混合ガスなどを使用で
きる。前記酸化剤ガスとしては、例えば空気又は酸素
（Ｏ2 ）と二酸化炭素（ＣＯ2 ）との混合ガスなどを使
用できる。As the fuel gas, for example, hydrogen (H
2 ) and carbon dioxide (CO 2 ) mixed gas can be used. As the oxidizing gas, for example, air or a mixed gas of oxygen (O 2 ) and carbon dioxide (CO 2 ) can be used.

【００１７】次に、（１）酸化剤側集電板の構成、
（２）集電板とインターコネクタとの接触部の構造、
（３）集電板の構造、について説明する。 （１）酸化剤側集電板の構成 前記酸化剤側集電板５は、オーステナイト系ステンレス
鋼からなる集電体本体の少なくともカソードと接する表
面にＦｅ２３〜４５重量％、Ｃｒ１２〜２７重量％、残
部Ｎｉおよび不可避的不純物１重量％以下の組成を有す
るＦｅ−Ｃｒ−Ｎｉ合金層が被覆され、かつ前記合金層
表面にニッケルフェライト系の不定比複合酸化物層が形
成された構造を有する。Next, (1) the structure of the oxidizer side current collector,
(2) Structure of contact part between current collector and interconnector,
(3) The structure of the current collector plate will be described. (1) Structure of oxidizer-side current collector plate The oxidizer-side current collector plate 5 has Fe23 to 45 wt% and Cr12 to 27 wt% on at least the surface of the current collector body made of austenitic stainless steel in contact with the cathode. It has a structure in which a balance of Ni and an Fe-Cr-Ni alloy layer having a composition of 1% by weight or less of unavoidable impurities is coated, and a nickel ferrite-based nonstoichiometric complex oxide layer is formed on the surface of the alloy layer.

【００１８】前記集電体本体を構成するステンレス鋼と
しては、例えば１０〜２７重量％のＣｒ、７．０〜２８
重量％のＮｉ、０．０８重量％以下のＣｏ、２．０重量
％以下のＭｎ、１．５重量％以下のＳｉ、残部がＦｅお
よび０．１重量％以下の不可避的不純物の組成を有する
ものが挙げられる。代表的なステンレス鋼としては、高
温強度に優れ、かつ高耐食性を有するＳＵＳ３１０Ｓ、
ＳＵＳ３１６Ｌが挙げられる。As the stainless steel constituting the current collector body, for example, 10 to 27% by weight of Cr, 7.0 to 28 is used.
It has a composition of wt% Ni, 0.08 wt% or less Co, 2.0 wt% or less Mn, 1.5 wt% or less Si, the balance Fe and 0.1 wt% or less unavoidable impurities. There are things. As typical stainless steel, SUS310S, which has excellent high temperature strength and high corrosion resistance,
SUS316L is mentioned.

【００１９】前記集電体本体は、２００〜４００μｍの
厚さを有するステンレス鋼薄板から形成されることが好
ましい。このような集電体本体を有する集電体は、燃料
電池に組み込んだ時に良好な高温強度と高耐食性が付与
される。The current collector body is preferably formed of a stainless steel thin plate having a thickness of 200 to 400 μm. A current collector having such a current collector body is provided with good high temperature strength and high corrosion resistance when incorporated in a fuel cell.

【００２０】前記Ｆｅ−Ｃｒ−Ｎｉ合金層は、カソード
と接する集電体本体表面の部位に少なくとも形成するこ
とが必要である。これは、カソードと接する集電板の表
面部位には電気抵抗の大きい鉄を含む腐食生成物が成長
し易く、電池の高性能化と長寿命化を阻害する。このた
め、前記表面部位に前記合金層を形成し、この合金層表
面に形成された電気伝導性および耐食性の優れた前記不
定比複合酸化物により鉄を含む腐食生成物の発生を防止
するものである。勿論、前記Ｆｅ−Ｃｒ−Ｎｉ合金層は
前記集電体本体のカソードと接する側の片面全体または
前記集電体本体の両面に形成してもよい。It is necessary that the Fe-Cr-Ni alloy layer is formed at least on the surface of the current collector body which is in contact with the cathode. This is because a corrosion product containing iron, which has a high electric resistance, easily grows on the surface portion of the current collector plate that is in contact with the cathode, which hinders high performance and long life of the battery. Therefore, the alloy layer is formed on the surface portion, and the non-stoichiometric complex oxide having excellent electrical conductivity and corrosion resistance formed on the surface of the alloy layer prevents generation of corrosion products containing iron. is there. Of course, the Fe-Cr-Ni alloy layer may be formed on the entire one surface of the current collector body on the side in contact with the cathode or on both surfaces of the current collector body.

【００２１】前記Ｆｅ−Ｃｒ−Ｎｉ合金層のＦｅおよび
Ｃｒの成分割合を規定したのは、次のような理由による
ものである。 ａ）Ｆｅ Ｆｅ成分の量を２３重量％未満にすると、前記合金層表
面に多孔質のＮｉＯ層が形成されて電解質の引き込み量
が増大し、燃料電池の高性能化が阻害される。一方、Ｆ
ｅ成分の量が４５重量％を越えると前記合金層表面に電
気抵抗の高い複合酸化物層が形成され易くなる。より好
ましいＦｅ成分の量は、２８〜４２重量％である。The proportions of Fe and Cr in the Fe-Cr-Ni alloy layer are defined for the following reasons. a) Fe If the amount of Fe component is less than 23% by weight, a porous NiO layer is formed on the surface of the alloy layer to increase the amount of electrolyte drawn in, impeding the performance enhancement of the fuel cell. On the other hand, F
When the amount of the component e exceeds 45% by weight, a complex oxide layer having high electric resistance is likely to be formed on the surface of the alloy layer. A more preferable amount of the Fe component is 28 to 42% by weight.

【００２２】ｂ）Ｃｒ Ｃｒ成分の量を１２重量％未満にすると、合金層表面に
形成された複合酸化物層の耐食性が低下する。一方、Ｃ
ｒ成分の量が２７重量％を越えると加工性が低下する。
より好ましいＣｒ成分の量は、１９〜２７重量％であ
る。B) Cr If the amount of Cr component is less than 12% by weight, the corrosion resistance of the complex oxide layer formed on the surface of the alloy layer decreases. On the other hand, C
If the amount of the r component exceeds 27% by weight, the workability is deteriorated.
A more preferable amount of Cr component is 19 to 27% by weight.

【００２３】前記Ｆｅ−Ｃｒ−Ｎｉ合金層は、前記集電
体本体の表面に例えばクラッド法により形成される。こ
のような合金層は、１５〜１５０μｍ、より好ましくは
５０〜１００μｍの厚さを有することが好ましい。前記
合金層の厚さを１５μｍ未満にすると、集電体の変形抑
制効果が低減される恐れがある。一方、前記合金層の厚
さが１５０μｍを越えるとオーステナイト系ステンレス
鋼からなる集電体本体と前記合金層との熱膨張係数差に
より発生する内部応力が大きくなって、カソードを押さ
え付ける力が大きくなってカソードを押し潰す恐れがあ
る。The Fe-Cr-Ni alloy layer is formed on the surface of the current collector body by, for example, a clad method. Such an alloy layer preferably has a thickness of 15 to 150 μm, more preferably 50 to 100 μm. If the thickness of the alloy layer is less than 15 μm, the effect of suppressing the deformation of the current collector may be reduced. On the other hand, if the thickness of the alloy layer exceeds 150 μm, the internal stress generated due to the difference in thermal expansion coefficient between the current collector body made of austenitic stainless steel and the alloy layer becomes large, and the force pressing the cathode becomes large. There is a risk of crushing the cathode.

【００２４】前記ニッケルフェライト系の不定比複合酸
化物は、ＮｉＦｅ2 Ｏ4 の化学量論組成の複合酸化物に
比べて、Ｎｉ、Ｆｅの量が酸素量に対して不足している
組成を有するものである。このような不定比複合酸化物
は、例えばＮｉ1-x Ｆｅ2-yＯ4 、ただしｘ、ｙは０＜
ｘ＜０．８５、−０．５＜ｙ＜１．０、０＜ｘ＋ｙを示
す、にて表されることが好ましい。なお、前記不定比複
合酸化物は燃料電池に前記集電体を組み込んで発電した
後の組成比が一定ではなく、集電体の面内の場所により
ばらついた値を示す。また、前記不定比複合酸化物はＬ
ｉが侵入または置換された形態を取ることを許容する。
ただし、いずれの場合もＸ線回折測定結果では酸化物が
スピネル型構造を示す。The nickel ferrite-based non-stoichiometric composite oxide has a composition in which the amounts of Ni and Fe are insufficient with respect to the amount of oxygen, as compared with the composite oxide having a stoichiometric composition of NiFe 2 O 4. It is a thing. Such a non-stoichiometric composite oxide is, for example, Ni 1-x Fe 2-y O 4, where x and y are 0 <
It is preferable that it is represented by x <0.85, -0.5 <y <1.0, and 0 <x + y. The composition ratio of the non-stoichiometric composite oxide is not constant after the current collector is incorporated into a fuel cell to generate electricity, and shows a value that varies depending on the position within the plane of the current collector. The non-stoichiometric composite oxide is L
Allow i to take invaded or permuted forms.
However, in any case, the oxide shows a spinel type structure in the X-ray diffraction measurement result.

【００２５】前記不定比複合酸化物層は、燃料電池を１
０００時間運転した後の状態で５０μｍ以下の厚さを有
することが好ましい。前記複合酸化物層の厚さは、薄け
れば薄いほど前記集電板の電気抵抗の値が小さくなるた
めを好ましい。前記複合酸化物層の厚さが５０μｍを越
えると、多孔質化して電解質の引き込み量が多くなり、
電池性能が低下する恐れがある。The non-stoichiometric composite oxide layer is used in a fuel cell.
It preferably has a thickness of 50 μm or less after being operated for 000 hours. It is preferable that the thinner the thickness of the complex oxide layer, the smaller the electric resistance value of the current collector plate. If the thickness of the complex oxide layer exceeds 50 μm, the complex oxide layer becomes porous and the amount of the electrolyte drawn therein increases,
Battery performance may decrease.

【００２６】前記不定比複合酸化物層は、例えば次のよ
うな方法により形成される。 ａ）前記集電板（ステンレス鋼からなる集電板本体と少
なくともカソード接する前記本体表面に形成されたＦｅ
−Ｃｒ−Ｎｉ合金層）を前記燃料電池に組み込む前に高
温酸化処理することによって、前記合金層表面に不定比
複合酸化物層を形成する。The nonstoichiometric complex oxide layer is formed by the following method, for example. a) Fe formed on the surface of the current collector plate (at least in cathode contact with the main body of the current collector plate made of stainless steel)
-Cr-Ni alloy layer) is subjected to a high temperature oxidation treatment before being incorporated into the fuel cell to form a nonstoichiometric complex oxide layer on the surface of the alloy layer.

【００２７】ｂ）前記集電板（ステンレス鋼からなる集
電板本体と少なくともカソード接する前記本体表面に形
成されたＦｅ−Ｃｒ−Ｎｉ合金層）を前記燃料電池に組
み込み、電池の稼働時に前記合金層表面に不定比複合酸
化物層を形成する。B) The current collector plate (a Fe-Cr-Ni alloy layer formed on the surface of the body at least in cathode contact with the body of the current collector plate made of stainless steel) is incorporated into the fuel cell, and the alloy is used when the cell is in operation. A nonstoichiometric complex oxide layer is formed on the layer surface.

【００２８】前記ｂ）の方法にように集電体を燃料電池
に組み込んで１０００時間程度稼働させると、厚さ５〜
２０μｍの不定比複合酸化物層が前記合金表面に形成さ
れる。When the current collector is incorporated in the fuel cell and operated for about 1000 hours as in the above method b), the thickness is 5 to 5.
A 20 μm non-stoichiometric complex oxide layer is formed on the alloy surface.

【００２９】前記ニッケルフェライト系の不定比複合酸
化物層は、前記合金層表面に組成比の異なる酸化物層が
２層以上積層して形成されていることを許容する。例え
ば、前記合金層表面にＦｅおよびＣｒを含む酸化物層と
前記ＮｉＦｅ2 Ｏ4 の化学量論組成に比べてＮｉ、Ｆｅ
の量が酸素量に対して不足している複合酸化物とがこの
順序で積層されたものを挙げることができる。The nickel ferrite-based non-stoichiometric composite oxide layer allows the formation of two or more oxide layers having different composition ratios on the surface of the alloy layer. For example, in comparison with the stoichiometric composition of the oxide layer containing Fe and Cr on the surface of the alloy layer and the NiFe 2 O 4 , Ni, Fe
The composite oxide in which the amount of oxygen is insufficient with respect to the amount of oxygen is laminated in this order.

【００３０】以上説明した酸化剤側集電板は、オーステ
ナイト系ステンレス鋼からなる集電体本体の少なくとも
カソードと接する表面にＦｅ２３〜４５重量％、Ｃｒ１
２〜２７重量％、残部Ｎｉおよび不可避的不純物１重量
％以下の組成を有するＦｅ−Ｃｒ−Ｎｉ合金層が被覆さ
れ、さらに前記合金層表面にニッケルフェライト系の不
定比複合酸化物層が形成された構造を有する。前記不定
比複合酸化物層は、電気伝導性に優れ、かつ電解質の引
き込み量が少なく、さらに優れた耐腐食性を有する。ま
た、前記集電体を組み込んだ燃料電池を発電した後の降
温時において、オーステナイト系ステンレス鋼からなる
集電体本体とＦｅ−Ｃｒ−Ｎｉ合金層との熱膨張係数の
差により発生する内部応力により前記集電体に接するカ
ソードを押さえ付ける力が働くため、前記集電体を前記
カソードに対して良好に密着させることができる。した
がって、このような酸化剤側集電板を備えた溶融炭酸塩
型燃料電池は高性能化、長寿命化が達成される。The oxidant-side current collector described above has Fe23 to 45% by weight and Cr1 on at least the surface of the current collector body made of austenitic stainless steel in contact with the cathode.
An Fe-Cr-Ni alloy layer having a composition of 2 to 27% by weight, the balance Ni and inevitable impurities of 1% by weight or less is coated, and a nickel ferrite-based nonstoichiometric complex oxide layer is further formed on the surface of the alloy layer. It has a different structure. The non-stoichiometric composite oxide layer has excellent electrical conductivity, a small amount of electrolyte drawn in, and excellent corrosion resistance. Further, at the time of temperature reduction after power generation of a fuel cell incorporating the current collector, internal stress generated due to a difference in thermal expansion coefficient between the current collector body made of austenitic stainless steel and the Fe-Cr-Ni alloy layer. As a result, a force for pressing the cathode in contact with the current collector acts, so that the current collector can be brought into good contact with the cathode. Therefore, the molten carbonate fuel cell provided with such an oxidant side current collector plate achieves high performance and long life.

【００３１】（２）集電板とインターコネクタとの接触
部の構造 図２に示すように波形の酸化剤側集電板５は前記インタ
ーコネクタ８の平面と所定の部位で接触し、前記部位は
両端に曲面を有する。バリア材１３は、前記インターコ
ネクタ８の平面と前記集電板５の部位の曲面との間で形
成される空間に充填されている。このようなバリア材１
３の充填によって、カソード３から滲み出した電解質が
前記隙間に引き込まれるのを防ぎ、高抵抗の腐食層が前
記接触面の内部まで成長して金属同士の接触部の面積が
減少することによる電気抵抗の増大を抑制することがで
きる。(2) Structure of the contact portion between the current collector plate and the interconnector As shown in FIG. 2, the corrugated oxidant side current collector plate 5 contacts the flat surface of the interconnector 8 at a predetermined portion, Has curved surfaces at both ends. The barrier material 13 is filled in the space formed between the flat surface of the interconnector 8 and the curved surface of the portion of the current collector plate 5. Such a barrier material 1
3 prevents the electrolyte exuded from the cathode 3 from being drawn into the gap, and a high resistance corrosion layer grows inside the contact surface to reduce the area of the metal-metal contact portion. It is possible to suppress an increase in resistance.

【００３２】前記集電板は、例えばＮｉ、０．０８重量
％以下のＣｏ、２．０重量％以下のＭｎ、１．５重量％
以下のＳｉ、残部がＦｅおよび０．１重量％以下の不可
避的不純物の組成を有するステンレス鋼から形成されて
いる。代表的なステンレス鋼としては、高温強度に優
れ、かつ高耐食性を有するＳＵＳ３１０Ｓ、ＳＵＳ３１
６Ｌが挙げられる。The current collector plate is made of, for example, Ni, 0.08% by weight or less Co, 2.0% by weight or less Mn, 1.5% by weight.
It is formed of the following Si, the balance being Fe, and stainless steel having a composition of unavoidable impurities of not more than 0.1% by weight. As typical stainless steel, SUS310S, SUS31 having excellent high temperature strength and high corrosion resistance
6L is mentioned.

【００３３】前記バリア材としては、次のような融点を
有する導電材料からなることが好ましい。 ａ）バリア材は、燃料電池の作動温度より融点の低い導
電材料、例えばアルミニウムろう、銀ろうからなる。こ
のような燃料電池の作動温度より融点が低いバリア材１
３を前記酸化剤側集電板５とインターコネクタ８との間
に形成される空間に充填することによって、燃料電池の
起動に伴い、溶融したバリア材が毛細管現象により前記
空間に引き込まれてその場で前記空間を充填することが
できる。その結果、集電板の熱変形にも柔軟に対応する
ことが可能になる。The barrier material is preferably made of a conductive material having the following melting point. a) The barrier material is made of a conductive material having a melting point lower than the operating temperature of the fuel cell, such as aluminum solder or silver solder. Barrier material 1 having a melting point lower than the operating temperature of such a fuel cell
By filling 3 into the space formed between the oxidizer side current collector plate 5 and the interconnector 8, the molten barrier material is drawn into the space by the capillary phenomenon when the fuel cell is activated. The space can be filled in the field. As a result, it is possible to flexibly cope with thermal deformation of the current collector plate.

【００３４】ｂ）バリア材は、電解質の融点より低い融
点を有する導電材料、例えば金はんだからなる。このよ
うな融点を有するバリア材１３を前記酸化剤側集電板５
とインターコネクタ８との間に形成される空間に充填す
ることによって、燃料電池の起動時において、電解質が
溶融して前記空間に滲み出す前にバリア材１３が溶融し
て前記空間を充填することができる。その結果、高抵抗
の腐食層が前記集電板５とインターコネクタ８との接触
部に生成されるのをより確実に防止することが可能にな
る。B) The barrier material is made of a conductive material having a melting point lower than that of the electrolyte, for example, gold solder. The barrier material 13 having such a melting point is used as the oxidizer-side current collector 5
And the interconnector 8 are filled in the space so that the barrier material 13 melts and fills the space at the time of starting the fuel cell before the electrolyte melts and oozes into the space. You can As a result, it is possible to more reliably prevent the corrosion layer having a high resistance from being generated in the contact portion between the current collector plate 5 and the interconnector 8.

【００３５】次に、前記集電板とインターコネクタとの
間に形成される空間にバリア材を充填する方法について
説明する。 ａ）燃料電池の作動温度より高い融点を有するバリア材
を用いる場合：まず、波形の酸化剤側集電板とインター
コネクタとを積層し、２ｋｇ／ｃｍ2の荷重をかける。
つづいて、前記集電板の部位の曲面とインターコネクタ
の平面とで形成される空間に、例えば金ろう線を置き、
９１０℃で１０分間熱処理して予め前記隙間に金ろうを
充填する。この後、前記集電板とインターコネクタとを
積層物を燃料電池に組み込む。Next, a method of filling the barrier material in the space formed between the current collector plate and the interconnector will be described. a) When using a barrier material having a melting point higher than the operating temperature of the fuel cell: First, a corrugated oxidant side current collector and an interconnector are laminated and a load of 2 kg / cm 2 is applied.
Subsequently, for example, a brazing wire is placed in the space formed by the curved surface of the portion of the current collector and the flat surface of the interconnector,
Heat treatment is performed at 910 ° C. for 10 minutes to fill the gap with gold solder in advance. Then, the laminated body of the current collector and the interconnector is assembled into a fuel cell.

【００３６】ｂ）燃料電池の作動温度より低い融点を有
するバリア材を用いる場合：波形の酸化剤側集電板とイ
ンターコネクタとを積層し、前記集電板の部位の曲面と
インターコネクタの平面とで形成される空間に、例えば
Ａｌ−Ｓｉろう線を置き、燃料電池に他の部材と共に組
み込む。つづいて、燃料電池を起動させ、６００℃前後
で前記Ａｌ−Ｓｉろう線を溶融して毛細管現象により前
記空間にバリア材を充填する。B) When a barrier material having a melting point lower than the operating temperature of the fuel cell is used: a corrugated oxidant side current collector plate and an interconnector are laminated, and the curved surface of the current collector plate portion and the flat surface of the interconnector. For example, an Al-Si brazing wire is placed in the space formed by and is incorporated in the fuel cell together with other members. Subsequently, the fuel cell is activated, and the Al—Si brazing wire is melted at around 600 ° C. to fill the space with the barrier material by the capillary phenomenon.

【００３７】ｃ）電解質の融点より低い融点を有するバ
リア材を用いる場合：波形の酸化剤側集電板とインター
コネクタとを積層し、前記集電板の部位の曲面とインタ
ーコネクタの平面とで形成される空間に、例えば金はん
だを置き、燃料電池に他の部材と共に組み込む。つづい
て、燃料電池を起動させ、電解質が溶融する前に３００
℃前後で前記金はんだを溶融して毛細管現象により前記
空間にバリア材を充填する。C) When a barrier material having a melting point lower than that of the electrolyte is used: a corrugated oxidant side current collector plate and an interconnector are laminated, and the curved surface of the current collector plate portion and the flat surface of the interconnector are laminated. Gold solder, for example, is placed in the formed space and incorporated in the fuel cell together with other members. Next, start the fuel cell, and before the electrolyte melts, 300
The space is filled with the barrier material by melting the gold solder at around ℃ and capillarity.

【００３８】前記ａ）〜ｃ）のバリア材の充填におい
て、ろう材やはんだは線材を始め、棒材、シート、粉
末、ペースト等の形態で用いられる。前記バリア材は、
前述したように導電材料からなることが好ましいが、低
融点ガラスのような絶縁体であってもよい。このような
低融点ガラスからなるバリア材は、次のような方法によ
り充填される。In the filling of the barrier material of the above a) to c), the brazing material and the solder are used in the form of wire, rod, sheet, powder, paste and the like. The barrier material is
As described above, it is preferably made of a conductive material, but may be an insulator such as low melting point glass. The barrier material made of such a low melting point glass is filled by the following method.

【００３９】まず、波形の酸化剤側集電板とインターコ
ネクタとを積層し、前記集電板の部位の曲面とインター
コネクタの平面とで形成される空間に、例えばＺｎＯ−
Ｂ2Ｏ3 粉末を撒き、燃料電池に他の部材と共に組み込
む。つづいて、燃料電池を起動させ、６００℃前後で前
記ＺｎＯ−Ｂ2 Ｏ3 粉末を溶融して毛細管現象により前
記空間にバリア材を充填する。First, a corrugated oxidant-side current collector plate and an interconnector are laminated, and a space formed by the curved surface of the collector plate portion and the flat surface of the interconnector is filled with, for example, ZnO--.
B 2 O 3 powder sprinkled, incorporated with other members in a fuel cell. Then, to activate the fuel cell is filled with barrier material in the space by capillary action to melt the ZnO-B 2 O 3 powder at about 600 ° C..

【００４０】以上説明したように、酸化剤ガス側集電板
は前記インターコネクタの平面と所定の部位で接触し、
前記部位は両端に曲面を有し、かつバリア材は前記イン
ターコネクタの平面と前記集電板の部位の曲面との間で
形成される空間に充填されているため、前記空間への電
解質の引き込みを防止することができる。その結果、酸
化剤ガス側集電板とインターコネクタとの接触部におけ
る腐食を防止してそれらの接触面積を初期状態（電池組
み込み時の状態）に維持できるため、前記集電板とイン
ターコネクタとの間の電気抵抗の増大を抑制して長寿命
の溶融炭酸塩型燃料電池を実現できる。As described above, the oxidant gas side current collector comes into contact with the flat surface of the interconnector at a predetermined portion,
Since the portion has curved surfaces at both ends, and the barrier material is filled in the space formed between the flat surface of the interconnector and the curved surface of the portion of the current collector plate, the electrolyte is drawn into the space. Can be prevented. As a result, corrosion can be prevented at the contact portion between the oxidant gas side current collector and the interconnector, and the contact area between them can be maintained in the initial state (state when the battery is installed). It is possible to realize a long-life molten carbonate fuel cell by suppressing an increase in electric resistance during the period.

【００４１】また、前記バリア材として燃料電池の作動
温度より融点の低い材料（特に導電材料）を用いること
により、稼働中の酸化剤ガス側集電板のおよびインター
コネクタの熱変形時においてバリア材を前記集電板とイ
ンターコネクタとで形成される空間に柔軟に追従させて
充填させることが可能になる。つまり、熱サイクルが加
わっても前記集電板の曲面とセパレータの平面により形
成される空間にバリア材を良好に充填できる。その結
果、酸化剤ガス側集電板とインターコネクタとの接触部
における腐食をより確実に防止してそれらの接触面積を
初期状態（電池組み込み時の状態）に維持できるため、
集電板とインターコネクタとの間の電気抵抗の増大を効
果的に抑制して長寿命の溶融炭酸塩型燃料電池を実現で
きる。Further, by using a material having a melting point lower than the operating temperature of the fuel cell (particularly, a conductive material) as the barrier material, the barrier material is used during the thermal deformation of the oxidant gas side current collector plate and the interconnector in operation. It is possible to flexibly follow and fill the space formed by the current collector and the interconnector. That is, even if a heat cycle is applied, the space formed by the curved surface of the current collector plate and the flat surface of the separator can be well filled with the barrier material. As a result, it is possible to more reliably prevent corrosion in the contact portion between the oxidant gas side current collector and the interconnector and maintain their contact area in the initial state (state when the battery is assembled).
It is possible to effectively suppress an increase in electric resistance between the current collector plate and the interconnector and realize a long-life molten carbonate fuel cell.

【００４２】（３）集電板の構造 波形の集電板４（または５）は、図３に示すようにアノ
ード２（またはカソード３）と接する第１面２１とイン
ターコネクタ８と接する第２面２２を有し、前記第１面
２１の幅Ｗ1 が前記第２面２２の幅Ｗ2 より広くなるよ
うに複数の波２３が形成されている。前記第１面２１に
は、複数のガス供給用貫通孔２４が開口されている。前
記第１面２１は、アノード２（またはカソード３）に向
かって円弧状に膨らまされている。特に、前記集電板４
（または５）は前記第１面２１の端部が互いに接触する
ようにすることが好ましい。このような形状の集電板４
（または５）は、燃料電池の稼働時においてアノード２
（またはカソード３）が集電板側に落ち込む等の変形を
抑えることができる。(3) Structure of Current Collector Plate The corrugated current collector plate 4 (or 5) has a first surface 21 in contact with the anode 2 (or cathode 3) and a second surface in contact with the interconnector 8 as shown in FIG. A plurality of waves 23 are formed so as to have a surface 22 and the width W 1 of the first surface 21 is wider than the width W 2 of the second surface 22. A plurality of gas supply through holes 24 are formed in the first surface 21. The first surface 21 is expanded in an arc shape toward the anode 2 (or the cathode 3). In particular, the current collector plate 4
It is preferable that (or 5) the end portions of the first surface 21 contact each other. Current collector plate 4 having such a shape
(Or 5) is the anode 2 when the fuel cell is in operation.
It is possible to suppress deformation such as (or the cathode 3) falling toward the current collector plate side.

【００４３】前記集電板は、高温強度および耐食性に優
れたオーステナイト系ステンレス鋼またはニッケル基合
金からなる。前記集電板に用いられるステンレス鋼とし
ては、例えば１０〜２７重量％のＣｒ、７．０〜２８重
量％のＮｉ、０．０８重量％以下のＣｏ、２．０重量％
以下のＭｎ、１．５重量％以下のＳｉ、残部がＦｅおよ
び０．１重量％以下の不可避的不純物の組成を有するも
の等が用いられる。なお、前記ステンレス鋼は５．５重
量％以下のＭｏを含むことを許容する。代表的なステン
レス鋼としては、ＳＵＳ３１０Ｓ、ＳＵＳ３１６Ｌが挙
げられる。ステンレス鋼からなる集電板において、少な
くとも電極と接する面に記Ｆｅ−Ｃｒ−Ｎｉ合金層を被
覆し、さらに前記合金層表面にニッケルフェライト系の
不定比複合酸化物層を形成してもよい。The current collector plate is made of austenitic stainless steel or nickel-base alloy which is excellent in high temperature strength and corrosion resistance. Examples of the stainless steel used for the current collector include 10 to 27% by weight of Cr, 7.0 to 28% by weight of Ni, 0.08% by weight or less of Co, and 2.0% by weight.
Those having the following Mn, Si of 1.5 wt% or less, the balance of Fe, and unavoidable impurities of 0.1 wt% or less are used. The stainless steel is allowed to contain 5.5% by weight or less of Mo. Representative stainless steels include SUS310S and SUS316L. In the current collector made of stainless steel, at least the surface in contact with the electrode may be coated with the Fe-Cr-Ni alloy layer, and a nickel ferrite-based nonstoichiometric complex oxide layer may be formed on the surface of the alloy layer.

【００４４】前記集電板に用いられるニッケル基合金と
しては、例えば１０〜２５重量％のＣｒ、３．０〜２２
重量％のＦｅ、０．０８重量％以下のＣｏ、２．０重量
％以下のＭｎ、１．５重量％以下のＳｉ、残部がＮｉお
よび０．１重量％以下の不可避的不純物の組成を有する
ものが用いられる。代表的なニッケル基合金としては、
インコネル６００が挙げられる。The nickel-base alloy used for the current collector plate is, for example, 10 to 25% by weight of Cr, 3.0 to 22.
It has a composition of wt% Fe, 0.08 wt% or less Co, 2.0 wt% or less Mn, 1.5 wt% or less Si, and the balance Ni and 0.1 wt% or less unavoidable impurities. Things are used. As a typical nickel-based alloy,
Inconel 600 is mentioned.

【００４５】前記オーステナイト系ステンレス鋼または
ニッケル基合金からなる集電板は、２０〜５５０μｍの
厚さを有することが好ましい。このような厚さの集電板
は、燃料電池の総重量を軽減することが可能になる。The current collector plate made of austenitic stainless steel or nickel-based alloy preferably has a thickness of 20 to 550 μm. The collector plate having such a thickness can reduce the total weight of the fuel cell.

【００４６】前記集電板の電極に向かって円弧状にした
第１面の突出高さは、５〜１００μｍにすることが好ま
しい。突出高さを５μｍ未満にすると、応力の分散効果
を十分に発揮することが困難になる。一方、突出高さが
１００μｍを越えると、前記集電板が接触される電極、
つまりアノード（またはカソード）が圧縮されて、ガス
の拡散に支障をきたす。その結果、燃料電池の性能劣化
を招く恐れがある。The protrusion height of the arc-shaped first surface toward the electrode of the current collector is preferably 5 to 100 μm. When the protrusion height is less than 5 μm, it becomes difficult to sufficiently exert the stress dispersion effect. On the other hand, when the protrusion height exceeds 100 μm, the electrode with which the current collector plate is contacted,
That is, the anode (or cathode) is compressed, which hinders gas diffusion. As a result, the performance of the fuel cell may be deteriorated.

【００４７】前記集電板の第１面の幅Ｗ1 は、５〜３０
ｍｍにすることが好ましい。前記第１面の幅Ｗ1 を５ｍ
ｍ未満にすると、集電板の成形が困難になる。一方、前
記第１面の幅Ｗ1 が３０ｍｍを越えると応力の分散効果
が弱く、高温クリープによる変形により電極側の面の一
部が電極から離れて密着性が低下する恐れがある。The width W 1 of the first surface of the collector plate is 5 to 30.
mm is preferable. The width W 1 of the first surface is 5 m
If it is less than m, it becomes difficult to form the current collector plate. On the other hand, if the width W 1 of the first surface exceeds 30 mm, the effect of dispersing stress is weak, and there is a risk that part of the surface on the electrode side will separate from the electrode due to deformation due to high temperature creep and the adhesion will be reduced.

【００４８】前記集電板の第１面は、幅方向のミリメー
タ当たり前記電極に向かう突出高さが０．２〜３０μｍ
であることが好ましい。以上説明したように本発明に係
わる溶融炭酸塩型燃料電池は、電極と接する第１面の幅
をインターコネクタと接する第２面の幅より広くなるよ
うに複数の波が形成され、前記第１面に複数のガス供給
用貫通孔が開口され、さらに前記第１面が前記電極に向
かって円弧状に膨らませた形状を有する集電板を備えて
いる。このような前記集電板において、前記第１面を電
極に向かって円弧状に膨らませることによって、前記集
電板と電極の間の応力を分散できるため、燃料電池を１
００００時間以上に亘って長時間稼働させて、前記集電
板が高温クリープにより変形が生じても、前記集電板と
前記電極との接触を初期状態（電池組み込み時の状態）
に維持できる。その結果、前記集電板と電極間の接触部
における電気抵抗の増大を抑制できるため、長寿命の溶
融炭酸塩型燃料電池を実現できる。The first surface of the current collector plate has a protrusion height of 0.2 to 30 μm toward the electrode per millimeter in the width direction.
It is preferred that As described above, in the molten carbonate fuel cell according to the present invention, a plurality of waves are formed such that the width of the first surface in contact with the electrode is wider than the width of the second surface in contact with the interconnector. The surface is provided with a plurality of through holes for gas supply, and further, the first surface is provided with a current collecting plate having a shape that bulges in an arc shape toward the electrode. In such a current collector plate, by expanding the first surface in an arc shape toward the electrode, the stress between the current collector plate and the electrode can be dispersed.
Even if the current collector is deformed due to high temperature creep after operating for 0000 hours or more for a long time, the contact between the current collector and the electrode is in an initial state (state when the battery is assembled).
Can be maintained at As a result, it is possible to suppress an increase in electric resistance at the contact portion between the current collector plate and the electrode, and thus it is possible to realize a long-life molten carbonate fuel cell.

【００４９】[0049]

【実施例】以下、本発明の好ましい実施例を前述した図
１〜図３を参照して詳細に説明する。 （実施例１）まず、ニッケル基合金の多孔質体からなる
アノードおよびカソードの間にＬｉＡｌＯ2 を主材料と
する多孔質板に混合アルカリ炭酸塩（Ｌｉ2 ＣＯ3 ；６
２モル％、Ｋ2 ＣＯ3 ；３８モル％）を含浸した構造の
電解質板を配置してユニットセルを作製した。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT A preferred embodiment of the present invention will now be described in detail with reference to FIGS. Example 1 First, a mixed alkali carbonate (Li 2 CO 3 ; 6) was added to a porous plate containing LiAlO 2 as a main material between an anode and a cathode made of a nickel-based alloy porous body.
2 mol%, K 2 CO 3 ; 38 mol%) was arranged to arrange an electrolyte plate to prepare a unit cell.

【００５０】また、厚さ３００μｍのＳＵＳ３１６Ｌの
薄板の両面に３５重量％Ｆｅ−２５重量％Ｃｒ−４０重
量％Ｎｉからなる厚さ５０μｍの合金層をクラッド法に
より形成した。この積層薄板にガス供給用貫通孔を開口
し、波形に加工した後、所定の寸法に切り出すことによ
り酸化剤ガス側集電板を作製した。An alloy layer made of 35 wt% Fe-25 wt% Cr-40 wt% Ni and having a thickness of 50 μm was formed on both surfaces of a thin plate of SUS316L having a thickness of 300 μm by the clad method. A gas supply through hole was opened in this laminated thin plate, processed into a corrugated shape, and then cut into a predetermined size to prepare an oxidant gas side current collector plate.

【００５１】さらに、平均径が１０μｍのアルミニウム
粉末７０重量％、スチレン系のバインダ３０重量％をケ
トン系溶剤で分散させたアルミニウムスラリーを、厚さ
０．４ｍｍのステンレス鋼（ＳＵＳ３１６Ｌ）からなる
薄板材の表面に一定量塗布した後、前記溶剤を揮散して
厚さ２００μｍのアルミニウム含有層を形成した。つづ
いて、薄板材を３％の水素を含むアルゴン雰囲気の炉に
設置し、４９０℃の温度で１２時間熱処理することによ
り前記アルミニウム含有層中のバインダを除去した。さ
らに、７５０℃の温度まで昇温し、その温度にて５時間
熱処理し、１℃／分の降温速度で炉冷することにより前
記薄板材表面に厚さ２５μｍの耐食層が形成されたエッ
ジシール板を作製した。Further, an aluminum slurry in which 70% by weight of an aluminum powder having an average diameter of 10 μm and 30% by weight of a styrene type binder are dispersed in a ketone type solvent is used as a thin plate material made of stainless steel (SUS316L) having a thickness of 0.4 mm. After a certain amount was applied to the surface of, the solvent was volatilized to form an aluminum-containing layer having a thickness of 200 μm. Subsequently, the thin plate material was placed in a furnace in an argon atmosphere containing 3% hydrogen and heat-treated at a temperature of 490 ° C. for 12 hours to remove the binder in the aluminum-containing layer. Furthermore, the edge seal having a corrosion-resistant layer having a thickness of 25 μm formed on the surface of the thin plate material is further heated to a temperature of 750 ° C., heat-treated at that temperature for 5 hours, and cooled in a furnace at a temperature decrease rate of 1 ° C./min. A plate was made.

【００５２】次いで、前記ユニットセルを５つ積層する
と共に、前記セルのカソード側に前記酸化剤ガス側集電
板を配置し、前記セルのアノード側に厚さ３００μｍの
ＳＵＳ３１６Ｌからなり、多数のガス供給用貫通孔を有
する波形の集電板を配置し、かつ互いに隣接する集電板
間、最上層の集電板上、および最下層の集電板下面にＳ
ＵＳ３１６Ｌからなるインターコネクタをそれぞれ配置
し、さらに前記電解質板の周縁部を前記エッジシール板
で挟持し、前記挟持部においてスプリング部材で前記エ
ッジシール板を押えることによって前述した図１に示す
構造で、ユニットセルが５つ積層された積層電池を組み
立てた。この積層電池を発電装置内に設置した。Next, five unit cells were laminated, the oxidant gas side current collector plate was arranged on the cathode side of the cell, and a large number of gas was formed on the anode side of the cell, which was made of SUS316L having a thickness of 300 μm. A corrugated current collector plate having through holes for supply is arranged, and S is provided between the current collector plates adjacent to each other, on the uppermost current collector plate, and on the lowermost current collector plate.
An interconnector made of US316L is arranged respectively, further, the peripheral edge of the electrolyte plate is clamped by the edge seal plate, and the edge seal plate is pressed by a spring member in the clamp part, which has the structure shown in FIG. 1 described above. A laminated battery in which five unit cells were laminated was assembled. This laminated battery was installed in the power generator.

【００５３】前記積層電池が設置された発電装置内に炭
酸ガス５０体積％、残部窒素からなるガスをパージガス
として流した。この後、通常の燃料電池の昇温手順に従
って、アノードと集電板とで形成された流路に燃料ガス
（Ｈ2 ）に供給すると共に、カソードと集電板とで形成
された流路に酸化剤ガス（空気またはＣＯ2 ）を供給
し、６５０℃の発電温度まで昇温することにより発電が
なされた。また、３ｋｇ／ｃｍ2 の面圧を前記エッジシ
ール板に付加し、１５０ｍＡ／ｃｍ2 で連続発電を実施
した。１０００時間毎に室温まで降温し、４５００時間
の発電を行った。合計４回の熱サイクルを加えた後の積
層電池の電圧を測定した。その結果、４．７Ｖと高い電
圧を取り出すことができた。A gas consisting of 50% by volume of carbon dioxide gas and the balance of nitrogen was flowed as a purge gas into the power generator in which the laminated battery was installed. Thereafter, fuel gas (H 2 ) is supplied to the flow path formed by the anode and the current collector plate, and the fuel gas (H 2 ) is supplied to the flow path formed by the cathode and the current collector plate in accordance with a normal fuel cell heating procedure. Power was generated by supplying an oxidizing gas (air or CO 2 ) and raising the temperature to a power generation temperature of 650 ° C. Further, a surface pressure of 3 kg / cm 2 was applied to the edge seal plate, and continuous power generation was performed at 150 mA / cm 2 . The temperature was lowered to room temperature every 1000 hours, and power was generated for 4500 hours. The voltage of the laminated battery was measured after applying a total of 4 thermal cycles. As a result, a voltage as high as 4.7 V could be obtained.

【００５４】発電試験後、積層電池を分解して酸化剤ガ
ス側集電板に付着している電解質量を測定した。その結
果、約０．７ｍｇ／ｃｍ2 と極めて少量の電解質しか付
着されていないかった。After the power generation test, the laminated battery was disassembled to measure the electrolytic mass adhering to the oxidant gas side current collector plate. As a result, it was found that only a very small amount of electrolyte of about 0.7 mg / cm 2 was attached.

【００５５】また、前記酸化剤ガス側集電板の一部を切
り取り、断面をＥＰＭＡにより分析した。その結果、集
電板のＦｅ−Ｃｒ−Ｎｉ合金層の表面にＬｉ0.4 Ｎｉ
0.6 Ｆｅ2 Ｏ4 で表される厚さ２１μｍのニッケルフェ
ライト系の不定比複合酸化物層が形成されていることが
確認された。Further, a part of the oxidant gas side current collector plate was cut out and the cross section was analyzed by EPMA. As a result, Li 0.4 Ni was formed on the surface of the Fe—Cr—Ni alloy layer of the current collector.
It was confirmed that a nickel ferrite-based non-stoichiometric composite oxide layer having a thickness of 21 μm and represented by 0.6 Fe 2 O 4 was formed.

【００５６】（実施例２）厚さ３００μｍのＳＵＳ３１
６Ｌの薄板の両面に４０重量％Ｆｅ−２５重量％Ｃｒ−
３５重量％Ｎｉからなる厚さ７０μｍの合金層をクラッ
ド法により形成した。この積層薄板に多数のガス供給用
貫通孔を開口し、波形に加工した後、所定の寸法に切り
出すことにより酸化剤ガス側集電板を作製した。この酸
化剤ガス側集電板を用いた以外、前述した図１に示す構
造で、実施例１と同様なユニットセルが５つ積層された
積層電池を組み立て、これを発電装置内に設置した。Example 2 SUS31 having a thickness of 300 μm
40 wt% Fe-25 wt% Cr-on both sides of a 6 L thin plate
An alloy layer having a thickness of 70 μm and made of 35 wt% Ni was formed by the clad method. A large number of through holes for gas supply were opened in this laminated thin plate, processed into a corrugated shape, and then cut into a predetermined size to prepare an oxidant gas side current collector plate. A laminated battery was constructed in which five unit cells similar to those in Example 1 were laminated with the structure shown in FIG. 1 except that this oxidant gas side current collector was used, and this was installed in a power generator.

【００５７】前記積層電池が設置された発電装置につい
て、実施例１と同様な連続発電を実施し、積層電池の電
圧を測定した。その結果、４．５Ｖと高い電圧を取り出
すことができた。With respect to the power generation device in which the laminated battery was installed, the same continuous power generation as in Example 1 was carried out and the voltage of the laminated battery was measured. As a result, a high voltage of 4.5 V could be obtained.

【００５８】発電試験後、積層電池を分解して酸化剤ガ
ス側集電板に付着している電解質量を測定した。その結
果、約０．６ｍｇ／ｃｍ2 と極めて少量の電解質しか付
着されていないかった。After the power generation test, the laminated battery was disassembled and the electrolytic mass adhering to the oxidant gas side current collector was measured. As a result, only a very small amount of about 0.6 mg / cm 2 of the electrolyte was attached.

【００５９】また、前記酸化剤ガス側集電板の一部を切
り取り、断面をＥＰＭＡにより分析した。その結果、集
電板のＦｅ−Ｃｒ−Ｎｉ合金層の表面にＬｉ2 ＮｉＦｅ
1.5Ｏ4 で表される厚さ２２μｍのニッケルフェライト
系の不定比複合酸化物層が形成されていることが確認さ
れた。Further, a part of the oxidant gas side current collector plate was cut out and the cross section was analyzed by EPMA. As a result, Li 2 NiFe was formed on the surface of the Fe-Cr-Ni alloy layer of the current collector plate.
It was confirmed that a nickel ferrite-based non-stoichiometric composite oxide layer having a thickness of 22 μm and represented by 1.5 O 4 was formed.

【００６０】（実施例３）厚さ２５０μｍのＳＵＳ３１
０Ｓの薄板の両面に３５重量％Ｆｅ−２５重量％Ｃｒ−
４０重量％Ｎｉからなる厚さ７μｍの合金層をクラッド
法により形成した。この積層薄板に多数のガス供給用貫
通孔を開口し、波形に加工した後、所定の寸法に切り出
すことにより酸化剤ガス側集電板を作製した。この酸化
剤ガス側集電板を用いた以外、前述した図１に示す構造
で、実施例１と同様なユニットセルが５つ積層された積
層電池を組み立て、これを発電装置内に設置した。Example 3 SUS31 having a thickness of 250 μm
35% by weight Fe-25% by weight Cr-on both sides of the 0S thin plate
An alloy layer having a thickness of 7 μm and made of 40 wt% Ni was formed by the clad method. A large number of through holes for gas supply were opened in this laminated thin plate, processed into a corrugated shape, and then cut into a predetermined size to prepare an oxidant gas side current collector plate. A laminated battery was constructed in which five unit cells similar to those in Example 1 were laminated with the structure shown in FIG. 1 except that this oxidant gas side current collector was used, and this was installed in a power generator.

【００６１】前記積層電池が設置された発電装置につい
て、実施例１と同様な連続発電を実施し、積層電池の電
圧を測定した。その結果、４．２Ｖと高い電圧を取り出
すことができた。With respect to the power generation device in which the laminated battery was installed, continuous power generation was carried out in the same manner as in Example 1, and the voltage of the laminated battery was measured. As a result, a high voltage of 4.2V could be obtained.

【００６２】発電試験後、積層電池を分解して酸化剤ガ
ス側集電板に付着している電解質量を測定した。その結
果、約０．８ｍｇ／ｃｍ2 と極めて少量の電解質しか付
着されていないかった。After the power generation test, the laminated battery was disassembled to measure the electrolytic mass adhering to the oxidant gas side current collector plate. As a result, it was found that only a very small amount of electrolyte of about 0.8 mg / cm 2 was attached.

【００６３】また、前記酸化剤ガス側集電板の一部を切
り取り、断面をＥＰＭＡにより分析した。その結果、集
電板のＦｅ−Ｃｒ−Ｎｉ合金層の表面にＬｉ0.4 Ｎｉ
0.6 Ｆｅ2 Ｏ4 で表される厚さ８μｍのニッケルフェラ
イト系の不定比複合酸化物層が形成されていることが確
認された。A part of the oxidant gas side current collector plate was cut out and the cross section was analyzed by EPMA. As a result, Li 0.4 Ni was formed on the surface of the Fe—Cr—Ni alloy layer of the current collector.
It was confirmed that a nickel ferrite-based non-stoichiometric composite oxide layer having a thickness of 8 μm and represented by 0.6 Fe 2 O 4 was formed.

【００６４】（実施例４）厚さ２５０μｍのＳＵＳ３１
０Ｓの薄板の両面に３５重量％Ｆｅ−２５重量％Ｃｒ−
４０重量％Ｎｉからなる厚さ２５０μｍの合金層をクラ
ッド法により形成した。この積層薄板に多数のガス供給
用貫通孔を開口し、波形に加工した後、所定の寸法に切
り出すことにより酸化剤ガス側集電板を作製した。この
酸化剤ガス側集電板を用いた以外、前述した図１に示す
構造で、実施例１と同様なユニットセルが５つ積層され
た積層電池を組み立て、これを発電装置内に設置した。Example 4 SUS31 having a thickness of 250 μm
35% by weight Fe-25% by weight Cr-on both sides of the 0S thin plate
An alloy layer of 40 wt% Ni having a thickness of 250 μm was formed by the clad method. A large number of through holes for gas supply were opened in this laminated thin plate, processed into a corrugated shape, and then cut into a predetermined size to prepare an oxidant gas side current collector plate. A laminated battery was constructed in which five unit cells similar to those in Example 1 were laminated with the structure shown in FIG. 1 except that this oxidant gas side current collector was used, and this was installed in a power generator.

【００６５】前記積層電池が設置された発電装置につい
て、実施例１と同様な連続発電を実施し、積層電池の電
圧を測定した。その結果、４．１Ｖと高い電圧を取り出
すことができた。With respect to the power generation device in which the laminated battery was installed, continuous power generation was carried out in the same manner as in Example 1, and the voltage of the laminated battery was measured. As a result, a high voltage of 4.1V could be obtained.

【００６６】発電試験後、積層電池を分解して酸化剤ガ
ス側集電板に付着している電解質量を測定した。その結
果、約０．８ｍｇ／ｃｍ2 と極めて少量の電解質しか付
着されていないかった。After the power generation test, the laminated battery was disassembled to measure the electrolytic mass adhering to the oxidant gas side current collector plate. As a result, it was found that only a very small amount of electrolyte of about 0.8 mg / cm 2 was attached.

【００６７】また、前記酸化剤ガス側集電板の一部を切
り取り、断面をＥＰＭＡにより分析した。その結果、集
電板のＦｅ−Ｃｒ−Ｎｉ合金層の表面にＬｉ0.4 Ｎｉ
0.6 Ｆｅ2 Ｏ4 で表される厚さ２０μｍのニッケルフェ
ライト系の不定比複合酸化物層が形成されていることが
確認された。Further, a part of the oxidant gas side current collector plate was cut out and the cross section was analyzed by EPMA. As a result, Li 0.4 Ni was formed on the surface of the Fe—Cr—Ni alloy layer of the current collector.
It was confirmed that a nickel ferrite-based non-stoichiometric composite oxide layer having a thickness of 20 μm and represented by 0.6 Fe 2 O 4 was formed.

【００６８】（比較例１）厚さ３００μｍのＳＵＳ３１
６Ｌの薄板に多数のガス供給用貫通孔を開口し、波形に
加工した後、所定の寸法に切り出すことにより酸化剤ガ
ス側集電板を作製した。この酸化剤ガス側集電板を用い
た以外、前述した図１に示す構造で、実施例１と同様な
ユニットセルが５つ積層された積層電池を組み立て、こ
れを発電装置内に設置した。(Comparative Example 1) SUS31 having a thickness of 300 μm
A large number of through holes for gas supply were opened in a thin plate of 6 L, processed into a corrugated shape, and then cut into a predetermined size to prepare an oxidant gas side current collector plate. A laminated battery was constructed in which five unit cells similar to those in Example 1 were laminated with the structure shown in FIG. 1 except that this oxidant gas side current collector was used, and this was installed in a power generator.

【００６９】前記積層電池が設置された発電装置内に炭
酸ガス５０体積％、残部窒素からなるガスをパージガス
として流した。この後、通常の燃料電池の昇温手順に従
って、アノードと集電板とで形成された流路に燃料ガス
（Ｈ2 ）に供給すると共に、カソードと集電板とで形成
された流路に酸化剤ガス（空気またはＣＯ2 ）を供給
し、６５０℃の発電温度まで昇温することにより発電が
なされた。また、３ｋｇ／ｃｍ2 の面圧を前記エッジシ
ール板に付加し、１５０ｍＡ／ｃｍ2 で連続発電を実施
した。１０００時間毎に室温まで降温し、３３００時間
の発電を行った。合計３回の熱サイクルを加えた後の積
層電池の電圧を測定した。その結果、実施例１〜４に比
べて発電時間が短く、熱サイクル数が少ないにも拘らず
２．５Ｖと低い電圧しか取り出すことができなかった。A gas consisting of 50% by volume of carbon dioxide gas and the balance of nitrogen was flowed as a purge gas into the power generator in which the laminated battery was installed. Thereafter, fuel gas (H 2 ) is supplied to the flow path formed by the anode and the current collector plate, and the fuel gas (H 2 ) is supplied to the flow path formed by the cathode and the current collector plate in accordance with a normal fuel cell heating procedure. Power was generated by supplying an oxidizing gas (air or CO 2 ) and raising the temperature to a power generation temperature of 650 ° C. Further, a surface pressure of 3 kg / cm 2 was applied to the edge seal plate, and continuous power generation was performed at 150 mA / cm 2 . The temperature was lowered to room temperature every 1000 hours, and power was generated for 3300 hours. The voltage of the laminated battery after the total of three thermal cycles was applied was measured. As a result, compared with Examples 1 to 4, the power generation time was shorter, and although the number of heat cycles was small, only a low voltage of 2.5 V could be taken out.

【００７０】発電試験後、積層電池を分解して酸化剤ガ
ス側集電板に付着している電解質量を測定した。その結
果、発電時間が３３００時間と短いにも拘らず約１．０
ｍｇ／ｃｍ2 の量の電解質が付着されていた。After the power generation test, the laminated battery was disassembled to measure the electrolytic mass adhering to the oxidant gas side current collector plate. As a result, the power generation time was as short as 3300 hours, but about 1.0
An amount of mg / cm 2 of electrolyte was deposited.

【００７１】また、前記酸化剤ガス側集電板の一部を切
り取り、断面をＥＰＭＡにより分析した。その結果、集
電板の表面にＬｉ2 Ｆｅ2 Ｏ4 で表される厚さ４０μｍ
の酸化物層が形成されていることが確認された。したが
って、比較例１の集電板では前述した実施例１〜４のよ
うなニッケルフェライト系の不定比複合酸化物層は形成
されなかった。Further, a part of the oxidant gas side current collector plate was cut out and the cross section was analyzed by EPMA. As a result, a thickness of 40 μm represented by Li 2 Fe 2 O 4 on the surface of the current collector plate.
It was confirmed that the oxide layer of 1 was formed. Therefore, in the current collector of Comparative Example 1, the nickel ferrite-based non-stoichiometric complex oxide layer as in Examples 1 to 4 described above was not formed.

【００７２】（比較例２）厚さ３００μｍのＳＵＳ３１
６Ｌの薄板の両面に厚さ５０μｍのＮｉ層をクラッド法
により形成した。この積層薄板に多数のガス供給用貫通
孔を開口し、波形に加工した後、所定の寸法に切り出す
ことにより酸化剤ガス側集電板を作製した。この酸化剤
ガス側集電板を用いた以外、前述した図１に示す構造
で、実施例１と同様なユニットセルが５つ積層された積
層電池を組み立て、これを発電装置内に設置した。(Comparative Example 2) SUS31 having a thickness of 300 μm
A Ni layer having a thickness of 50 μm was formed on both surfaces of a 6 L thin plate by a clad method. A large number of through holes for gas supply were opened in this laminated thin plate, processed into a corrugated shape, and then cut into a predetermined size to prepare an oxidant gas side current collector plate. A laminated battery was constructed in which five unit cells similar to those in Example 1 were laminated with the structure shown in FIG. 1 except that this oxidant gas side current collector was used, and this was installed in a power generator.

【００７３】前記積層電池が設置された発電装置内に炭
酸ガス５０体積％、残部窒素からなるガスをパージガス
として流した。この後、通常の燃料電池の昇温手順に従
って、アノードと集電板とで形成された流路に燃料ガス
（Ｈ2 ）に供給すると共に、カソードと集電板とで形成
された流路に酸化剤ガス（空気またはＣＯ2 ）を供給
し、６５０℃の発電温度まで昇温することにより発電が
なされた。また、３ｋｇ／ｃｍ2 の面圧を前記エッジシ
ール板に付加し、１５０ｍＡ／ｃｍ2 で連続発電を実施
した。１０００時間毎に室温まで降温し、３５００時間
の発電を行った。合計３回の熱サイクルを加えた後の積
層電池の電圧を測定した。その結果、実施例１〜４に比
べて発電時間が短く、熱サイクル数が少ないにも拘らず
３．０Ｖと低い電圧しか取り出すことができなかった。A gas consisting of 50% by volume of carbon dioxide gas and the balance of nitrogen gas was caused to flow as a purge gas into the power generator in which the laminated battery was installed. Thereafter, fuel gas (H 2 ) is supplied to the flow path formed by the anode and the current collector plate, and the fuel gas (H 2 ) is supplied to the flow path formed by the cathode and the current collector plate in accordance with a normal fuel cell heating procedure. Power was generated by supplying an oxidizing gas (air or CO 2 ) and raising the temperature to a power generation temperature of 650 ° C. Further, a surface pressure of 3 kg / cm 2 was applied to the edge seal plate, and continuous power generation was performed at 150 mA / cm 2 . The temperature was lowered to room temperature every 1000 hours, and power was generated for 3500 hours. The voltage of the laminated battery after the total of three thermal cycles was applied was measured. As a result, power generation time was shorter than in Examples 1 to 4, and only a low voltage of 3.0 V could be taken out despite the small number of heat cycles.

【００７４】発電試験後、積層電池を分解して酸化剤ガ
ス側集電板に付着している電解質量を測定した。その結
果、発電時間が３５００時間と短いにも拘らず約２．１
ｍｇ／ｃｍ2 の量の電解質が付着されていた。After the power generation test, the laminated battery was disassembled and the electrolytic mass adhering to the oxidant gas side current collector was measured. As a result, the power generation time was as short as 3500 hours, but about 2.1
An amount of mg / cm 2 of electrolyte was deposited.

【００７５】また、前記酸化剤ガス側集電板の一部を切
り取り、断面をＥＰＭＡにより分析した。その結果、集
電板の表面にＮｉＯで表される厚さ５５μｍの酸化物層
が形成されていることが確認された。したがって、比較
例２の集電板では前述した実施例１〜４のようなニッケ
ルフェライト系の不定比複合酸化物層は形成されなかっ
た。Further, a part of the current collector plate on the oxidant gas side was cut out and the cross section was analyzed by EPMA. As a result, it was confirmed that a 55 μm-thick oxide layer represented by NiO was formed on the surface of the current collector plate. Therefore, in the current collector of Comparative Example 2, the nickel ferrite-based non-stoichiometric complex oxide layer as in Examples 1 to 4 described above was not formed.

【００７６】（比較例３）厚さ３００μｍのＳＵＳ３１
６Ｌの薄板の両面に５０重量％Ｆｅ−２０重量％Ｃｒ−
３０重量％Ｎｉからなる厚さ７０μｍの合金層をクラッ
ド法により形成した。この積層薄板に多数のガス供給用
貫通孔を開口し、波形に加工した後、所定の寸法に切り
出すことにより酸化剤ガス側集電板を作製した。この酸
化剤ガス側集電板を用いた以外、前述した図１に示す構
造で、実施例１と同様なユニットセルが５つ積層された
積層電池を組み立て、これを発電装置内に設置した。Comparative Example 3 SUS31 having a thickness of 300 μm
50 wt% Fe-20 wt% Cr-on both sides of a 6 L thin plate
An alloy layer of 30 wt% Ni having a thickness of 70 μm was formed by the clad method. A large number of through holes for gas supply were opened in this laminated thin plate, processed into a corrugated shape, and then cut into a predetermined size to prepare an oxidant gas side current collector plate. A laminated battery was constructed in which five unit cells similar to those in Example 1 were laminated with the structure shown in FIG. 1 except that this oxidant gas side current collector was used, and this was installed in a power generator.

【００７７】前記積層電池が設置された発電装置内に炭
酸ガス５０体積％、残部窒素からなるガスをパージガス
として流した。この後、通常の燃料電池の昇温手順に従
って、アノードと集電板とで形成された流路に燃料ガス
（Ｈ2 ）に供給すると共に、カソードと集電板とで形成
された流路に酸化剤ガス（空気またはＣＯ2 ）を供給
し、６５０℃の発電温度まで昇温することにより発電が
なされた。また、３ｋｇ／ｃｍ2 の面圧を前記エッジシ
ール板に付加し、１５０ｍＡ／ｃｍ2 で連続発電を実施
した。１０００時間毎に室温まで降温し、４３００時間
の発電を行った。合計４回の熱サイクルを加えた後の積
層電池の電圧を測定した。その結果、３．５Ｖと低い電
圧しか取り出すことができなかった。A gas consisting of 50% by volume of carbon dioxide gas and the balance of nitrogen was passed as a purge gas into the power generator in which the laminated battery was installed. Thereafter, fuel gas (H 2 ) is supplied to the flow path formed by the anode and the current collector plate, and the fuel gas (H 2 ) is supplied to the flow path formed by the cathode and the current collector plate in accordance with a normal fuel cell heating procedure. Power was generated by supplying an oxidizing gas (air or CO 2 ) and raising the temperature to a power generation temperature of 650 ° C. Further, a surface pressure of 3 kg / cm 2 was applied to the edge seal plate, and continuous power generation was performed at 150 mA / cm 2 . The temperature was lowered to room temperature every 1000 hours, and power was generated for 4300 hours. The voltage of the laminated battery was measured after applying a total of 4 thermal cycles. As a result, only a voltage as low as 3.5 V could be taken out.

【００７８】発電試験後、積層電池を分解して酸化剤ガ
ス側集電板に付着している電解質量を測定した。その結
果、約０．８ｍｇ／ｃｍ2 の量の電解質が付着されてい
た。また、前記集電板の一部を切り取り、断面をＥＰＭ
Ａにより分析した。その結果、集電板のＦｅ−Ｃｒ−Ｎ
ｉ合金層の表面にＬｉＦｅ2 Ｏ4 で表される厚さ４５μ
ｍの酸化物層が形成されていることが確認された。した
がって、比較例３の集電板では前記Ｆｅ−Ｃｒ−Ｎｉ合
金層中のＦｅ成分が本発明の範囲（２３〜４５重量％）
より多く含まれいるため、前述した実施例１〜４のよう
なニッケルフェライト系の不定比複合酸化物層は形成さ
れなかった。After the power generation test, the laminated battery was disassembled and the electrolytic mass adhering to the oxidant gas side current collector was measured. As a result, about 0.8 mg / cm 2 of the electrolyte was attached. In addition, a part of the current collector plate is cut out and the cross section is EPM
Analyzed by A. As a result, the Fe-Cr-N of the current collector plate
The surface of the i-alloy layer has a thickness of 45 μm represented by LiFe 2 O 4.
It was confirmed that an oxide layer of m was formed. Therefore, in the current collector of Comparative Example 3, the Fe component in the Fe—Cr—Ni alloy layer is within the range of the present invention (23 to 45 wt%).
Since it was contained in a larger amount, the nickel ferrite-based non-stoichiometric composite oxide layer as in Examples 1 to 4 described above was not formed.

【００７９】（比較例４）厚さ３００μｍのＳＵＳ３１
６Ｌの薄板の両面に１５重量％Ｆｅ−１５重量％Ｃｒ−
７０重量％Ｎｉからなる厚さ７０μｍの合金層をクラッ
ド法により形成した。この積層薄板に多数のガス供給用
貫通孔を開口し、波形に加工した後、所定の寸法に切り
出すことにより酸化剤ガス側集電板を作製した。この酸
化剤ガス側集電板を用いた以外、前述した図１に示す構
造で、実施例１と同様なユニットセルが５つ積層された
積層電池を組み立て、これを発電装置内に設置した。(Comparative Example 4) SUS31 having a thickness of 300 μm
15 wt% Fe-15 wt% Cr-on both sides of a 6 L thin plate
A 70 μm thick alloy layer made of 70 wt% Ni was formed by the clad method. A large number of through holes for gas supply were opened in this laminated thin plate, processed into a corrugated shape, and then cut into a predetermined size to prepare an oxidant gas side current collector plate. A laminated battery was constructed in which five unit cells similar to those in Example 1 were laminated with the structure shown in FIG. 1 except that this oxidant gas side current collector was used, and this was installed in a power generator.

【００８０】前記積層電池が設置された発電装置内に炭
酸ガス５０体積％、残部窒素からなるガスをパージガス
として流した。この後、通常の燃料電池の昇温手順に従
って、アノードと集電板とで形成された流路に燃料ガス
（Ｈ2 ）に供給すると共に、カソードと集電板とで形成
された流路に酸化剤ガス（空気またはＣＯ2 ）を供給
し、６５０℃の発電温度まで昇温することにより発電が
なされた。また、３ｋｇ／ｃｍ2 の面圧を前記エッジシ
ール板に付加し、１５０ｍＡ／ｃｍ2 で連続発電を実施
した。１０００時間毎に室温まで降温し、４５００時間
の発電を行った。合計４回の熱サイクルを加えた後の積
層電池の電圧を測定した。その結果、３．７Ｖと低い電
圧しか取り出すことができなかった。A gas consisting of 50% by volume of carbon dioxide gas and the balance of nitrogen was passed as a purge gas into the power generator in which the laminated battery was installed. Thereafter, fuel gas (H 2 ) is supplied to the flow path formed by the anode and the current collector plate, and the fuel gas (H 2 ) is supplied to the flow path formed by the cathode and the current collector plate in accordance with a normal fuel cell heating procedure. Power was generated by supplying an oxidizing gas (air or CO 2 ) and raising the temperature to a power generation temperature of 650 ° C. Further, a surface pressure of 3 kg / cm 2 was applied to the edge seal plate, and continuous power generation was performed at 150 mA / cm 2 . The temperature was lowered to room temperature every 1000 hours, and power was generated for 4500 hours. The voltage of the laminated battery was measured after applying a total of 4 thermal cycles. As a result, only a low voltage of 3.7V could be taken out.

【００８１】発電試験後、積層電池を分解して酸化剤ガ
ス側集電板に付着している電解質量を測定した。その結
果、約１．７ｍｇ／ｃｍ2 の量の電解質が付着されてい
た。また、前記酸化剤ガス側集電板の一部を切り取り、
断面をＥＰＭＡにより分析した。その結果、集電板のＦ
ｅ−Ｃｒ−Ｎｉ合金層の表面に厚さ７５μｍのＮｉＯか
らなる酸化物層が形成されていることが確認された。し
たがって、比較例４の集電板では前記Ｆｅ−Ｃｒ−Ｎｉ
合金層中のＦｅ成分が本発明の範囲（２３〜４５重量
％）より少ない量で含まれているため、前述した実施例
１〜４のようなニッケルフェライト系の不定比複合酸化
物層は形成されなかった。After the power generation test, the laminated battery was disassembled and the electrolytic mass adhering to the oxidant gas side current collector was measured. As a result, an amount of electrolyte of about 1.7 mg / cm 2 was attached. Further, a part of the oxidant gas side current collector plate is cut off,
The cross section was analyzed by EPMA. As a result, F of the current collector
It was confirmed that an oxide layer made of NiO having a thickness of 75 μm was formed on the surface of the e-Cr-Ni alloy layer. Therefore, in the current collector of Comparative Example 4, the Fe-Cr-Ni
Since the Fe component in the alloy layer is contained in an amount smaller than the range of the present invention (23 to 45% by weight), the nickel ferrite-based non-stoichiometric complex oxide layer as in Examples 1 to 4 described above is formed. Was not done.

【００８２】（実施例５）まず、ニッケル基合金の多孔
質体からなるアノードおよびカソードの間にＬｉＡｌＯ
2 を主材料とする多孔質板に混合アルカリ炭酸塩（Ｌｉ
2 ＣＯ3 ；６２モル％、Ｋ2 ＣＯ3 ；３８モル％）を含
浸した構造の電解質板を配置してユニットセルを作製し
た。(Embodiment 5) First, LiAlO 2 is provided between an anode and a cathode made of a nickel-base alloy porous material.
Porous plate in the mixed alkali carbonate to 2 as a main material (Li
2 CO 3 ; 62 mol%, K 2 CO 3 ; 38 mol%) were arranged to form an electrolyte plate to prepare a unit cell.

【００８３】また、厚さ３００μｍのＳＵＳ３１０Ｓの
薄板に多数のガス供給用貫通孔を開口し、波形に加工し
た後、所定の寸法に切り出すことにより集電板を作製し
た。さらに、平均径が１０μｍのアルミニウム粉末７０
重量％、スチレン系のバインダ３０重量％をケトン系溶
剤で分散させたアルミニウムスラリーを、厚さ０．４ｍ
ｍのステンレス鋼（ＳＵＳ３１６Ｌ）からなる薄板材の
表面に一定量塗布した後、前記溶剤を揮散して厚さ２０
０μｍのアルミニウム含有層を形成した。つづいて、薄
板材を３％の水素を含むアルゴン雰囲気の炉に設置し、
４９０℃の温度で１２時間熱処理することにより前記ア
ルミニウム含有層中のバインダを除去した。さらに、７
５０℃の温度まで昇温し、その温度にて５時間熱処理
し、１℃／分の降温速度で炉冷することにより前記薄板
材表面に厚さ２５μｍの耐食層が形成されたエッジシー
ル板を作製した。Further, a large number of through holes for gas supply were opened in a thin plate of SUS310S having a thickness of 300 μm, processed into a corrugated shape, and then cut into a predetermined size to prepare a current collector plate. Further, aluminum powder 70 having an average diameter of 10 μm
An aluminum slurry in which 30% by weight of a styrene-based binder and 30% by weight of a styrene-based binder are dispersed in a ketone-based solvent has a thickness of 0.4 m.
m of stainless steel (SUS316L) is applied on the surface of a thin plate, and the solvent is evaporated to a thickness of 20.
An aluminum-containing layer of 0 μm was formed. Subsequently, the thin plate material was placed in a furnace with an argon atmosphere containing 3% hydrogen,
The binder in the aluminum-containing layer was removed by heat treatment at a temperature of 490 ° C. for 12 hours. In addition, 7
The edge seal plate having a 25 μm-thick corrosion resistant layer formed on the surface of the thin plate material is heated to a temperature of 50 ° C., heat-treated at that temperature for 5 hours, and cooled in the furnace at a temperature decrease rate of 1 ° C./min. It was made.

【００８４】次いで、前記ユニットセルを５つ積層する
と共に、前記セルのカソードおよびアノード側に前記集
電板をそれぞれ配置し、かつ互いに隣接する集電板間、
最上層の集電板上、および最下層の集電板下面にＳＵＳ
３１０Ｓからなるインターコネクタをそれぞれ配置し、
さらに前記電解質板の周縁部を前記エッジシール板で挟
持し、前記挟持部においてスプリング部材で前記エッジ
シール板を押えることによって前述した図１に示す構造
で、ユニットセルが５つ積層された積層電池を組み立て
た。なお、前記酸化剤ガス側集電板は前記インターコネ
クタの平面と所定の部位で接触し、前記所定の部位は両
端で曲面を有し、金はんだは前記インターコネクタの平
面と前記集電板の所定の部位の曲面とで形成される空間
に置いた。このような積層電池を発電装置内に設置し
た。Next, five unit cells were laminated, the current collector plates were respectively arranged on the cathode and anode sides of the cells, and between the current collector plates adjacent to each other,
SUS on the uppermost current collector plate and on the lowermost current collector plate
Arrange the interconnectors consisting of 310S,
Further, a peripheral battery of the electrolyte plate is clamped by the edge seal plate, and the edge seal plate is pressed by a spring member in the clamp portion, and the structure shown in FIG. Assembled. The oxidant gas side current collector plate is in contact with the flat surface of the interconnector at a predetermined portion, the predetermined portion has curved surfaces at both ends, and gold solder is the flat surface of the interconnector and the collector plate. It was placed in a space formed by the curved surface of a predetermined part. Such a laminated battery was installed in the power generator.

【００８５】前記積層電池が設置された発電装置内に炭
酸ガス５０体積％、残部窒素からなるガスをパージガス
として流した。この後、通常の燃料電池の昇温手順に従
って、アノードと集電板とで形成された流路に燃料ガス
（Ｈ2 ）に供給すると共に、カソードと集電板とで形成
された流路に酸化剤ガス（空気またはＣＯ2 ）を供給
し、６５０℃の発電温度まで昇温することにより発電が
なされた。また、３ｋｇ／ｃｍ2 の面圧を前記エッジシ
ール板に付加し、１５０ｍＡ／ｃｍ2 で連続発電を実施
した。４００時間毎に室温まで降温し、２回の熱サイク
ルを掛けて１０００時間経過させた。この間の内部抵抗
を下記表１に示す。A gas consisting of 50% by volume of carbon dioxide gas and the balance of nitrogen gas was caused to flow as a purge gas into the power generator in which the laminated battery was installed. Thereafter, fuel gas (H 2 ) is supplied to the flow path formed by the anode and the current collector plate, and the fuel gas (H 2 ) is supplied to the flow path formed by the cathode and the current collector plate in accordance with a normal fuel cell heating procedure. Power was generated by supplying an oxidizing gas (air or CO 2 ) and raising the temperature to a power generation temperature of 650 ° C. Further, a surface pressure of 3 kg / cm 2 was applied to the edge seal plate, and continuous power generation was performed at 150 mA / cm 2 . The temperature was lowered to room temperature every 400 hours, and two thermal cycles were applied for 1000 hours. The internal resistance during this period is shown in Table 1 below.

【００８６】（実施例６）波形の酸化剤ガス側集電板
は、インターコネクタの平面と所定の部位で接触し、前
記所定の部位は両端で曲面を有する。Ａｌ−Ｓｉろう線
は、前記インターコネクタの平面と前記集電板の所定の
部位の曲面とで形成される空間に置いた。なお、前記集
電板は厚さ３００μｍのＳＵＳ３１０Ｓからなり、前記
インターコネクタはＳＵＳ３１０Ｓからなる。このよう
な集電板およびインターコネクタを用いた以外、前述し
た図１に示す構造で、実施例５と同様なユニットセルが
５つ積層された積層電池を組み立て、これを発電装置内
に設置した。(Embodiment 6) The corrugated oxidant gas side current collector is in contact with the flat surface of the interconnector at predetermined portions, and the predetermined portions have curved surfaces at both ends. The Al-Si brazing wire was placed in the space formed by the flat surface of the interconnector and the curved surface of a predetermined portion of the current collector plate. The current collector plate is made of SUS310S having a thickness of 300 μm, and the interconnector is made of SUS310S. A laminated battery was constructed in which five unit cells similar to those of Example 5 were laminated with the structure shown in FIG. 1 except that such a current collector plate and interconnector were used, and this was installed in a power generator. .

【００８７】前記積層電池が設置された発電装置につい
て、実施例５と同様に１０００時間の連続発電を実施し
た。この間の内部抵抗を下記表１に示す。 （実施例７）波形の酸化剤ガス側集電板は、インターコ
ネクタの平面と所定の部位で接触し、前記所定の部位は
両端で曲面を有する。Ａｇろう線は、前記インターコネ
クタの平面と前記集電板の所定の部位の曲面とで形成さ
れる空間に置いた。なお、前記集電板は厚さ３００μｍ
のＳＵＳ３１０Ｓからなり、前記インターコネクタはＳ
ＵＳ３１０Ｓからなる。このような集電板およびインタ
ーコネクタを用いた以外、前述した図１に示す構造で、
実施例５と同様なユニットセルが５つ積層された積層電
池を組み立て、これを発電装置内に設置した。With respect to the power generation device in which the laminated battery was installed, continuous power generation was carried out for 1000 hours in the same manner as in Example 5. The internal resistance during this period is shown in Table 1 below. (Embodiment 7) The corrugated oxidant gas side current collector is in contact with the flat surface of the interconnector at a predetermined portion, and the predetermined portion has curved surfaces at both ends. The Ag brazing wire was placed in the space formed by the flat surface of the interconnector and the curved surface of a predetermined portion of the current collector plate. The current collector plate has a thickness of 300 μm.
SUS310S, and the interconnector is S
It consists of US310S. With the structure shown in FIG. 1 except that the current collector plate and the interconnector are used,
A laminated battery in which five unit cells similar to those in Example 5 were laminated was assembled and installed in a power generator.

【００８８】前記積層電池が設置された発電装置につい
て、実施例５と同様に１０００時間の連続発電を実施し
た。この間の内部抵抗を下記表１に示す。 （実施例８）波形の酸化剤ガス側集電板は、インターコ
ネクタの平面と所定の部位で接触し、前記所定の部位は
両端で曲面を有する。ＺｎＯ−Ｂ2 Ｏ3 （低融点ガラ
ス）粉末は、前記インターコネクタの平面と前記集電板
の所定の部位の曲面とで形成される空間に撒かれた。な
お、前記集電板は厚さ３００μｍのＳＵＳ３１０Ｓから
なり、前記インターコネクタはＳＵＳ３１０Ｓからな
る。このような集電板およびインターコネクタを用いた
以外、前述した図１に示す構造で、実施例５と同様なユ
ニットセルが５つ積層された積層電池を組み立て、これ
を発電装置内に設置した。With respect to the power generation device in which the laminated battery was installed, continuous power generation for 1000 hours was carried out in the same manner as in Example 5. The internal resistance during this period is shown in Table 1 below. (Embodiment 8) The corrugated oxidant gas side current collector comes into contact with the flat surface of the interconnector at predetermined portions, and the predetermined portions have curved surfaces at both ends. ZnO-B 2 O 3 (low melting glass) powder was sprinkled in the space formed by the predetermined site curved plane and the collector plate of the interconnector. The current collector plate is made of SUS310S having a thickness of 300 μm, and the interconnector is made of SUS310S. A laminated battery was constructed in which five unit cells similar to those of Example 5 were laminated with the structure shown in FIG. 1 except that such a current collector plate and interconnector were used, and this was installed in a power generator. .

【００８９】前記積層電池が設置された発電装置につい
て、実施例５と同様に１０００時間の連続発電を実施し
た。この間の内部抵抗を下記表１に示す。 （実施例９）波形の酸化剤ガス側集電板は、インターコ
ネクタの平面と所定の部位で接触し、前記所定の部位は
両端で曲面を有する。金ろう線は、前記インターコネク
タの平面と前記集電板の所定の部位の曲面とで形成され
る空間に置かれた。これをセル外で２ｋｇ／ｃｍ2 の面
圧を加えて９１０℃、１０分間熱処理して予め前記空間
に金ろうを充填した。なお、前記集電板は厚さ３００μ
ｍのＳＵＳ３１０Ｓからなり、前記インターコネクタは
ＳＵＳ３１０Ｓからなる。このような集電板およびイン
ターコネクタを用いた以外、前述した図１に示す構造
で、実施例５と同様なユニットセルが５つ積層された積
層電池を組み立て、これを発電装置内に設置した。With respect to the power generation device in which the laminated battery was installed, continuous power generation was carried out for 1000 hours in the same manner as in Example 5. The internal resistance during this period is shown in Table 1 below. (Example 9) The corrugated oxidant gas side current collector is in contact with the flat surface of the interconnector at a predetermined portion, and the predetermined portion has curved surfaces at both ends. The brazing wire was placed in a space formed by the flat surface of the interconnector and the curved surface of a predetermined portion of the current collector plate. A surface pressure of 2 kg / cm 2 was applied outside the cell, and heat treatment was performed at 910 ° C. for 10 minutes to fill the space with gold brazing in advance. The current collector plate has a thickness of 300 μm.
m SUS310S, and the interconnector is SUS310S. A laminated battery was constructed in which five unit cells similar to those of Example 5 were laminated with the structure shown in FIG. 1 except that such a current collector plate and interconnector were used, and this was installed in a power generator. .

【００９０】前記積層電池が設置された発電装置につい
て、実施例５と同様に１０００時間の連続発電を実施し
た。この間の内部抵抗を下記表１に示す。 （実施例１０）波形の酸化剤ガス側集電板は、インター
コネクタの平面と所定の部位で接触し、前記所定の部位
は両端で曲面を有する。パラジウムろう線は、前記イン
ターコネクタの平面と前記集電板の所定の部位の曲面と
で形成される空間に置かれた。これをセル外で２ｋｇ／
ｃｍ2 の面圧を加えて９００℃、１０分間熱処理して予
め前記空間にＢＰｄ−２パラジウムろうを充填した。な
お、前記集電板は厚さ３００μｍのＳＵＳ３１０Ｓから
なり、前記インターコネクタはＳＵＳ３１０Ｓからな
る。このような集電板およびインターコネクタを用いた
以外、前述した図１に示す構造で、実施例５と同様なユ
ニットセルが５つ積層された積層電池を組み立て、これ
を発電装置内に設置した。With respect to the power generation device in which the laminated battery was installed, continuous power generation for 1000 hours was carried out in the same manner as in Example 5. The internal resistance during this period is shown in Table 1 below. (Example 10) The corrugated oxidant gas side current collector is in contact with the flat surface of the interconnector at a predetermined portion, and the predetermined portion has curved surfaces at both ends. The palladium brazing wire was placed in a space formed by the flat surface of the interconnector and the curved surface of a predetermined portion of the current collector plate. This is 2kg / outside the cell
A surface pressure of cm 2 was applied and heat treatment was performed at 900 ° C. for 10 minutes to fill the space with BPd-2 palladium braze in advance. The current collector plate is made of SUS310S having a thickness of 300 μm, and the interconnector is made of SUS310S. A laminated battery was constructed in which five unit cells similar to those of Example 5 were laminated with the structure shown in FIG. 1 except that such a current collector plate and interconnector were used, and this was installed in a power generator. .

【００９１】前記積層電池が設置された発電装置につい
て、実施例５と同様に１０００時間の連続発電を実施し
た。この間の内部抵抗を下記表１に示す。 （比較例６）厚さ３００μｍのＳＵＳ３１０Ｓからなる
波形の酸化剤ガス側集電板とＳＵＳ３１０Ｓからなるイ
ンターコネクタとを単に積層した以外、前述した図１に
示す構造で、実施例５と同様なユニットセルが５つ積層
された積層電池を組み立て、これを発電装置内に設置し
た。With respect to the power generation device in which the laminated battery was installed, continuous power generation was performed for 1000 hours as in Example 5. The internal resistance during this period is shown in Table 1 below. (Comparative Example 6) A unit similar to that of Example 5 except that the corrugated oxidant gas side current collector plate made of SUS310S having a thickness of 300 μm and the interconnector made of SUS310S were simply laminated. A laminated battery in which five cells were laminated was assembled and installed in a power generator.

【００９２】前記積層電池が設置された発電装置につい
て、実施例５と同様に１０００時間の連続発電を実施し
た。この間の内部抵抗を下記表１に示す。 （比較例７）厚さ３００μｍのＳＵＳ３１０Ｓからなる
波形の酸化剤ガス側集電板とＳＵＳ３１０Ｓからなるイ
ンターコネクタを積層し、前記集電板凸部とインターコ
ネクタの接触面に金ろう箔を挟んだ。これを９１０℃で
炉中にてろう付けした。このような集電板およびインタ
ーコネクタを用いた以外、前述した図１に示す構造で、
実施例５と同様なユニットセルが５つ積層された積層電
池を組み立て、これを発電装置内に設置した。With respect to the power generation device in which the laminated battery was installed, continuous power generation was carried out for 1000 hours in the same manner as in Example 5. The internal resistance during this period is shown in Table 1 below. (Comparative Example 7) A corrugated oxidant gas side current collector made of SUS310S having a thickness of 300 μm and an interconnector made of SUS310S were laminated, and a gold brazing foil was sandwiched between the convex portion of the current collector and the contact surface of the interconnector. . This was brazed at 910 ° C. in a furnace. With the structure shown in FIG. 1 except that the current collector plate and the interconnector are used,
A laminated battery in which five unit cells similar to those in Example 5 were laminated was assembled and installed in a power generator.

【００９３】前記積層電池が設置された発電装置につい
て、実施例５と同様に１０００時間の連続発電を実施し
た。この間の内部抵抗を下記表１に示す。 （比較例８）ＳＵＳ３１０Ｓからなる１２５ｍｍ角の酸
化剤ガス側集電板とＳＵＳ３１０Ｓからなるインターコ
ネクタを積層し、前記集電板凸部とインターコネクタの
接触面にＮｉろう箔を挟んだ。これを１０００℃で炉中
にてろう付けした。このような集電板およびインターコ
ネクタを用いた以外、前述した図１に示す構造で、実施
例５と同様なユニットセルが５つ積層された積層電池を
組み立て、これを発電装置内に設置した。With respect to the power generation device in which the laminated battery was installed, continuous power generation was carried out for 1000 hours in the same manner as in Example 5. The internal resistance during this period is shown in Table 1 below. (Comparative Example 8) A 125 mm square oxidant gas side current collector plate made of SUS310S and an interconnector made of SUS310S were laminated, and a Ni brazing foil was sandwiched between the contact surfaces of the convex part of the current collector plate and the interconnector. This was brazed at 1000 ° C. in a furnace. A laminated battery was constructed in which five unit cells similar to those of Example 5 were laminated with the structure shown in FIG. 1 except that such a current collector plate and interconnector were used, and this was installed in a power generator. .

【００９４】前記積層電池が設置された発電装置につい
て、実施例５と同様に１０００時間の連続発電を実施し
た。この間の内部抵抗を下記表１に示す。 表１ バリア材 内部抵抗増加 ｍΩ・ｃｍ2 実施例５ 金はんだ ９ 実施例６ Ａｌ−Ｓｉろう １３ 実施例７ 銀ろう １４ 実施例８ ＺｎＯ−Ｂ2 Ｏ3 １６ 実施例９ 金ろう ２６ 実施例10 パラジウムろう ２８ 比較例６ な し １１２ 比較例７ なし＊ ６３ 比較例８ なし＊＊ ９６ ＊：集電板とインターコネクタの接触面に金ろう付 ＊＊：集電板とインターコネクタの接触面にＮｉろう付 前記表１から明らかなように実施例５〜１０の燃料電池
では、２回の熱サイクルを含む１０００時間の運転後も
抵抗増加は３０ｍΩ・ｃｍ2 以下に治まっている。特
に、バリア材の融点が燃料電池の作動温度より低い実施
例５〜８においては抵抗増加が２０ｍΩ・ｃｍ2 以下で
あり、電池の内部抵抗増加を十分に抑制できることがわ
かる。With respect to the power generator having the above-mentioned laminated battery, continuous power generation was carried out for 1000 hours in the same manner as in Example 5. The internal resistance during this period is shown in Table 1 below. Table 1 Increase in internal resistance of barrier material mΩ · cm 2 Example 5 Gold solder 9 Example 6 Al-Si solder 13 Example 7 Silver solder 14 Example 8 ZnO-B 2 O 3 16 Example 9 Gold solder 26 Example 10 Palladium braze 28 Comparative Example 6 None 112 Comparative Example 7 None * 63 Comparative Example 8 None ** 96 *: Gold brazing on the contact surface between the current collector and the interconnector **: On the contact surface between the current collector and the interconnector Ni brazing As is clear from Table 1 above, in the fuel cells of Examples 5 to 10, the increase in resistance subsided to 30 mΩ · cm 2 or less even after 1000 hours of operation including two thermal cycles. Particularly, in Examples 5 to 8 in which the melting point of the barrier material is lower than the operating temperature of the fuel cell, the increase in resistance was 20 mΩ · cm 2 or less, and it can be seen that the increase in internal resistance of the cell can be sufficiently suppressed.

【００９５】これに対し、比較例６〜８の燃料電池にお
いては、２回の熱サイクルを含む１０００時間の運転後
の抵抗増加が６０ｍΩ・ｃｍ2 以上であり、電池の性能
劣化が著しいことがわかる。On the other hand, in the fuel cells of Comparative Examples 6 to 8, the resistance increase after the operation for 1000 hours including the two thermal cycles was 60 mΩ · cm 2 or more, and the performance deterioration of the cells was remarkable. Recognize.

【００９６】（実施例１１）まず、ニッケル基合金の多
孔質体からなるアノードおよびカソードの間にＬｉＡｌ
Ｏ2 を主材料とする多孔質板に混合アルカリ炭酸塩（Ｌ
ｉ2 ＣＯ3 ；６２モル％、Ｋ2 ＣＯ3 ；３８モル％）を
含浸した構造の電解質板を配置してユニットセルを作製
した。(Embodiment 11) First, LiAl is formed between an anode and a cathode made of a nickel-base alloy porous material.
The O 2 in the porous plate to the main material mixed alkali carbonate (L
i 2 CO 3 ; 62 mol%, K 2 CO 3 ; 38 mol%) was arranged, and an electrolyte plate having a structure impregnated was arranged to produce a unit cell.

【００９７】また、厚さ２５０μｍのＳＵＳ３１０Ｓの
薄板の片面に３５重量％Ｆｅ−２５重量％Ｃｒ−４０重
量％Ｎｉからなる厚さ５０μｍの合金層をクラッド法に
より形成した。この積層薄板に多数のガス供給用貫通孔
を開口し、波形に加工した後、所定寸法に切り出すこと
により前述した図３に示すように複数の波２３を有する
形状の酸化剤ガス側集電板を作製した。すなわち、得ら
れた前記集電板は図３に示すようにカソードと接する第
１面２１および前記インターコネクタ８と接する第２面
２２を有し、前記第１面２１の前記カソード側は前記合
金層が被覆されている。前記第１面２１の幅Ｗ1 は、前
記第２面２２の幅Ｗ2 より広く、かつ前記第１面２１の
端部は互いに接触されている。前記第１面２１には、複
数のガス供給用貫通孔２４が開口されている。また、前
記第１面２１はカソードに向かって円弧状に膨らまされ
ている。なお、前記第１面２１において電極に向かって
円弧状に突出した高さを５０μｍ、その幅を１５ｍｍに
した。An alloy layer made of 35 wt% Fe-25 wt% Cr-40 wt% Ni and having a thickness of 50 μm was formed on one surface of a 250 μm-thick SUS310S thin plate by the clad method. A large number of gas supply through-holes are opened in this laminated thin plate, processed into a corrugated shape, and then cut out into a predetermined size to form an oxidant gas side current collector plate having a plurality of waves 23 as shown in FIG. Was produced. That is, the obtained current collector plate has a first surface 21 in contact with the cathode and a second surface 22 in contact with the interconnector 8 as shown in FIG. 3, and the cathode side of the first surface 21 is formed of the alloy. The layers are coated. The width W 1 of the first surface 21 is wider than the width W 2 of the second surface 22, and the ends of the first surface 21 are in contact with each other. A plurality of gas supply through holes 24 are formed in the first surface 21. Further, the first surface 21 is expanded in an arc shape toward the cathode. The height of the first surface 21 protruding in an arc shape toward the electrode was 50 μm, and the width thereof was 15 mm.

【００９８】さらに、平均径が１０μｍのアルミニウム
粉末７０重量％、スチレン系のバインダ３０重量％をケ
トン系溶剤で分散させたアルミニウムスラリーを、厚さ
０．４ｍｍのステンレス鋼（ＳＵＳ３１６Ｌ）からなる
薄板材の表面に一定量塗布した後、前記溶剤を揮散して
厚さ２００μｍのアルミニウム含有層を形成した。つづ
いて、薄板材を３％の水素を含むアルゴン雰囲気の炉に
設置し、４９０℃の温度で１２時間熱処理することによ
り前記アルミニウム含有層中のバインダを除去した。さ
らに、７５０℃の温度まで昇温し、その温度にて５時間
熱処理し、１℃／分の降温速度で炉冷することにより前
記薄板材表面に厚さ２５μｍの耐食層が形成されたエッ
ジシール板を作製した。Further, an aluminum slurry in which 70% by weight of an aluminum powder having an average diameter of 10 μm and 30% by weight of a styrene type binder are dispersed in a ketone type solvent is used as a thin plate material made of stainless steel (SUS316L) having a thickness of 0.4 mm. After a certain amount was applied to the surface of, the solvent was volatilized to form an aluminum-containing layer having a thickness of 200 μm. Subsequently, the thin plate material was placed in a furnace in an argon atmosphere containing 3% hydrogen and heat-treated at a temperature of 490 ° C. for 12 hours to remove the binder in the aluminum-containing layer. Furthermore, the edge seal having a corrosion-resistant layer having a thickness of 25 μm formed on the surface of the thin plate material is further heated to a temperature of 750 ° C., heat-treated at that temperature for 5 hours, and cooled in a furnace at a temperature decrease rate of 1 ° C./min. A plate was made.

【００９９】次いで、前記ユニットセルを５つ積層する
と共に、前記セルのカソード側に前記酸化剤ガス側集電
板を配置し、前記セルのアノード側に厚さ３００μｍの
インコネル６００からなり、多数のガス供給用貫通孔を
有する波形の集電板を配置し、かつ互いに隣接する集電
板間、最上層の集電板上、および最下層の集電板下面に
ＳＵＳ３１６Ｌからなるインターコネクタをそれぞれ配
置し、さらに前記電解質板の周縁部を前記エッジシール
板で挟持し、前記挟持部においてスプリング部材で前記
エッジシール板を押えることによって前述した図１に示
す構造で、ユニットセルが５つ積層された積層電池を組
み立てた。この積層電池を発電装置内に設置した。Next, five unit cells were laminated, the oxidant gas side current collector plate was arranged on the cathode side of the cell, and a large number of Inconel 600 having a thickness of 300 μm was formed on the anode side of the cell. Arranging corrugated current collectors having through holes for gas supply, and disposing interconnectors made of SUS316L between the current collectors adjacent to each other, on the uppermost current collector, and on the lowermost current collector. Further, by sandwiching the peripheral edge portion of the electrolyte plate with the edge seal plate and pressing the edge seal plate with a spring member at the sandwiching portion, five unit cells are stacked in the structure shown in FIG. 1 described above. A laminated battery was assembled. This laminated battery was installed in the power generator.

【０１００】前記積層電池が設置された発電装置内に炭
酸ガス５０体積％、残部窒素からなるガスをパージガス
として流した。この後、通常の燃料電池の昇温手順に従
って、アノードと集電板とで形成された流路に燃料ガス
（Ｈ2 ）に供給すると共に、カソードと集電板とで形成
された流路に酸化剤ガス（空気またはＣＯ2 ）を供給
し、６５０℃の発電温度まで昇温することにより発電が
なされた。また、３ｋｇ／ｃｍ2 の面圧を前記エッジシ
ール板に付加し、１５０ｍＡ／ｃｍ2 で発電を実施し
た。その結果、１５０００時間に亘って連続稼働させた
時の出力は４．７Ｖを示した。A gas consisting of 50% by volume of carbon dioxide gas and the balance of nitrogen was passed as a purge gas into the power generator in which the laminated battery was installed. Thereafter, fuel gas (H 2 ) is supplied to the flow path formed by the anode and the current collector plate, and the fuel gas (H 2 ) is supplied to the flow path formed by the cathode and the current collector plate in accordance with a normal fuel cell heating procedure. Power was generated by supplying an oxidizing gas (air or CO 2 ) and raising the temperature to a power generation temperature of 650 ° C. A surface pressure of 3 kg / cm 2 was applied to the edge seal plate, and power was generated at 150 mA / cm 2 . As a result, the output when continuously operated for 15,000 hours was 4.7V.

【０１０１】（比較例９）厚さ２５０μｍのＳＵＳ３１
０Ｓの薄板に多数のガス供給用貫通孔を開口し、波形に
加工した後、所定寸法に切り出すことにより酸化剤ガス
側集電板を作製した。すなわち、得られた前記集電板は
カソードと接する第１面およびインターコネクタと接す
る第２面を有し、前記第１面の前記カソード側は前記合
金層が被覆されている。前記第１面の幅Ｗ1 は、前記第
２面の幅Ｗ2 より広く、かつ前記第１面の端部は互いに
接触されている。前記第１面２１は、平坦でかつ複数の
ガス供給用貫通孔が開口された形状を有する。このよう
な酸化剤ガス側集電板を用いた以外、前述した図１に示
す構造で、実施例１１と同様なユニットセルが５つ積層
された積層電池を組み立て、これを発電装置内に設置し
た。Comparative Example 9 SUS31 having a thickness of 250 μm
A large number of through holes for gas supply were opened in a thin plate of 0S, processed into a corrugated shape, and then cut into a predetermined size to prepare an oxidant gas side current collector plate. That is, the obtained current collector plate has a first surface in contact with the cathode and a second surface in contact with the interconnector, and the cathode layer of the first surface is covered with the alloy layer. The width W 1 of the first surface is wider than the width W 2 of the second surface, and the ends of the first surface are in contact with each other. The first surface 21 has a flat shape and a plurality of through holes for gas supply are opened. Assembling a laminated battery in which five unit cells similar to those in Example 11 were laminated with the structure shown in FIG. 1 described above except that such an oxidant gas side current collector was used, and installed in a power generator. did.

【０１０２】前記積層電池が設置された発電装置内に炭
酸ガス５０体積％、残部窒素からなるガスをパージガス
として流した。この後、通常の燃料電池の昇温手順に従
って、アノードと集電板とで形成された流路に燃料ガス
（Ｈ2 ）に供給すると共に、カソードと集電板とで形成
された流路に酸化剤ガス（空気またはＣＯ2 ）を供給
し、６５０℃の発電温度まで昇温することにより発電が
なされた。また、３ｋｇ／ｃｍ2 の面圧を前記エッジシ
ール板に付加し、１５０ｍＡ／ｃｍ2 で発電を実施し
た。その結果、１４０００時間の連続稼働させた時の出
力は２．０Ｖを低い値しか示さなかった。A gas consisting of 50% by volume of carbon dioxide gas and the balance of nitrogen was flowed as a purge gas into the power generator in which the laminated battery was installed. Thereafter, fuel gas (H 2 ) is supplied to the flow path formed by the anode and the current collector plate, and the fuel gas (H 2 ) is supplied to the flow path formed by the cathode and the current collector plate in accordance with a normal fuel cell heating procedure. Power was generated by supplying an oxidizing gas (air or CO 2 ) and raising the temperature to a power generation temperature of 650 ° C. A surface pressure of 3 kg / cm 2 was applied to the edge seal plate, and power was generated at 150 mA / cm 2 . As a result, the output when continuously operated for 14000 hours showed a low value of 2.0V.

【０１０３】[0103]

【発明の効果】以上説明したように本発明によれば、優
れた電気伝導性を有し、電解質の引き込みが少なく耐食
性の優れた不定比複合酸化物層が表面に形成され、さら
に昇降温の熱サイクルを受けてもカソードと良好に密着
された酸化剤ガス側集電板を備えた高性能、長寿命の溶
融炭酸塩型燃料電池を提供できる。As described above, according to the present invention, a non-stoichiometric composite oxide layer having excellent electric conductivity, little electrolyte entrainment and excellent corrosion resistance is formed on the surface, and the temperature rise / decrease is further increased. It is possible to provide a high-performance, long-life molten carbonate fuel cell including an oxidant gas side current collector that is in good contact with the cathode even when subjected to a thermal cycle.

【０１０４】また、本発明によれば酸化剤ガス側集電板
とインターコネクタとの接触部の腐食を防止して、それ
らの接触面積を初期状態（電池組み込み時の状態）に維
持できる、前記集電板とインターコネクタとの間の電気
抵抗の増大が抑制された長寿命の溶融炭酸塩型燃料電池
を提供できる。Further, according to the present invention, it is possible to prevent corrosion of the contact portion between the oxidant gas side current collector plate and the interconnector and maintain the contact area between them in the initial state (state when the battery is assembled). It is possible to provide a long-life molten carbonate fuel cell in which an increase in electric resistance between the current collector plate and the interconnector is suppressed.

【０１０５】さらに、本発明によれば１００００時間以
上の長時間に亘って稼働させても、電極と良好に密着し
た集電板を備えた高性能の溶融炭酸塩型燃料電池を提供
できる。Further, according to the present invention, it is possible to provide a high-performance molten carbonate fuel cell provided with a current collector plate which is in good contact with the electrodes even when operated for a long time of 10,000 hours or more.

【図面の簡単な説明】[Brief description of drawings]

【図１】本発明に係わる溶融炭酸塩型燃料電池の一例を
示す断面図。FIG. 1 is a cross-sectional view showing an example of a molten carbonate fuel cell according to the present invention.

【図２】燃料電池を構成する酸化剤側集電板とインター
コネクタとの接触部にバリア材を充填した状態を示す断
面図。FIG. 2 is a cross-sectional view showing a state in which a barrier material is filled in a contact portion between an oxidant-side current collector plate and a interconnector that form a fuel cell.

【図３】別の形態の集電板を示す斜視図。FIG. 3 is a perspective view showing another embodiment of a current collector plate.

【符号の説明】[Explanation of symbols]

１…電解質板、２…アノード、３…カソード、４、５…
集電板、８…インターコネクタ、１３…バリア材、２１
…第１面、２２…第２面、２４…ガス供給用貫通孔。1 ... Electrolyte plate, 2 ... Anode, 3 ... Cathode, 4, 5 ...
Current collector, 8 ... Interconnector, 13 ... Barrier material, 21
... 1st surface, 22 ... 2nd surface, 24 ... Through holes for gas supply.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 中川 和明 神奈川県川崎市幸区小向東芝町１番地 株 式会社東芝研究開発センター内 (72)発明者 富松 師浩 神奈川県川崎市幸区小向東芝町１番地 株 式会社東芝研究開発センター内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Kazuaki Nakagawa, Komukai-shi Toshiba-cho, Kawasaki-shi, Kanagawa 1 Komatsu-shi, Toshiba Research and Development Center (72) Inventor Toshimatsu Shimo-Ku, Kawasaki-shi, Kanagawa Muko Toshiba Town No. 1 Inside Toshiba Research and Development Center, a stock company

Claims (10)

【特許請求の範囲】[Claims] 【請求項１】 多孔質体に炭酸塩を含浸して形成された
電解質板と、この電解質板の両面に配置されたカソード
およびアノードとからなるセルユニット；前記セルユニ
ットの前記アノード表面および前記カソード表面にそれ
ぞれ配置された波形状を有する集電板；および前記集電
板表面にそれぞれ配置されたインターコネクタ；を具備
し、 前記カソード側の前記集電板は、オーステナイト系ステ
ンレス鋼からなる集電体本体と、少なくとも前記カソー
ドと接する前記集電体本体表面に被覆されたＦｅ２３〜
４５重量％、Ｃｒ１２〜２７重量％、残部Ｎｉおよび不
可避的不純物１重量％以下の組成を有するＦｅ−Ｃｒ−
Ｎｉ合金層と、前記合金層表面に形成されたニッケルフ
ェライト系の不定比複合酸化物層とからなることを特徴
とする溶融炭酸塩型燃料電池。1. A cell unit comprising an electrolyte plate formed by impregnating a porous body with a carbonate, and a cathode and an anode arranged on both surfaces of the electrolyte plate; the anode surface of the cell unit and the cathode. A current collector plate having a corrugated shape disposed on each surface; and an interconnector disposed on each surface of the current collector plate, wherein the current collector plate on the cathode side is a current collector made of austenitic stainless steel. Fe23 covering the body main body and at least the surface of the current collector body in contact with the cathode
Fe-Cr- having a composition of 45 wt%, Cr 12 to 27 wt%, balance Ni and inevitable impurities of 1 wt% or less.
A molten carbonate fuel cell comprising a Ni alloy layer and a nickel ferrite-based non-stoichiometric composite oxide layer formed on the surface of the alloy layer. 【請求項２】 前記ニッケルフェライト系の不定比複合
酸化物層は、スピネル型構造を有することを特徴とする
請求項１記載の溶融炭酸塩型燃料電池。2. The molten carbonate fuel cell according to claim 1, wherein the nickel ferrite-based non-stoichiometric composite oxide layer has a spinel structure. 【請求項３】 前記ニッケルフェライト系の不定比複合
酸化物層は、Ｎｉ1-x Ｆｅ2-y Ｏ4 、ここでｘ、ｙは０
＜ｘ＜０．８５、−０．５ｙ＜１．０、０＜ｘ＋ｙであ
る、で表されることを特徴とする請求項１記載の溶融炭
酸塩型燃料電池。3. The nickel ferrite-based non-stoichiometric composite oxide layer is Ni 1-x Fe 2-y O 4 , where x and y are 0.
<X <0.85, -0.5y <1.0, 0 <x + y, It is represented by these, The molten carbonate fuel cell of Claim 1 characterized by the above-mentioned. 【請求項４】 前記ニッケルフェライト系の不定比複合
酸化物層は、リチウムが侵入もしくは置換された形態を
有することを特徴とする請求項１記載の溶融炭酸塩型燃
料電池。4. The molten carbonate fuel cell according to claim 1, wherein the nickel ferrite-based non-stoichiometric composite oxide layer has a form in which lithium is invaded or replaced. 【請求項５】 多孔質体に炭酸塩を含浸して形成された
電解質板と、この電解質板の両面に配置されたカソード
およびアノードとからなるセルユニット；前記セルユニ
ットの前記アノード表面および前記カソード表面にそれ
ぞれ配置された波形状を有する集電板；および前記集電
板表面にそれぞれ配置されたインターコネクタ；を具備
し、 前記カソード側の集電板は、前記インターコネクタの平
面と所定の部位で接触し、前記部位は両端に曲面を有
し、かつバリア材は前記インターコネクタの平面と前記
集電板の部位の曲面との間で形成される空間に充填され
ていることを特徴とする溶融炭酸塩型燃料電池。5. A cell unit comprising an electrolyte plate formed by impregnating a porous body with a carbonate, and a cathode and an anode arranged on both sides of the electrolyte plate; the anode surface of the cell unit and the cathode. A current collector plate having a corrugated shape disposed on each surface thereof; and an interconnector disposed on each surface of the current collector plate, wherein the cathode-side current collector plate is a plane of the interconnector and a predetermined portion. And the barrier material is filled in the space formed between the flat surface of the interconnector and the curved surface of the portion of the current collector plate. Molten carbonate fuel cell. 【請求項６】 前記バリア材は、燃料電池の作動温度よ
り融点の低い導電材料からなることを特徴とする請求項
５記載の溶融炭酸塩型燃料電池。6. The molten carbonate fuel cell according to claim 5, wherein the barrier material is made of a conductive material having a melting point lower than the operating temperature of the fuel cell. 【請求項７】 前記バリア材は、電解質の融点より低い
融点を有する導電材料からなることを特徴とする請求項
５記載の溶融炭酸塩型燃料電池。7. The molten carbonate fuel cell according to claim 5, wherein the barrier material is made of a conductive material having a melting point lower than that of the electrolyte. 【請求項８】 前記バリア材は、低融点ガラスからなる
ことを特徴とする請求項５記載の溶融炭酸塩型燃料電
池。8. The molten carbonate fuel cell according to claim 5, wherein the barrier material is made of a low melting point glass. 【請求項９】 多孔質体に炭酸塩を含浸して形成された
電解質板と、この電解質板の両面に配置された一対の電
極とからなるセルユニット；前記セルユニットの前記各
電極の表面にそれぞれ配置された波形状を有する集電
板；および前記集電板表面にそれぞれ配置されたインタ
ーコネクタ；を具備し、 前記波形状の集電板は、前記電極と接する第１面および
前記インターコネクタと接する第２面を有し、前記第１
面の幅は前記第２面の幅より広く、かつ前記第１面は複
数のガス供給用貫通孔が開口され、さらに前記第１面は
前記電極に向かって円弧状に膨らんでいることを特徴と
する溶融炭酸塩型燃料電池。9. A cell unit comprising an electrolyte plate formed by impregnating a porous body with a carbonate, and a pair of electrodes arranged on both sides of the electrolyte plate; on the surface of each electrode of the cell unit. A current collecting plate having a corrugated shape arranged respectively; and an interconnector arranged on a surface of the current collecting plate; the corrugated current collecting plate has a first surface in contact with the electrode and the interconnector. Has a second surface in contact with
The width of the surface is wider than the width of the second surface, a plurality of through holes for gas supply are opened in the first surface, and the first surface bulges in an arc shape toward the electrode. And a molten carbonate fuel cell. 【請求項１０】 前記集電体の第１面は、幅方向のミリ
メータ当たり前記電極に向かう突出高さが０．２〜３０
μｍであることを特徴とする請求項９記載の溶融炭酸塩
型燃料電池。10. The first surface of the current collector has a protrusion height of 0.2 to 30 per millimeter in the width direction toward the electrode.
The molten carbonate fuel cell according to claim 9, wherein the molten carbonate fuel cell has a thickness of μm.
JP7288684A 1994-11-11 1995-11-07 Molten carbonate type fuel cell Pending JPH0992307A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP7288684A JPH0992307A (en) 1994-11-11 1995-11-07 Molten carbonate type fuel cell

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP27743994 1994-11-11
JP6-277439 1994-11-11
JP18428795 1995-07-20
JP7-184287 1995-07-20
JP7288684A JPH0992307A (en) 1994-11-11 1995-11-07 Molten carbonate type fuel cell

Publications (1)

Publication Number Publication Date
JPH0992307A true JPH0992307A (en) 1997-04-04

Family

ID=27325402

Family Applications (1)

Application Number Title Priority Date Filing Date
JP7288684A Pending JPH0992307A (en) 1994-11-11 1995-11-07 Molten carbonate type fuel cell

Country Status (1)

Country Link
JP (1) JPH0992307A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003178776A (en) * 2001-10-01 2003-06-27 Toyota Motor Corp Separator for fuel cell
JP2006324084A (en) * 2005-05-18 2006-11-30 Hitachi Ltd Fuel cell
JP2007519187A (en) * 2004-01-16 2007-07-12 ゼネラル・モーターズ・コーポレーション Channel flow field with extremely short high pressure gradient
JP2007207668A (en) * 2006-02-03 2007-08-16 Ngk Spark Plug Co Ltd Solid electrolyte fuel cell and solid electrolyte fuel cell stack
KR100887430B1 (en) * 2001-05-31 2009-03-10 플란제 에스이 Current collector for SOFC fuel cells
JP4897928B2 (en) * 2009-03-24 2012-03-14 パナソニック株式会社 Polymer electrolyte fuel cell and separator for polymer electrolyte fuel cell
JP2013093184A (en) * 2011-10-25 2013-05-16 Nissan Motor Co Ltd Fuel cell stack

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100887430B1 (en) * 2001-05-31 2009-03-10 플란제 에스이 Current collector for SOFC fuel cells
JP2003178776A (en) * 2001-10-01 2003-06-27 Toyota Motor Corp Separator for fuel cell
JP2007519187A (en) * 2004-01-16 2007-07-12 ゼネラル・モーターズ・コーポレーション Channel flow field with extremely short high pressure gradient
JP4740880B2 (en) * 2004-01-16 2011-08-03 ゼネラル・モーターズ・コーポレーション Channel flow field with extremely short high pressure gradient
JP2006324084A (en) * 2005-05-18 2006-11-30 Hitachi Ltd Fuel cell
JP2007207668A (en) * 2006-02-03 2007-08-16 Ngk Spark Plug Co Ltd Solid electrolyte fuel cell and solid electrolyte fuel cell stack
JP4897928B2 (en) * 2009-03-24 2012-03-14 パナソニック株式会社 Polymer electrolyte fuel cell and separator for polymer electrolyte fuel cell
JP2013093184A (en) * 2011-10-25 2013-05-16 Nissan Motor Co Ltd Fuel cell stack

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