JP3131085B2 - Fuel cell and method of manufacturing the same - Google Patents

Fuel cell and method of manufacturing the same

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Publication number
JP3131085B2
JP3131085B2 JP05282330A JP28233093A JP3131085B2 JP 3131085 B2 JP3131085 B2 JP 3131085B2 JP 05282330 A JP05282330 A JP 05282330A JP 28233093 A JP28233093 A JP 28233093A JP 3131085 B2 JP3131085 B2 JP 3131085B2
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JP
Japan
Prior art keywords
air electrode
solid electrolyte
fuel cell
metal oxide
current collecting
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.)
Expired - Fee Related
Application number
JP05282330A
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Japanese (ja)
Other versions
JPH07134999A (en
Inventor
雅英 秋山
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.)
Kyocera Corp
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Kyocera Corp
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Priority to JP05282330A priority Critical patent/JP3131085B2/en
Publication of JPH07134999A publication Critical patent/JPH07134999A/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は、空気極としてランタン
マンガナイト系セラミックスを利用した燃料電池セルに
関し、固体電解質あるいはインターコネクタなどの集電
部材を気相法で形成する場合の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel cell using a lanthanum manganite ceramic as an air electrode, and relates to an improvement in a case where a current collecting member such as a solid electrolyte or an interconnector is formed by a gas phase method.

【０００２】[0002]

【従来技術】現在、固体電解質型燃料電池は第３世代の
燃料電池として、種々の機関において研究開発が精力的
に行われている。固体電解質型燃料電池セルには、円筒
型のものと平板型のもの等がある。そこで、図３に従来
の円筒型燃料電池セルの構造の斜視図を示した。図３に
よれば、円筒型の単セルは開気孔率４０％程度のＣａＯ
安定化ＺｒＯ2 を支持管１とし、その上にスラリ−ディ
ップ法により多孔質の空気極２としてＬａＭｎＯ3 系材
料を塗布し、その表面に気相合成法（ＥＶＤ）や、ある
いは溶射法により固体電解質３であるＹ2 Ｏ3 安定化Ｚ
ｒＯ2 膜を被覆し、さらにこの表面に多孔質のＮｉ−ジ
ルコニア（Ｙ2 Ｏ3 含有）の燃料極４を設けられてい
る。燃料電池のモジュ−ルにおいては、各単セルは気相
合成法や、あるいは溶射法により作製したＣａ、Ｓｒ、
Ｍｇを添加したＬａＣｒＯ3 のインターコネクタと呼ば
れる集電部材５を介して接続される。発電は、支持管内
部に空気（酸素）を、外部に燃料（水素）を流し、１０
００〜１０５０℃の温度で行われる。2. Description of the Related Art At present, research and development of a solid oxide fuel cell as a third generation fuel cell are being vigorously carried out in various organizations. The solid oxide fuel cell includes a cylindrical type and a flat type. Therefore, FIG. 3 shows a perspective view of the structure of a conventional cylindrical fuel cell. According to FIG. 3, a cylindrical single cell is a CaO having an open porosity of about 40%.
Stabilized ZrO 2 is used as a support tube 1, and a LaMnO 3 material is applied thereon as a porous air electrode 2 by a slurry-dip method, and a solid is formed on the surface by a vapor phase synthesis method (EVD) or a thermal spray method. Electrolyte 3, Y 2 O 3 stabilized Z
An rO 2 film is coated, and a fuel electrode 4 made of porous Ni-zirconia (containing Y 2 O 3 ) is provided on the surface. In the fuel cell module, each single cell is composed of Ca, Sr,
The connection is made via a current collecting member 5 called an interconnector made of LaCrO 3 to which Mg is added. Power generation is performed by flowing air (oxygen) inside the support tube and fuel (hydrogen) outside,
It is performed at a temperature of 00 to 1050 ° C.

【０００３】近年、このセルの作製工程においてプロセ
スを単純化するため、空気極材料であるＬａＭｎＯ3 系
材料を直接多孔質の支持管として使用する試みもなされ
ている。空気極としての機能を合せ持つ支持管材料とし
ては、ＬａをＣａで２０％あるいはＳｒで１０〜１５％
置換したＬａＭｎＯ3 固溶体材料が好適に用いられてい
る。In recent years, attempts have been made to use a LaMnO 3 -based material, which is an air electrode material, directly as a porous support tube in order to simplify the process of fabricating the cell. As a support tube material having the function as an air electrode, La is 20% by Ca or 10 to 15% by Sr.
Substituted LaMnO 3 solid solution materials are preferably used.

【０００４】[0004]

【発明が解決しようとする問題点】空気極である多孔質
のＬａＭｎＯ3 固溶体表面に上述の気相合成法により固
体電解質３および集電部材５を作製する場合、固体電解
質ではＹ、Ｚｒを含有するハロゲンガスが、また集電部
材ではＬａ、Ｃｒ、Ｍｇ含有のハロゲンガスが用いら
れ、これと酸素とを反応させることにより金属酸化物膜
が形成される。これらのハロゲンガスは膜の被覆工程の
初期において、空気極と直接接することになるが、この
時、このハロゲンガスは、空気極表面を腐食させ、被膜
の接着力を低下させるという問題があった。また、合わ
せて空気極材料中のＭｎが選択的にハロゲンガスとして
放出され空気極の表面組成が変化して空気極としての機
能を低下させる等の問題も生じていた。When the solid electrolyte 3 and the current collecting member 5 are formed on the surface of a porous LaMnO 3 solid solution as an air electrode by the above-described vapor phase synthesis method, the solid electrolyte contains Y and Zr. A halogen gas containing La, Cr, and Mg is used for the current collector, and a metal oxide film is formed by reacting the gas with oxygen. These halogen gases come into direct contact with the air electrode in the initial stage of the film coating process. At this time, however, this halogen gas corrodes the air electrode surface and lowers the adhesive strength of the film. . In addition, Mn in the air electrode material is selectively emitted as a halogen gas, and the surface composition of the air electrode changes, thereby causing a problem that the function as the air electrode is lowered.

【０００５】[0005]

【問題を解決するための手段】上記の問題を解決すべ
く、検討を重ねた結果、気相法により固体電解質やイン
ターコネクタが形成される空気極表面にハロゲンガスに
対する耐食性に優れた層を形成したのちに気相法により
各種の膜を形成することにより、上記問題点を解決し
た。[Means for Solving the Problems] As a result of repeated studies to solve the above problems, a layer having excellent corrosion resistance to halogen gas is formed on the surface of the air electrode on which the solid electrolyte and the interconnector are formed by a gas phase method. After that, various problems were solved by forming various films by a vapor phase method.

【０００６】即ち、本発明の燃料電池セルは、ＬａＭｎ
Ｏ3 系固溶体よりなる円筒状の多孔質空気極の表面に、
酸化物系固体電解質と、金属と金属酸化物とのサーメッ
トからなる多孔質の燃料極を順次積層するとともに、前
記空気極の一部に導電性金属酸化物からなる集電部材を
積層してなる燃料電池セルにおいて、前記空気極と前記
固体電解質との間、あるいは前記空気極と前記集電部材
との間に下記化１That is, the fuel cell of the present invention has a LaMn
On the surface of a cylindrical porous air electrode made of an O 3 -based solid solution,
An oxide solid electrolyte and a porous fuel electrode composed of a cermet of a metal and a metal oxide are sequentially laminated, and a current collecting member composed of a conductive metal oxide is laminated on a part of the air electrode. In the fuel cell, between the air electrode and the solid electrolyte or between the air electrode and the current collecting member,

【０００７】[0007]

【化１】 Embedded image

【０００８】で表されるペロブスカイト複合酸化物から
なり、式中、Ａは周期律表第３ａ族元素から選ばれる少
なくとも１種、Ｂはアルカリ土類元素から選ばれる少な
くとも１種、ＣはＭｎ、Ｎｉ、Ｆｅ、Ｃｅ、Ｚｒから選
ばれる少なくとも１種の元素からなり、式中のｘ、ｙ、
ｚおよびｐが ０ ≦ ｘ ≦ ０．４０ ０．０５ ≦ ｙ ≦ ０．５５ ０．９０ ≦ ｚ ≦ １．０５ ０．１０ ≦ ｐ ≦ ０．９０ を満足する層を介在させたことを特徴とするものであ
る。Wherein A is at least one element selected from Group 3a elements of the periodic table, B is at least one element selected from alkaline earth elements, C is Mn, It consists of at least one element selected from Ni, Fe, Ce, and Zr, and x, y,
A layer in which z and p satisfy 0 ≦ x ≦ 0.40 0.05 ≦ y ≦ 0.55 0.90 ≦ z ≦ 1.05 0.10 ≦ p ≦ 0.90 is interposed. Is what you do.

【０００９】また、本発明の燃料電池セルの製造方法に
よれば、ＬａＭｎＯ3 系固溶体よりなる円筒状の多孔質
空気極の表面に前記化１のペロブスカイト複合酸化物か
らなる中間層を形成する工程と、金属ハロゲンガスおよ
び酸素含有ガスの気相反応により、金属酸化物からなる
固体電解質あるいは金属酸化物からなる集電部材を形成
する工程と、該固体電解質の表面に金属と金属酸化物と
の複合体からなる多孔質の燃料極を形成する工程とを具
備したことを特徴とするものである。Further, according to the method of manufacturing a fuel cell of the present invention, a step of forming an intermediate layer made of the perovskite composite oxide of the above formula 1 on the surface of a cylindrical porous air electrode made of a LaMnO 3 -based solid solution. Forming a solid electrolyte made of a metal oxide or a current collecting member made of a metal oxide by a gas phase reaction between a metal halogen gas and an oxygen-containing gas; and forming a metal and a metal oxide on the surface of the solid electrolyte. Forming a porous fuel electrode made of a composite.

【００１０】本発明の燃料電池セルの構造を図１に示し
た。図中、従来品である図３と実質的同一の部材には同
一の番号を付した。本発明によれば、図１に示されるよ
うに、空気極２と固体電解質３、あるいは空気極２とイ
ンターコネクタ（集電部材）５との間に中間層６が形成
されている点が最も重要である。この中間層６は、前記
化１で示されるようなペロブスカイト型結晶の複合酸化
物からなるものであるが、本発明において、化１中の
ｘ、ｙ、ｚ、ｐを上記の比率に限定した理由について説
明すると、まず、Ｌａに対する周期律表第３ａ族元素の
置換比率ｘが０．４より大きいと空気極との化学反応性
が低くなり、空気極への接着力が弱く、保護層の役目を
果たさない。またＬａに対するアルカリ土類元素の置換
比率ｙが０．０５より小さいと８００℃付近の温度にお
ける相変態が抑制出来ず空気極から剥離し、ｙが０．５
５より大きいと空気極との化学反応性が小さくなり同様
に空気極との接着が弱い。ＡサイトとＢサイトの原子比
率ｚが０．９より小さいとＢサイト成分の金属酸化物が
析出し剥離が生じ、ｚが１．０５を越えると、Ｌａ2Ｏ
3 が析出し、空気中の水分あるいは炭酸ガスと反応して
被覆層が短時間に分解する。Ｃｒに対するＭｎ、Ｎｉ等
の置換比率ｐが０．１０より小さいと電気伝導度が低下
し、また空気極への密着性が低下する。ｐが０．９０よ
り大きいと空気極との接着性は良好なもののハロゲンガ
スへの耐食性が低下する。FIG. 1 shows the structure of a fuel cell unit according to the present invention. In the drawing, the members substantially the same as those in FIG. 3 which is a conventional product are denoted by the same reference numerals. According to the present invention, as shown in FIG. 1, the most important point is that an intermediate layer 6 is formed between the air electrode 2 and the solid electrolyte 3 or between the air electrode 2 and the interconnector (current collecting member) 5. is important. The intermediate layer 6 is made of a complex oxide of a perovskite-type crystal as shown in Chemical Formula 1, but in the present invention, x, y, z, and p in Chemical Formula 1 are limited to the above ratios. Explaining the reason, first, when the substitution ratio x of the Group 3a element of the periodic table with La is larger than 0.4, the chemical reactivity with the air electrode becomes low, the adhesive force to the air electrode is weak, and the protective layer Does not play a role. On the other hand, if the substitution ratio y of the alkaline earth element with respect to La is smaller than 0.05, the phase transformation at a temperature around 800 ° C. cannot be suppressed, and peels off from the air electrode.
If it is larger than 5, the chemical reactivity with the air electrode becomes small, and the adhesion with the air electrode is similarly weak. When the atomic ratio z between the A site and the B site is smaller than 0.9, a metal oxide of the B site component is precipitated and peels off, and when z exceeds 1.05, La 2 O
3 precipitates and reacts with moisture or carbon dioxide gas in the air to decompose the coating layer in a short time. If the substitution ratio p of Mn, Ni, etc. to Cr is less than 0.10, the electrical conductivity decreases and the adhesion to the air electrode decreases. If p is greater than 0.90, the adhesion to the air electrode is good, but the corrosion resistance to halogen gas is reduced.

【００１１】本発明における望ましい範囲は、 ０ ≦ ｘ ≦ ０．２ ０．１０ ≦ ｙ ≦ ０．３ ０．９５ ≦ ｚ ≦ １．０ ０．２０ ≦ ｐ ≦ ０．８０ の範囲である。また、この中間層の厚みは５〜１００μ
ｍが望ましい。A desirable range in the present invention is a range of 0 ≦ x ≦ 0.20.10 ≦ y ≦ 0.30.95 ≦ z ≦ 1.00.20 ≦ p ≦ 0.80. The thickness of the intermediate layer is 5 to 100 μm.
m is desirable.

【００１２】本発明において用いられる空気極は、Ｌａ
ＭｎＯ3 のＬａをＣａ、Ｂａ、Ｓｒなどのアルカリ土類
元素で１０〜３０％置換した材料、あるいはＬａをＹ，
Ｙｂ等の周期律表第３ａ族元素でアルカリ土類と同時に
置換した材料が好ましい。この空気極は、支持管として
も機能させる場合には、１．５〜３ｍｍの厚みで形成さ
れ、所定の支持管表面に形成される場合には１〜２ｍｍ
の厚みで形成される。The air electrode used in the present invention is La
A material in which La of MnO 3 is substituted with 10 to 30% of an alkaline earth element such as Ca, Ba, or Sr, or La is Y,
A material which is simultaneously substituted with an alkaline earth by a Group 3a element of the periodic table such as Yb is preferable. The air electrode is formed to have a thickness of 1.5 to 3 mm when functioning also as a support tube, and is formed to be 1 to 2 mm when formed on a predetermined support tube surface.
It is formed with the thickness of.

【００１３】一方、空気極の表面に前記の中間層を介し
て形成される固体電解質としては、ＺｒＯ2 あるいはＣ
ｅＯ2 にＣａＯを１０〜１５ｍｏｌ％あるいはＹ
2 Ｏ3 ，Ｙｂ2 Ｏ3 等の希土類酸化物を７〜１５ｍｏｌ
％添加した酸化物が用いられ、この固体電解質は、５〜
２００μｍの厚みで形成される。On the other hand, as a solid electrolyte formed on the surface of the air electrode via the intermediate layer, ZrO 2 or C
10 to 15 mol% of CaO in eO 2 or Y
7 to 15 mol of rare earth oxides such as 2 O 3 and Yb 2 O 3
% Of the solid oxide is used.
It is formed with a thickness of 200 μm.

【００１４】燃料極としては、Ｎｉ，Ｃｏなどの金属
と、Ｙ2 Ｏ3 を含有するＺｒＯ2 などの金属酸化物との
複合体からなるサーメットが望ましい。また、インター
コネクタなどの集電部材としては、Ｌａの１０〜２０原
子％をＳｒ、Ｃａ等で置換したＬａＣｒＯ3 あるいはＣ
ｒの１０〜１５原子％をＭｇで置換したＬａＣｒＯ3 固
溶体が好適に用いられる。As the fuel electrode, a cermet made of a composite of a metal such as Ni or Co and a metal oxide such as ZrO 2 containing Y 2 O 3 is desirable. Further, as a current collecting member such as an interconnector, LaCrO 3 or C in which 10 to 20 atomic% of La is substituted with Sr, Ca or the like.
A LaCrO 3 solid solution in which 10 to 15 atomic% of r is substituted by Mg is preferably used.

【００１５】次に、本発明に基づく燃料電池セルの製造
方法について説明する。ここでは空気極が支持管として
も機能する円筒状型燃料電池セルを例にして説明する。
まず、空気極として、前述したようなＬａＭｎＯ3 系組
成からなる空気極組成物の粉末を用いて押出成形や射出
成形などにより円筒状に成形した後、焼成し円筒状の焼
結体を作製する。次に、この円筒状焼結体の表面に前述
した化１で示されるような組成からなる中間層を形成す
る。Next, a method of manufacturing a fuel cell according to the present invention will be described. Here, a cylindrical fuel cell in which the air electrode also functions as a support tube will be described as an example.
First, as a cathode, a powder of the above-described LaMnO 3 -based composition is used to form a cylindrical sintered body by extrusion molding, injection molding, or the like, and then fired to produce a cylindrical sintered body. . Next, on the surface of the cylindrical sintered body, an intermediate layer having a composition as shown in Chemical Formula 1 is formed.

【００１６】この中間層を形成する方法としては、例え
ば、化１で示される組成の金属酸化物の混合粉末を１４
００〜１６００℃の酸化性雰囲気中で仮焼し、粉砕して
固溶体化処理した後、この粉末を水溶液に分散する。そ
して、この分散液中に空気極の円筒状焼結体を浸漬する
か、あるいは分散液を焼結体表面に塗布し乾燥後、１２
００〜１５００℃で焼付け処理することにより形成する
ことができる。また、上記の他に溶射法やスパッタ法に
よっても作製することができる。このようにして得られ
る中間層はそれ自体多孔質であることも必要であり、２
５〜４５％の開気孔率を有することは望ましい。As a method of forming the intermediate layer, for example, a mixed powder of a metal oxide having the
After calcining in an oxidizing atmosphere at 00 to 1600 ° C, pulverizing and solid-solution-treating, the powder is dispersed in an aqueous solution. Then, the cylindrical sintered body of the air electrode is immersed in the dispersion, or the dispersion is applied to the surface of the sintered body and dried.
It can be formed by baking at 00 to 1500 ° C. Further, in addition to the above, it can be manufactured by a thermal spraying method or a sputtering method. The intermediate layer obtained in this way must itself be porous,
It is desirable to have an open porosity of 5-45%.

【００１７】このようにして中間層を形成した後、これ
を気相合成装置の反応炉内に設置し、固体電解質あるい
は集電部材を形成する。例えば、固体電解質としてＹ2
Ｏ3含有安定化ＺｒＯ2 を形成する場合にはＹＣｌ3 、
ＺｒＣｌ4 などの金属ハロゲンガスとともに酸素ガスを
導入し、気相合成によりＹ2 Ｏ3 −ＺｒＯ2 の固体電解
質膜を５〜２００μｍの厚みで形成する。一方、例えば
ＬａＣｒＯ3 系材料からなる集電部材を形成する場合に
は、ＬａＣｌ3 、ＣｒＣｌ3 などの金属ハロゲンガスと
同時に酸素含有ガスを導入することにより、ＬａＣｒＯ
3 系材料からなる集電部材を形成することができる。After the formation of the intermediate layer in this manner, the intermediate layer is placed in a reaction furnace of a gas phase synthesis apparatus to form a solid electrolyte or a current collecting member. For example, as a solid electrolyte, Y 2
When forming O 3 -containing stabilized ZrO 2 , YCl 3 ,
An oxygen gas is introduced together with a metal halogen gas such as ZrCl 4 and a solid electrolyte membrane of Y 2 O 3 —ZrO 2 is formed with a thickness of 5 to 200 μm by vapor phase synthesis. On the other hand, in the case of forming a current collecting member made of LaCrO 3 material, for example, an oxygen-containing gas is introduced simultaneously with a metal halogen gas such as LaCl 3 or CrCl 3 , whereby LaCrO 3 is introduced.
It is possible to form the current collecting member made of a 3 based material.

【００１８】このようにして固体電解質および集電部材
を形成した後、燃料極を固体電解質膜の表面に形成す
る。その燃料極は、例えば、Ｎｉなどの金属粉末と、Ｙ
2 Ｏ3を含むジルコニアの粉末との混合粉末を溶媒中に
分散させ、固体電解質の任意の場所に塗布しこれを１３
００〜１５００℃で焼き付けることによりセルを作製す
ることができる。After forming the solid electrolyte and the current collecting member in this manner, a fuel electrode is formed on the surface of the solid electrolyte membrane. The fuel electrode is made of, for example, a metal powder such as Ni and Y
A mixed powder with zirconia powder containing 2 O 3 is dispersed in a solvent, applied to an arbitrary place of a solid electrolyte, and
By baking at 00 to 1500 ° C., a cell can be manufactured.

【００１９】なお、本発明によれば、空気極と固体電解
質、あるいは空気極と集電部材との間に前記化１で示さ
れた組成からなるＬａＣｒＯ3 系複合酸化物を中間層と
して介在させるものであるが、この中間層は例えば、Ｃ
ａＯ安定化ＺｒＯ2 を支持管としその上に空気極を被覆
し、その上に固体電解質、燃料極を形成したセル、ある
いは、空気極自体を支持管として固体電解質、燃料極を
形成したセルのいずれにも適用することができる。According to the present invention, a LaCrO 3 -based composite oxide having the composition shown in Chemical Formula 1 is interposed between the air electrode and the solid electrolyte or between the air electrode and the current collecting member as an intermediate layer. The intermediate layer is, for example, C
aO-stabilized ZrO 2 as a support tube and a cathode coated thereon with an air electrode and a solid electrolyte and a fuel electrode formed thereon, or a cell where the air electrode itself is used as a support tube and a solid electrolyte and a fuel electrode are formed It can be applied to any of them.

【００２０】さらに、上記説明では円筒状燃料電池セル
を例に説明したが、平板状燃料電池セルにおいても、空
気極と固体電解質との間、空気極と集電部材であるセパ
レータとの間に上述したような中間層を形成した場合で
も同様な効果が得られるものである。In the above description, a cylindrical fuel cell has been described as an example. However, a flat fuel cell may also be provided between an air electrode and a solid electrolyte, or between an air electrode and a separator as a current collecting member. Similar effects can be obtained even when the intermediate layer as described above is formed.

【００２１】[0021]

【作用】気相合成法によりＹ2 Ｏ3 安定化ＺｒＯ2 から
成る固体電解質膜を被覆する場合、被成膜体を１０５０
〜１１００℃の温度の加熱し、減圧下でＹおよびＺｒを
含有するハロゲンガスと酸素を供給して下記化２[Action] When coating the solid electrolyte film made of Y 2 O 3 stabilized ZrO 2 by a vapor phase synthesis method, the deposition target object 1050
Heating at a temperature of about 1100 ° C., and supplying a halogen gas containing Y and Zr and oxygen under reduced pressure to produce

【００２２】[0022]

【化２】 Embedded image

【００２３】の反応により合成する。The compound is synthesized by the following reaction.

【００２４】この際、ＹＣｌ3 やＺｒＣｌ2 などのハロ
ゲンガスは空気極を腐食し、例えば、空気極が（Ｌａ，
Ｃａ）ＭｎＯ3 からなる場合、ＬａＣｌ3 、ＣａＣ
ｌ2 、ＭｎＣｌ4 が生成しこれらの成分が蒸発すること
となる。特に、ＬａＭｎＯ3 系固溶体においては、Ｍｎ
含有のハロゲンガスが生成しやすい。このため、空気極
の表面組成が変化し、固体電解質膜との付着力を低下さ
せたり、あるいは空気極として、酸素をイオン化すると
いう重要な触媒機能が損なわれる。また、Ｌａ、Ｃｒ等
を含有したハロゲンガスを用いてインターコネクタ膜を
合成する場合は、被成膜体の保持温度が１３００〜１４
００℃と高いためにこのハロゲンガスによる空気極の腐
食がさらに大きくなる。At this time, a halogen gas such as YCl 3 or ZrCl 2 corrodes the air electrode.
Ca) When composed of MnO 3 , LaCl 3 , CaC
l 2 and MnCl 4 are produced, and these components evaporate. In particular, in a LaMnO 3 -based solid solution, Mn
Contained halogen gas is easily generated. For this reason, the surface composition of the air electrode changes, and the adhesion to the solid electrolyte membrane is reduced, or the important catalytic function of ionizing oxygen as the air electrode is impaired. In the case where an interconnector film is synthesized using a halogen gas containing La, Cr, or the like, the holding temperature of the object to be formed is 1300 to 14
Since the temperature is as high as 00 ° C., the corrosion of the air electrode by the halogen gas is further increased.

【００２５】本発明は、このようなハロゲンガスによる
腐食に対して、空気極の表面に前述したように化１で示
されるようなペロブスカイト型複合酸化物を形成させて
おくことにより、優れた耐腐食性を有すると同時に、高
い導電性を有するとともに空気極との密着性に優れると
いった性質を有するために、燃料電池セルとしての機能
を何ら損なうことなく、前述した問題点を解決すること
ができる。According to the present invention, the perovskite-type composite oxide as shown in Chemical Formula 1 is formed on the surface of the air electrode as described above to prevent the corrosion by the halogen gas, thereby providing excellent resistance. At the same time as having corrosiveness, it has the property of having high conductivity and excellent adhesion to the air electrode, so that the above-mentioned problem can be solved without impairing the function as a fuel cell at all. .

【００２６】これは、化１で表される化合物において、
Ｃｒ成分を含んだペロブスカイト酸化物がハロゲンガス
に対する耐蝕性が高いことと、空気極中に含まれるＬａ
と置換した元素と同族の元素を含む組成系が電気伝導度
が大きく、空気極との接着に優れることの相乗的作用に
よるものと推測される。In the compound represented by the formula 1,
The perovskite oxide containing Cr component has high corrosion resistance to halogen gas and La contained in the air electrode.
It is presumed that the synergistic effect of a composition system containing an element of the same family as the element substituted with a high electric conductivity and excellent adhesion to the air electrode.

【００２７】よって、本発明によれば、燃料電池セルの
作製においてハロゲンガスによる腐食を防止できること
によりセル製造時の歩留りを高めるとともに、セルの長
期にわたる安定性と信頼性を高めることができる。Therefore, according to the present invention, it is possible to prevent the corrosion by the halogen gas in the production of the fuel cell, thereby improving the yield at the time of producing the cell and improving the long-term stability and reliability of the cell.

【００２８】[0028]

【実施例】次に、本発明を実施例に基づき説明する。 実施例１（ハロゲンガスへの耐食性、電気伝導度測定） 市販の純度９９．９％のＬａ2 Ｏ3 、ＳｒＣＯ3 、Ｃａ
ＣＯ3 、ＢａＣＯ3 、Ｙ2 Ｏ3 、Ｙｂ2 Ｏ3 、Ｓｃ2 Ｏ
3 、Ｅｒ2 Ｏ3 、Ｎｄ2 Ｏ3 、Ｇｄ2 Ｏ3 、Ｄｙ
2 Ｏ3 、Ｓｍ2 Ｏ3 、ＭｎＯ2 、Ｃｒ2 Ｏ3 、ＮｉＯ、
Ｆｅ2 Ｏ3 、ＣｅＯ2、ＺｒＯ2 を出発原料とし、これ
を表１、表２の所定の組成になるように調合し、ジルコ
ニアボ−ルを用いて１０時間混合した後、１５００℃で
５時間固相反応させた。この粉末をジルコニアボ−ルを
用いて、さらに２０〜２５時間粉砕し、得られた平均粒
子径２〜４μｍの粉末を得た。Next, the present invention will be described based on embodiments. Example 1 (Measurement of corrosion resistance to halogen gas and electric conductivity) La 2 O 3 , SrCO 3 , and Ca having a purity of 99.9% commercially available
CO 3 , BaCO 3 , Y 2 O 3 , Yb 2 O 3 , Sc 2 O
3, Er 2 O 3, Nd 2 O 3, Gd 2 O 3, Dy
2 O 3 , Sm 2 O 3 , MnO 2 , Cr 2 O 3 , NiO,
Fe 2 O 3 , CeO 2 , and ZrO 2 were used as starting materials, and they were mixed so as to have the prescribed compositions shown in Tables 1 and 2, mixed with zirconia balls for 10 hours, and then mixed at 1500 ° C. for 5 hours. The solid phase reaction was carried out for a period of time. This powder was further pulverized with a zirconia ball for 20 to 25 hours to obtain a powder having an average particle diameter of 2 to 4 μm.

【００２９】この粉末を用いてハロゲンガスへの耐食
性、電気伝導度の測定、空気極材料との密着性について
調査した。Using this powder, the corrosion resistance to halogen gas, the measurement of electric conductivity, and the adhesion to the air electrode material were investigated.

【００３０】（ハロゲンガスへの耐食性）この粉末を、
円板状に成形し１４００〜１５００℃にて焼成し、理論
密度比が７２〜７６％で、厚み約３ｍｍ、直径３０ｍｍ
φの円板状焼結体を得、この焼結体を、１０００℃で５
％ＨＣｌ／９５％Ａｒの混合ガスを流しながら１時間焼
鈍して試料の重量減少を測定した。(Corrosion resistance to halogen gas)
It is shaped into a disc and fired at 1400-1500 ° C., with a theoretical density ratio of 72-76%, a thickness of about 3 mm and a diameter of 30 mm.
φ disk-shaped sintered body was obtained, and this sintered body was
The sample was annealed for 1 hour while flowing a mixed gas of% HCl / 95% Ar to measure the weight loss of the sample.

【００３１】（電気伝導度測定）上記のようにして得ら
れた円板状焼結体より長さ約２×２×２０ｍｍの角柱状
試料を切り出し４端子法により電気伝導度を測定し、結
果は表１、表２に示した。なお、各特性評価方法は下記
の通りである。(Measurement of Electric Conductivity) A prismatic sample having a length of about 2 × 2 × 20 mm was cut out from the disk-shaped sintered body obtained as described above, and the electric conductivity was measured by a four-terminal method. Are shown in Tables 1 and 2. In addition, each characteristic evaluation method is as follows.

【００３２】（空気極との密着性）上述の２０〜２５時
間粉砕した平均粒子径２〜４μｍの粉末をエチレングリ
コ−ルと混合してペ−スト状にした。一方、市販の純度
９９．９％のＬａ2 Ｏ3 、ＳｒＣＯ3 ，ＣａＣＯ3 、Ｂ
ａＣＯ3 、Ｙ2 Ｏ3 、ＭｎＯ2 を出発原料として、これ
を（Ｌａ0.8 Ｃａ0.2 ）ＭｎＯ3 の組成となるように調
合し、ジルコニアボ−ルを用いて１０時間混合した後、
１５００℃で５時間固相反応させた。この粉末をジルコ
ニアボ−ルを用いて、さらに１０〜１６時間粉砕した。
この後、円板状に成形し１４８０〜１５００℃にて焼成
し、理論密度比が７０〜７３％で、厚み約３ｍｍ、直径
３０ｍｍφの空気極に相当する焼結体を得た。(Adhesion to Air Electrode) The powder having an average particle diameter of 2 to 4 μm ground for 20 to 25 hours was mixed with ethylene glycol to form a paste. On the other hand, commercially available La 2 O 3 , SrCO 3 , CaCO 3 , B 99.9% pure
Using aCO 3 , Y 2 O 3 , and MnO 2 as starting materials, they were mixed so as to have a composition of (La 0.8 Ca 0.2 ) MnO 3 , and mixed for 10 hours using a zirconia ball.
The solid phase reaction was performed at 1500 ° C. for 5 hours. This powder was further ground for 10 to 16 hours using a zirconia ball.
Then, it was shaped into a disk and fired at 1480 to 1500 ° C. to obtain a sintered body having a theoretical density ratio of 70 to 73% and corresponding to an air electrode having a thickness of about 3 mm and a diameter of 30 mmφ.

【００３３】そして、先に調製したペ−ストをスクリ−
ン印刷にて約３０μｍの厚みに上記の円板状焼結体表面
に塗布し１３００℃で４時間加熱して粉末を焼き付けた
後、剥離の有無を調べ、剥離が発生したものに×、剥離
が何ら見られないものに○を付した。Then, the paste prepared above is screened.
After applying the powder on the surface of the disc-shaped sintered body to a thickness of about 30 μm by heating printing and heating at 1300 ° C. for 4 hours to burn the powder, the presence or absence of peeling is examined. A circle was given to a sample in which no sample was seen.

【００３４】[0034]

【表１】 [Table 1]

【００３５】[0035]

【表２】 [Table 2]

【００３６】表１、表２によれば、Ｂサイト中のＣｒに
対する他の金属の置換量が増加するに従い、電気伝導度
が高くなるとともに空気極との密着性が良好であるが、
ハロゲンガスによる耐食性が低下する傾向にあり、Ｃｒ
に対するＭｎ等の置換比率ｐが０．１より小さい試料Ｎ
o.８、９、１０、３６、３７では電気伝導度が低下する
とともに空気極との剥離が観察された。Ｃｒに対するＭ
ｎ、Ｎｉ等の置換比率が０．９を越える試料Ｎo.１で
は、ハロゲンガスによる腐食性が大きかった。また、Ａ
サイトとＢサイトの原子の存在比率ｚに関して、ｚが
０．９より小さい試料Ｎo.１１ではＭｎ2 Ｏ3 が析出
し、１．０５を越える試料Ｎo.１５ではＬａ2Ｏ3 が析
出し、いずれも接着力が小さい。さらに、Ｃａ等による
Ｌａの置換比率ｙが０．０５より小さいか、あるいは
０．５５より大きい試料Ｎo.１６、２２でも接着力が弱
い。また、Ｙ等によるＬａの置換比率ｘが０．４より大
きい試料Ｎo.２６でも同様に接着力が小さかった。According to Tables 1 and 2, as the substitution amount of Cr to other metals in the B site increases, the electric conductivity increases and the adhesion to the air electrode is good.
Corrosion resistance due to halogen gas tends to decrease.
N in which the substitution ratio p of Mn or the like with respect to
In o, 8, 9, 10, 36, and 37, the electrical conductivity was reduced and peeling from the air electrode was observed. M for Cr
In Sample No. 1 in which the substitution ratio of n, Ni, etc. exceeded 0.9, the corrosiveness by the halogen gas was large. Also, A
Regarding the abundance ratio z of the atom between the site and the B site, Mn 2 O 3 is precipitated in Sample No. 11 where z is smaller than 0.9, and La 2 O 3 is precipitated in Sample No. 15 in which z exceeds 1.05. All have low adhesive strength. Further, even in Samples Nos. 16 and 22 in which the substitution ratio y of La by Ca or the like is smaller than 0.05 or larger than 0.55, the adhesive strength is weak. Sample No. 26 in which the substitution ratio x of La by Y or the like was larger than 0.4 also had a small adhesive force.

【００３７】これらの比較例に対して本発明品はいずれ
も電気伝導度が１０ｓ／ｃｍ以上と高く、ハロゲンガス
に対する腐食性も０．６％以下と低く、さらに空気極と
の密着性についても良好な特性を示した。In contrast to these comparative examples, the products of the present invention all have a high electric conductivity of 10 s / cm or more, a low corrosivity to halogen gas of 0.6% or less, and a low adhesion to the air electrode. Good characteristics were shown.

【００３８】実施例２ Ｌａ0.8 Ｃａ0.2 ＭｎＯ3 組成の粉末を用いて、これを
１５５０℃で焼成して、密度が理論密度比７０〜７２％
で外径１６ｍｍ、内径１２ｍｍ、長さ２００ｍｍの一端
封じの中空円筒状焼結体を作製し空気極としての機能を
付与したセルの支持管とした。また、一方、実施例１の
表１、表２中Ｎｏ．４、２３、３４組成の粉末をＰＶＡ
を含んだ水溶液中に分散させ、この水溶液にＬａ0.8 Ｃ
ａ0.2 ＭｎＯ3 の円筒状支持管を浸漬して支持管表面に
粉末を塗布した後、１３００℃で２時間焼き付け約２０
μｍの中間層を形成した。Example 2 A powder having a composition of La 0.8 Ca 0.2 MnO 3 was fired at 1550 ° C., and the density was reduced to a theoretical density ratio of 70 to 72%.
In this manner, a hollow cylindrical sintered body having an outer diameter of 16 mm, an inner diameter of 12 mm, and a length of 200 mm sealed at one end was prepared and used as a support tube for a cell having a function as an air electrode. On the other hand, in Tables 1 and 2 in Example 1, No. 4, 23, 34 powder of PVA
And dispersed in an aqueous solution containing La 0.8 C.
a Dip a cylindrical support tube of 0.2 MnO 3 to apply powder on the surface of the support tube, and bake at 1300 ° C. for 2 hours for about 20 hours.
A μm intermediate layer was formed.

【００３９】この後、それぞれ気相合成法により、１１
００℃でこの円筒状焼結体の外周表面にＹＣｌ3 ，Ｚｒ
Ｃｌ4 を原料として固体電解質膜（１０ｍｏｌ％Ｙ2 Ｏ
3 −９０ｍｏｌ％ＺｒＯ2 ）を約５０μｍの厚みに被覆
し、さらにこの上に燃料極として、スラリ−ディップ法
により、約４０μｍの厚みに７０重量％Ｎｉ−３０重量
％ジルコニア（８ｍｏｌ％Ｙ2 Ｏ3 −９２ｍｏｌ％Ｚｒ
Ｏ2 ）を被覆し単セルを作製した。このセルを１０００
℃の電気炉中に保持し、セルの内側に酸素ガスを、また
外側に水素ガスを流しながら、発電特性を調べた。Thereafter, 11
At 00 ° C., YCl 3 , Zr
Solid electrolyte membrane Cl 4 as a raw material (10mol% Y 2 O
3 -90 mol% ZrO 2) was coated to a thickness of about 50 [mu] m, further as the fuel electrode thereon, a slurry - by dipping, about 40μm thickness 70 wt% Ni-30 wt% zirconia (8 mol% Y 2 O 3 -92mol% Zr
O 2 ) to produce a single cell. 1000 cells
The temperature was maintained in an electric furnace at ℃, and the power generation characteristics were examined while flowing oxygen gas inside the cell and hydrogen gas outside.

【００４０】結果を図２に示した。これより、保護層を
形成していない従来品はいずれも出力が低下しているの
に対して、本発明により保護層を形成したものはいずれ
も高い安定した出力を示すことが分かる。FIG. 2 shows the results. From this, it can be seen that the output of any of the conventional products without the protective layer is reduced, while the output of the protective layer according to the present invention shows a high and stable output.

【００４１】[0041]

【発明の効果】以上詳述したように、本発明によれば、
空気極材料の表面にハロゲンガスに対する耐蝕性に優れ
た中間層を設けることにより空気極の機能を損なうこと
なく固体電解質や集電部材を作製することが出来と同時
に性能の優れたセルを作製できる。この結果、本発明は
固体電解質型燃料電池セルに用いた場合、長期安定性の
あるセルを高い良品率で提供できる。As described in detail above, according to the present invention,
By providing an intermediate layer having excellent corrosion resistance to halogen gas on the surface of the air electrode material, it is possible to manufacture a solid electrolyte or a current collecting member without impairing the function of the air electrode, and at the same time to manufacture a cell having excellent performance. . As a result, when the present invention is used for a solid oxide fuel cell, a cell having long-term stability can be provided at a high yield rate.

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

【図１】本発明の円筒型燃料電池セルの構造を説明する
ための斜視図である。FIG. 1 is a perspective view illustrating the structure of a cylindrical fuel cell according to the present invention.

【図２】実施例２における発電時間の出力密度との関係
を示す図である。FIG. 2 is a diagram showing a relationship between power generation time and output density in Example 2.

【図３】従来の円筒型燃料電池セルの構造を説明するた
めの斜視図である。FIG. 3 is a perspective view illustrating the structure of a conventional cylindrical fuel cell.

【符号の説明】[Explanation of symbols]

１ 支持管 ２ 空気極 ３ 固体電解質 ４ 燃料極 ５ 集電部材 ６ 中間層 DESCRIPTION OF SYMBOLS 1 Support pipe 2 Air electrode 3 Solid electrolyte 4 Fuel electrode 5 Current collecting member 6 Intermediate layer

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 8/02 H01M 4/88 H01M 8/12 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. 7 , DB name) H01M 8/02 H01M 4/88 H01M 8/12

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】ＬａＭｎＯ3 系固溶体よりなる円筒状の多
孔質空気極の表面に、金属酸化物系固体電解質と、金属
と金属酸化物との複合体からなる多孔質の燃料極を順次
積層するとともに、前記空気極の一部に導電性金属酸化
物からなる集電部材を積層してなる燃料電池セルにおい
て、前記空気極と前記固体電解質との間、あるいは前記
空気極と前記集電部材との間に下記化１ 【化１】 で表されるペロブスカイト複合酸化物からなり、式中、
Ａは周期律表第３ａ族元素から選ばれる少なくとも１
種、Ｂはアルカリ土類元素から選ばれる少なくとも１
種、ＣはＭｎ、Ｎｉ、Ｆｅ、Ｃｅ、Ｚｒから選ばれる少
なくとも１種の元素からなり、式中のｘ、ｙ、ｚおよび
ｐが ０ ≦ ｘ ≦ ０．４０ ０．０５ ≦ ｙ ≦ ０．５５ ０．９０ ≦ ｚ ≦ １．０５ ０．１０ ≦ ｐ ≦ ０．９０ を満足する中間層を介在させたことを特徴とする燃料電
池セル。1. A metal oxide solid electrolyte and a porous fuel electrode made of a composite of a metal and a metal oxide are sequentially laminated on the surface of a cylindrical porous air electrode made of a LaMnO 3 -based solid solution. In addition, in a fuel cell obtained by laminating a current collecting member made of a conductive metal oxide on a part of the air electrode, between the air electrode and the solid electrolyte, or between the air electrode and the current collecting member During the following formula 1 Consisting of a perovskite composite oxide represented by the formula:
A is at least one selected from Group 3a elements of the periodic table
Species, B is at least one selected from alkaline earth elements
The species C is composed of at least one element selected from Mn, Ni, Fe, Ce, and Zr, where x, y, z and p in the formula are 0 ≦ x ≦ 0.40 0.05 ≦ y ≦ 0. 55. A fuel cell comprising an intermediate layer that satisfies 55 0.90 ≤ z ≤ 1.05 0.10 ≤ p ≤ 0.90. 【請求項２】ＬａＭｎＯ3 系固溶体よりなる円筒状の多
孔質空気極の表面に下記化１ 【化１】 で表されるペロブスカイト複合酸化物からなり、式中、
Ａは周期律表第３ａ族元素から選ばれる少なくとも１
種、Ｂはアルカリ土類元素から選ばれる少なくとも１
種、ＣはＭｎ、Ｎｉ、Ｆｅ、Ｃｅ、Ｚｒから選ばれる少
なくとも１種の元素からなり、式中のｘ、ｙ、ｚおよび
ｐが ０ ≦ ｘ ≦ ０．４０ ０．０５ ≦ ｙ ≦ ０．５５ ０．９０ ≦ ｚ ≦ １．０５ ０．１０ ≦ ｐ ≦ ０．９０ を満足する中間層を形成する工程と、金属ハロゲンガス
および酸素含有ガスの気相反応により、金属酸化物から
なる固体電解質あるいは金属酸化物からなる集電部材を
形成する工程と、該固体電解質の表面に金属と金属酸化
物との複合体からなる多孔質の燃料極を形成する工程と
を具備したことを特徴とする燃料電池セルの製造方法。2. The surface of a cylindrical porous air electrode made of a LaMnO 3 -based solid solution is represented by the following formula 1. Consisting of a perovskite composite oxide represented by the formula:
A is at least one selected from Group 3a elements of the periodic table
Species, B is at least one selected from alkaline earth elements
The species C is composed of at least one element selected from Mn, Ni, Fe, Ce, and Zr, where x, y, z and p in the formula are 0 ≦ x ≦ 0.40 0.05 ≦ y ≦ 0. A solid electrolyte made of a metal oxide by a step of forming an intermediate layer satisfying 55 0.90 ≤ z ≤ 1.05 0.10 ≤ p ≤ 0.90 and a gas phase reaction of a metal halogen gas and an oxygen-containing gas. Alternatively, the method includes a step of forming a current collecting member made of a metal oxide, and a step of forming a porous fuel electrode made of a composite of a metal and a metal oxide on the surface of the solid electrolyte. A method for manufacturing a fuel cell.
JP05282330A 1993-11-11 1993-11-11 Fuel cell and method of manufacturing the same Expired - Fee Related JP3131085B2 (en)

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JP4102877B2 (en) * 2003-08-28 2008-06-18 独立行政法人産業技術総合研究所 Method for producing hybrid molded porous tube
JP4093321B2 (en) * 2007-07-20 2008-06-04 独立行政法人産業技術総合研究所 Hybrid porous tube
JP5256897B2 (en) 2007-08-03 2013-08-07 三菱マテリアル株式会社 Metal oxide sintered body for thermistor, thermistor element, thermistor temperature sensor, and method for producing metal oxide sintered body for thermistor

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