JP3502685B2 - Air electrode support - Google Patents
Air electrode supportInfo
- Publication number
- JP3502685B2 JP3502685B2 JP03732295A JP3732295A JP3502685B2 JP 3502685 B2 JP3502685 B2 JP 3502685B2 JP 03732295 A JP03732295 A JP 03732295A JP 3732295 A JP3732295 A JP 3732295A JP 3502685 B2 JP3502685 B2 JP 3502685B2
- Authority
- JP
- Japan
- Prior art keywords
- air electrode
- solid electrolyte
- support member
- zirconia
- electrode
- 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
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
-
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、固体電解質型燃料電池
等に用いられる、空気極用支持部材に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an air electrode support member used in a solid oxide fuel cell or the like.
【０００２】[0002]
【従来の技術】近年、燃料電池発電システムは、エネル
ギー問題、地球環境問題を背景に大きな貢献をするもの
として、世界的にますますその期待が高まっている。燃
料電池発電システムは、燃料が有する化学エネルギーを
直接電気エネルギーに変換できるシステムでカルノーサ
イクルの制約を受けないため、本質的に高いエネルギー
変換効率を有し、燃料の多様化が可能で、低公害で、し
かも発電効率が設備規模によって影響されず、極めて有
望な技術である。2. Description of the Related Art In recent years, fuel cell power generation systems have been increasingly expected worldwide as they make a great contribution against the backdrop of energy problems and global environmental problems. The fuel cell power generation system is a system that can directly convert the chemical energy of the fuel into electric energy and is not restricted by the Carnot cycle. Therefore, it has essentially high energy conversion efficiency, can diversify the fuel, and has low pollution. Moreover, the power generation efficiency is not affected by the scale of the facility, and is a very promising technology.
【０００３】特に、固体電解質型燃料電池はリン酸型燃
料電池、溶融炭酸塩型燃料電池と異なり、液体、融体を
用いないため電池の構成がシンプルであり、高温の排熱
利用も含めるとエネルギー効率８０〜９０％が期待でき
る。Particularly, unlike the phosphoric acid type fuel cell and the molten carbonate type fuel cell, the solid electrolyte type fuel cell has a simple cell structure because it does not use a liquid or a melt, and includes the use of high temperature exhaust heat. Energy efficiency of 80 to 90% can be expected.
【０００４】一般的な固体電解質型燃料電池の単セルの
構造は、図１に示すように多孔性の管状をした支持部材
１、空気極２、固体電解質３、燃料極４から構成され
る。支持部材１は、通常ＣａＯを含む安定化ＺｒＯ2 セ
ラミックスからなり、耐熱性とともに適度に気体を通す
ように開気孔率が２０〜４０％程度の多孔質体となって
いる。また、支持部材１の外表面には、Ｌａを１０〜２
０原子％のＣａ，Ｓｒで置換したＬａＭｎＯ3 やＬａＣ
ｏＯ3 の空気極２、Ｙ2 Ｏ3 を含有する緻密質のＺｒＯ
2 からなる固体電解質３、およびＮｉ−ＺｒＯ2 （Ｙ2
Ｏ3 を含有）サーメットからなる燃料極４が順次設けら
れている。また、セルには単セルを直列に接続するため
のＬａＣｒＯ3 系材料からなるインターコネクタ５が形
成されている。As shown in FIG. 1, the structure of a unit cell of a general solid oxide fuel cell is composed of a porous tubular supporting member 1, an air electrode 2, a solid electrolyte 3 and a fuel electrode 4. The support member 1 is usually made of stabilized ZrO 2 ceramics containing CaO, and is a porous body having heat resistance and an open porosity of about 20 to 40% so as to allow appropriate gas passage. In addition, La is 10 to 2 on the outer surface of the support member 1.
LaMnO 3 and LaC substituted with 0 atomic% of Ca and Sr
Air electrode 2 of oO 3 and dense ZrO containing Y 2 O 3
Solid electrolyte 3 composed of 2 and Ni—ZrO 2 (Y 2
A fuel electrode 4 made of cermet (containing O 3 ) is sequentially provided. Further, an interconnector 5 made of LaCrO 3 system material for connecting the single cells in series is formed in the cell.
【０００５】そして、上記支持部材１の内側には空気６
を、電池の外側にはＨ2 やメタンガスの改質ガス７を各
々供給し、これらが支持部材１、空気極２、固体電解質
３、燃料極４を介して反応する時のエネルギーを直接電
力の形式で取り出すものである。また、上記構造の他に
空気極２を外側、燃料極４を内側にした逆転構造のもの
も提案されている。あるいは、板状の固体電解質を用い
た平板型の燃料電池もある。Then, air 6 is placed inside the support member 1.
H 2 and reformed gas 7 of methane gas are supplied to the outside of the cell, respectively, and the energy when these react through the support member 1, the air electrode 2, the solid electrolyte 3 and the fuel electrode 4 is directly converted into electric power. It is taken out in the form. In addition to the above structure, a reverse structure having the air electrode 2 on the outside and the fuel electrode 4 on the inside has also been proposed. Alternatively, there is also a flat plate type fuel cell using a plate-shaped solid electrolyte.
【０００６】図１に示す燃料電池の製造方法は、ＣａＯ
安定化ジルコニアセラミックスからなる多孔質の支持部
材１の外表面に前記空気極２、固体電解質３及び燃料極
４をＣＶＤ、ＥＶＤ、プラズマ溶射、減圧プラズマ溶射
等の製膜技術を用いて製膜する。特に溶射法を用いる場
合は、高温に溶融された各電極材料や固体電解質材料を
母材である支持部材１の表面に吹き付けて各電極、固体
電解質を製膜するものである。The method of manufacturing the fuel cell shown in FIG.
The air electrode 2, the solid electrolyte 3 and the fuel electrode 4 are formed on the outer surface of the porous support member 1 made of stabilized zirconia ceramics by using a film forming technique such as CVD, EVD, plasma spraying or low pressure plasma spraying. . Particularly when the thermal spraying method is used, each electrode material or solid electrolyte material melted at high temperature is sprayed onto the surface of the support member 1 as a base material to form each electrode or solid electrolyte film.
【０００７】また、上記固体電解質３として用いられる
セラミックスとしては、ＺｒＯ2 、ＣｅＯ2 、Ｔｈ
Ｏ2 、Ｂｉ2 Ｏ3 等を主成分とするものがある。固体電
解質セラミックスとして要求される特性は、
イオン導電率が大きい
電子導電性がほとんどない
高温で化学的に安定している
高温で十分な機械的用度を持つ
資源的に豊富で価格が安い
等がある。The ceramics used as the solid electrolyte 3 include ZrO 2 , CeO 2 , Th.
Some have O 2 and Bi 2 O 3 as main components. The characteristics required for solid electrolyte ceramics are high ionic conductivity, almost no electronic conductivity, and chemically stable at high temperatures. Has sufficient mechanical utility at high temperatures. is there.
【０００８】これらの条件を満たすものとして一般的に
用いられるものの一つがＹ2 Ｏ3 、ＣａＯ、ＭｇＯ、Ｙ
ｂ2 Ｏ3 等で安定化されたジルコニアセラミックスであ
る。このジルコニアセラミックスにおいて、ＺｒＯ2 の
結晶構造は蛍石型であり、一部の格子点が４価のＺｒに
代わり２価のＣａや３価のＹ等に置き換えられる。その
分だけ酸素が占めるべき格子点が空席となり、空格子点
の存在が酸素イオンの結晶内移動を可能にして、固体電
解質としての作用を成すのである。また、ＣａＯ、Ｙ2
Ｏ3 等を含むことにより、ＺｒＯ2 は立方晶の結晶とな
り結晶転移を起こさず、安定化の役割も果たしている。One of those generally used to satisfy these conditions is Y 2 O 3 , CaO, MgO, Y.
Zirconia ceramics stabilized with b 2 O 3 or the like. In this zirconia ceramic, the crystal structure of ZrO 2 is fluorite type, and some lattice points are replaced with divalent Ca, trivalent Y or the like instead of tetravalent Zr. The lattice points that oxygen should occupy are vacant by that amount, and the existence of the vacancy points enables the movement of oxygen ions in the crystal, and functions as a solid electrolyte. Also, CaO, Y 2
By containing O 3 and the like, ZrO 2 becomes a cubic crystal and does not cause crystal transition, and also plays a stabilizing role.
【０００９】そして図１に示すように燃料電池に用いる
場合は、固体電解質３を空気極２と燃料極４で挟み込む
ため、これらの電極材料と熱膨張係数が近いジルコニア
セラミックスが最も一般的に用いられている。When used in a fuel cell as shown in FIG. 1, since the solid electrolyte 3 is sandwiched between the air electrode 2 and the fuel electrode 4, zirconia ceramics whose thermal expansion coefficient is close to those of these electrode materials are most commonly used. Has been.
【００１０】[0010]
【００１１】[0011]
【００１２】[0012]
【発明が解決しようとする課題】上記のＣａＯ安定化Ｚ
ｒＯ2からなる支持部材１を用いた燃料電池セルの製造
工程や、あるいは燃料電池セルの長時間発電において、
支持部材１中のＣａ成分が空気極２に拡散侵入し、空気
極２の電気伝導性やあるいは酸素をイオン化させる触媒
能が低下し、その結果セルの発電特性を劣化させるとい
う問題があった。The above CaO-stabilized Z
In the manufacturing process of the fuel cell using the support member 1 made of rO 2 or in the long-term power generation of the fuel cell,
There is a problem that the Ca component in the support member 1 diffuses and enters the air electrode 2, and the electric conductivity of the air electrode 2 or the catalytic ability to ionize oxygen is reduced, resulting in deterioration of the power generation characteristics of the cell.
【００１３】[0013]
【発明の目的】そこで、本発明の目的はＣａ成分の拡散
を防ぐ空気極用支持部材を得ることである。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to obtain an air electrode support member which prevents the diffusion of Ca component.
【００１４】[0014]
【００１５】[0015]
【００１６】[0016]
【００１７】[0017]
【００１８】[0018]
【００１９】[0019]
【００２０】[0020]
【００２１】[0021]
【課題を解決するための手段】また本発明の目的を達成
するために、１０〜２０モル％のＣａＯを含み、開気孔
率が２０〜４５％のジルコニアセラミックスの表面に、
５〜１０モル％のＹ2Ｏ3を含むジルコニアセラミックス
からなる保護層を備えて空気極用支持部材を構成した。In order to achieve the object of the present invention, the surface of zirconia ceramics containing 10 to 20 mol% of CaO and having an open porosity of 20 to 45%,
A supporting member for an air electrode was constructed by including a protective layer made of zirconia ceramics containing 5 to 10 mol% of Y 2 O 3 .
【００２２】つまり、空気極用支持部材の少なくとも表
面をＹ2Ｏ3を含むジルコニアセラミックスで形成したこ
とによって、空気極や固体電解質体等へのＣａ成分の拡
散を防止するようにしたのである。That is, at least the surface of the air electrode support member is formed of zirconia ceramics containing Y2O3 to prevent the diffusion of the Ca component into the air electrode and the solid electrolyte body.
【００２３】また、燃料電池セルでは図１に示した構造
の他に、同様な材料を用い支持部材の表面にＮｉ−Ｚｒ
Ｏ2 （Ｙ2 Ｏ3 含有）の燃料極を形成した後、その上に
固体電解質、さらに空気極を設けた構造も提案されてい
る。この構造においても、本発明の支持部材を用いるこ
とが可能である。Further, in the fuel cell, in addition to the structure shown in FIG. 1, the same material is used and Ni-Zr is formed on the surface of the supporting member.
A structure in which a fuel electrode of O 2 (containing Y 2 O 3 ) is formed, and then a solid electrolyte and an air electrode are provided thereon is also proposed. Also in this structure, the supporting member of the present invention can be used.
【００２４】[0024]
【実施例】参考例１
まず固体電解質セラミックスに関する本発明の実施例を
説明する。EXAMPLES Reference Example 1 First, examples of the present invention relating to solid electrolyte ceramics will be described.
【００２５】Ｙ2 Ｏ3 を８モル％含む平均粒径１〜２μ
ｍのＺｒＯ2 原料粉末を共沈法で作製し、この原料粉末
に平均粒径０．２〜１μｍのＡｌ2 Ｏ3 粉末を表１に示
す種々の比率で添加し、ボールミルで２０時間湿式混合
を行い、乾燥、造粒、成形後１５００℃で２時間焼成し
てＪＩＳ Ｒ１６０１に基づく曲げ試験片形状のセラミ
ック焼結体を得た。この焼結体の曲げ強度と熱膨張率の
測定結果を表１に示す。Average particle size of 1 to 2 μm containing 8 mol% of Y 2 O 3
m ZrO 2 raw material powder was prepared by a coprecipitation method, and Al 2 O 3 powder having an average particle diameter of 0.2 to 1 μm was added to the raw material powder at various ratios shown in Table 1 and wet-mixed in a ball mill for 20 hours. After drying, granulating, and molding, firing was performed at 1500 ° C. for 2 hours to obtain a ceramic sintered body in the shape of a bending test piece based on JIS R1601. Table 1 shows the measurement results of the bending strength and the coefficient of thermal expansion of this sintered body.
【００２６】一般に固体電解質の曲げ強度は３０ｋｇ／
ｍｍ2 以上であれば電極形成時のハンドリング等での破
損が殆どなくなるため、曲げ強度が３０ｋｇ／ｍｍ2 以
上であるかどうかを判定基準とした。従って、表１より
Ａｌ2 Ｏ3 の添加量を０．５重量％以上とすればこの基
準を満たすことがわかる。Generally, the bending strength of a solid electrolyte is 30 kg /
If it is mm 2 or more, there is almost no damage due to handling at the time of forming an electrode, so that whether the bending strength is 30 kg / mm 2 or more was used as a criterion for judgment. Therefore, it can be seen from Table 1 that this criterion is satisfied when the addition amount of Al 2 O 3 is 0.5% by weight or more.
【００２７】また、ジルコニアが燃料電池用固体電解質
として利用される理由の一つに熱膨張率が電極材料に近
いと言うことがあるが、電極材料の熱膨張率（常温〜１
０００℃）は１１×１０-6／℃程度であることから、固
体電解質の熱膨張率（常温〜１０００℃）は９．０×１
０-6／℃以上であることが必要であり、従って表１から
Ａｌ2 Ｏ3 添加量は１５重量％以下が適切となる。One of the reasons why zirconia is used as a solid electrolyte for fuel cells is that it has a coefficient of thermal expansion close to that of the electrode material, but the coefficient of thermal expansion of the electrode material (from room temperature to 1
(000 ° C.) is about 11 × 10 −6 / ° C., the thermal expansion coefficient (normal temperature to 1000 ° C.) of the solid electrolyte is 9.0 × 1.
It is necessary to be 0 -6 / ° C or higher, and therefore, from Table 1, it is appropriate that the amount of Al 2 O 3 added be 15% by weight or less.
【００２８】以上によりＡｌ2 Ｏ3 添加量が０．５〜１
５重量％であれば適切な材料が得られる。From the above, the added amount of Al 2 O 3 is 0.5 to 1
A suitable material is obtained with 5% by weight.
【００２９】[0029]
【表１】 [Table 1]
【００３０】以上のような参考例の固体電解質セラミッ
クスは、円柱状あるいは平板状として固体電解質型燃料
電池や酸素分離膜用素子等に好適に用いることができ
る。The solid electrolyte ceramics of the reference example as described above can be suitably used in a solid electrolyte fuel cell, an oxygen separation membrane element or the like in the form of a column or a plate.
【００３１】参考例２
次に空気極用支持部材に関する本発明の参考例を説明す
る。Reference Example 2 Next, a reference example of the present invention relating to a support member for an air electrode will be described.
【００３２】共沈法を用いて合成されたＹ2 Ｏ3 添加量
５、８、１０モル％、ＣａＯ添加量１０、１５、１７モ
ル％の安定化ＺｒＯ2 原料粉末を各々１２００℃で、１
０時間仮焼した後、ジルコニアボールを用いて振動ミル
により所定の粒度まで粉砕し評価用原料を作製した。次
に成形用バインダーとして、得られた原料粉末に対し固
形分で５％添加量となるように、ＰＶＡ１００％水溶液
を攪拌混合しながら添加した。１２０℃で、１０時間乾
燥した後８０番のナイロンメッシュを通してプレス成形
用の原料を作製した。この原料を直径３０ｍｍの金型を
用い、成形圧力１ｔ／ｃｍ2 で成形した後、大気中、１
２５０〜１７００℃で焼成して多孔質ジルコニアセラミ
ックスを得、これを評価用の支持部材の試料とした。Stabilized ZrO 2 raw material powders prepared by the coprecipitation method with Y 2 O 3 addition amounts of 5, 8, 10 mol% and CaO addition amounts of 10, 15, 17 mol% were each prepared at 1200 ° C.
After calcination for 0 hour, a zirconia ball was used to grind to a predetermined particle size by a vibration mill to prepare a raw material for evaluation. Next, as a molding binder, a 100% PVA aqueous solution was added while stirring and mixing so that the solid content was 5% with respect to the obtained raw material powder. After drying at 120 ° C. for 10 hours, a raw material for press molding was produced through a No. 80 nylon mesh. This raw material was molded at a molding pressure of 1 t / cm 2 using a mold having a diameter of 30 mm, and then, in the atmosphere,
A porous zirconia ceramic was obtained by firing at 250 to 1700 ° C., which was used as a sample of a supporting member for evaluation.
【００３３】次に、空気極材料として純度９９．７％、
平均粒子径が３μｍの市販のＬａ0.9 Ｓｒ0.1 ＭｎＯ3
粉末をスラリーとして上記評価用の支持部材表面に１０
０μｍの厚みとなるように塗布し、大気中１２００℃で
５００時間熱処理した。その後、切断面についてＣａ及
びＹの空気極への拡散侵入深さをＥＰＭＡ装置により測
定した。Next, as an air electrode material, a purity of 99.7%,
Commercially available La 0.9 Sr 0.1 MnO 3 having an average particle size of 3 μm
The powder is used as a slurry on the surface of the supporting member for evaluation described above.
It was applied so as to have a thickness of 0 μm, and heat-treated in the air at 1200 ° C. for 500 hours. After that, the diffusion penetration depth of Ca and Y into the air electrode of the cut surface was measured by an EPMA apparatus.
【００３４】表２に結果を示すように、比較例であるＣ
ａＯを含むジルコニアセラミックスからなる支持部材に
ついては添加したＣａＯ量や焼結体の粒径、開気孔率に
よらず全てのもので空気極材料中へのＣａ成分の拡散が
見られた。As the results are shown in Table 2, C which is a comparative example.
Diffusion of the Ca component into the air electrode material was observed in all of the supporting members made of zirconia ceramics containing aO, regardless of the amount of CaO added, the particle size of the sintered body, and the open porosity.
【００３５】これに対し、参考例であるＹ2Ｏ3を含むジ
ルコニアセラミックスからなる支持部材については、全
ての試料においてＹ成分の拡散状態は見られなかった。
しかし、Ｙ2Ｏ3を含むジルコニアセラミックスであって
も、粒径が５μｍ未満のものでは、熱処理温度と同様の
焼成温度１３００℃での開気孔率が規格値である２０〜
４５％を満足せず、また粒径が５０μｍ以上のもので
は、焼結性が悪く１８００℃の高温焼成でも上記開気孔
率の規格を満足することができなかったため、空気極用
支持部材としては不適であった。On the other hand, with respect to the supporting member made of zirconia ceramics containing Y 2 O 3 which is a reference example, the diffusion state of the Y component was not observed in all the samples.
However, even for zirconia ceramics containing Y 2 O 3 , if the particle size is less than 5 μm, the open porosity at a firing temperature of 1300 ° C., which is similar to the heat treatment temperature, is 20% which is the standard value.
If it does not satisfy 45% and the particle size is 50 μm or more, the sinterability is poor and the above open porosity standard cannot be satisfied even at a high temperature of 1800 ° C. Therefore, as a support member for an air electrode. It was unsuitable.
【００３６】また、参考例では、支持部材の全体がＹ2
Ｏ3安定化ジルコニアセラミックスからなるため、機械
的強度を高くすることができる。In the reference example, the entire supporting member is Y 2
Since it is made of O 3 stabilized zirconia ceramics, the mechanical strength can be increased.
【００３７】[0037]
【表２】 [Table 2]
【００３８】実施例
次に空気極用支持部材に関する本発明の他の実施例を説
明する。Examples Next, other examples of the present invention relating to the support member for the air electrode will be described.
【００３９】共沈法を用いて合成されたＣａＯ添加量１
０、１５、２０モル％の安定化ＺｒＯ2 原料粉末を各々
１３００℃で、３時間仮焼した後、ジルコニアボールを
用いて振動ミルにより平均粒径１０μｍまで粉砕し評価
用原料を作製した。成形用バインダーとして、上記原料
粉末に対し固形分で５％添加量となるようにＰＶＡ１０
０％水溶液を攪拌混合しながら添加した。１２０℃で、
１０時間乾燥した後、８０番のナイロンメッシュを通し
プレス成形用原料を作製した。Addition amount of CaO synthesized by coprecipitation method 1
Each of 0, 15, and 20 mol% of the stabilized ZrO 2 raw material powder was calcined at 1300 ° C. for 3 hours, and then pulverized to a mean particle size of 10 μm with a vibration mill using zirconia balls to prepare a raw material for evaluation. As a molding binder, PVA10 is added so that the solid content is 5% with respect to the above raw material powder.
A 0% aqueous solution was added with stirring and mixing. At 120 ℃,
After drying for 10 hours, a No. 80 nylon mesh was passed through to prepare a raw material for press molding.
【００４０】得られた原料を直径３０ｍｍの金型を用
い、成形圧力１ｔ／ｃｍ2 で成形した後、大気中、１４
５０〜１７００℃で焼成し、開気孔率の異なった多孔質
ジルコニアセラミックスから成る支持部材の試料を作製
した。The obtained raw material was molded at a molding pressure of 1 t / cm 2 using a mold having a diameter of 30 mm, and was then molded in the atmosphere at 14
By firing at 50 to 1700 ° C., a sample of a supporting member made of porous zirconia ceramics having different open porosities was prepared.
【００４１】さらに、保護膜の材料として、前記同様共
沈法を用いて合成されたＹ2 Ｏ3 添加量５、８、１０モ
ル％の安定化ＺｒＯ2 原料を１２５０℃で、３時間仮焼
した後、ジルコニアボールを用いて振動ミルにより、各
々平均粒径２、５、８、１０、１５μｍに粉砕し原料粉
末を作製した。得られた原料粉末に対し、固形分で２％
添加量となるようにＰＶＡ８０％水溶液を攪拌混合しな
がら添加し、ジルコニアペーストを得た。Further, as a material for the protective film, a stabilized ZrO 2 raw material having a Y 2 O 3 addition amount of 5, 8, and 10 mol% synthesized by the same coprecipitation method as described above was calcined at 1250 ° C. for 3 hours. After that, a zirconia ball was used to pulverize the particles into an average particle size of 2, 5, 8, 10, and 15 μm by a vibration mill to prepare a raw material powder. 2% in solid content based on the obtained raw material powder
An 80% PVA aqueous solution was added with stirring and mixing so that the addition amount was obtained, to obtain a zirconia paste.
【００４２】このジルコニアペーストを上記支持部材の
表面へ厚み５０μｍ程度になるように印刷し、１２０℃
で、２時間乾燥した後、大気中にて、１４００℃で２時
間焼きつけＹ2 Ｏ3 安定化ジルコニアからなる保護層を
形成した。This zirconia paste was printed on the surface of the supporting member so that the thickness was about 50 μm, and the temperature was 120 ° C.
Then, after drying for 2 hours, it was baked in air at 1400 ° C. for 2 hours to form a protective layer made of Y 2 O 3 -stabilized zirconia.
【００４３】さらに、空気極材料として純度９９．７
％、平均粒子径が３μｍの市販のＬａ0.9 Ｓｒ0.1 Ｍｎ
Ｏ3 粉末をスラリーとして上記評価用の支持部材表面に
１００μｍの厚みとなるように塗布し、大気中１２００
℃で５００時間熱処理した。その後、切断面についてＣ
ａ及びＹの空気極への拡散侵入深さをＥＰＭＡ装置によ
り測定した。Further, the purity of the air electrode material is 99.7.
%, Commercially available La 0.9 Sr 0.1 Mn having an average particle size of 3 μm
O 3 powder was applied as a slurry to the surface of the supporting member for evaluation so as to have a thickness of 100 μm, and was applied in air at 1200
It heat-processed at 500 degreeC for 500 hours. After that, regarding the cut surface, C
The diffusion penetration depths of a and Y into the air electrode were measured by an EPMA device.
【００４４】表３、４に結果を示すように、比較例であ
る保護層を形成しないＣａＯ安定化ジルコニアセラミッ
クスのみからなる支持部材については、添加したＣａＯ
量及び焼結体の気孔率によらず全てのもので空気極材料
中へＣａ成分の拡散が見られた。As shown in the results in Tables 3 and 4, the supporting member made of only CaO-stabilized zirconia ceramics without forming a protective layer, which is a comparative example, was added with CaO.
Diffusion of the Ca component was observed in the air electrode material in all of them regardless of the amount and the porosity of the sintered body.
【００４５】これに対しＹ2 Ｏ3 安定化ジルコニアの保
護層を設けた本発明の支持部材については、Ｙ2 Ｏ3 量
にかかわらず全ての試料においてＣａ成分の拡散が遮断
されており、燃料極材料中への拡散は見られなかった。
また、Ｙの空気極への拡散も見られなかった。On the other hand, in the case of the support member of the present invention provided with the protective layer of Y 2 O 3 stabilized zirconia, the diffusion of the Ca component was blocked in all the samples regardless of the amount of Y 2 O 3 , and No diffusion into the polar material was observed.
Further, no diffusion of Y to the air electrode was observed.
【００４６】なお、上記保護層の厚みについては、種々
実験の結果５μｍ以上、好ましくは１０μｍ以上あれ
ば、Ｃａ成分の拡散を防止できることがわかった。As a result of various experiments, it was found that the thickness of the protective layer was 5 μm or more, preferably 10 μm or more, so that the diffusion of the Ca component could be prevented.
【００４７】また、本実施例では支持部材の大部分がＣ
ａＯ安定化ジルコニアセラミックスから成るため、安価
に製造することができる。In this embodiment, most of the supporting members are C
Since it is made of aO-stabilized zirconia ceramics, it can be manufactured at low cost.
【００４８】[0048]
【表３】 [Table 3]
【００４９】[0049]
【表４】 [Table 4]
【００５０】以上のような本発明の空気極用支持部材
は、円筒状や平板状等として固体電解質燃料電池等に好
適に使用することができる。The air electrode support member of the present invention as described above can be suitably used in a solid electrolyte fuel cell or the like in a cylindrical shape or a flat plate shape.
【００５１】[0051]
【００５２】本発明によれば、１０〜２０モル％のＣａ
Ｏを含み、開気孔率が２０〜４５％のジルコニアセラミ
ックスの表面に、５〜１０モル％のＹ2Ｏ3を含むジルコ
ニアセラミックスからなる保護層を備えて空気極用支持
部材を構成したことによって、燃料電池としての製造工
程中の熱処理での空気極中へのＣａ成分の拡散を防止
し、長時間作動可能な燃料電池発電セルを製造すること
が可能となる。According to the invention, 10 to 20 mol% Ca
By constructing the air electrode support member, the surface of the zirconia ceramic containing O and having an open porosity of 20 to 45% is provided with a protective layer made of zirconia ceramic containing 5 to 10 mol% of Y 2 O 3 . It is possible to prevent the diffusion of the Ca component into the air electrode during the heat treatment during the manufacturing process of the fuel cell, and to manufacture the fuel cell power generation cell that can operate for a long time.
【図１】一般的な固体電解質型燃料電池の構造を示す一
部破断斜視図である。FIG. 1 is a partially cutaway perspective view showing a structure of a general solid oxide fuel cell.
１：支持部材 ２：空気極 ３：固体電解質 ４：燃料極 ５：インターコネクタ ６：空気 ７：燃料 1: Support member 2: Air electrode 3: Solid electrolyte 4: Fuel electrode 5: Interconnector 6: Air 7: Fuel
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 35/48 - 35/488 H01M 4/86 - 4/98 H01M 8/02 H01M 8/12 B01D 71/02 500 ─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. 7 , DB name) C04B 35/48-35/488 H01M 4/86-4/98 H01M 8/02 H01M 8/12 B01D 71 / 02 500
Claims (2)
率が２０〜４５％のジルコニアセラミックスの表面に、
５〜１０モル％のＹ2Ｏ3を含むジルコニアセラミックス
の保護層を備えてなる空気極用支持部材。1. A surface of zirconia ceramic containing 10 to 20 mol% of CaO and having an open porosity of 20 to 45%,
A support member for an air electrode comprising a protective layer of zirconia ceramics containing 5 to 10 mol% of Y 2 O 3 .
とする請求項１記載の空気極用支持部材。 2. The protective layer has a thickness of 5 μm or more.
The support member for an air electrode according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03732295A JP3502685B2 (en) | 1994-03-31 | 1995-02-24 | Air electrode support |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-62737 | 1994-03-31 | ||
| JP6273794 | 1994-03-31 | ||
| JP03732295A JP3502685B2 (en) | 1994-03-31 | 1995-02-24 | Air electrode support |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07315922A JPH07315922A (en) | 1995-12-05 |
| JP3502685B2 true JP3502685B2 (en) | 2004-03-02 |
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ID=26376459
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03732295A Expired - Fee Related JP3502685B2 (en) | 1994-03-31 | 1995-02-24 | Air electrode support |
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| JPH1097859A (en) * | 1996-09-24 | 1998-04-14 | Mitsubishi Heavy Ind Ltd | Solid electrolyte type electrochemical cell and manufacture thereof |
| JPH11329462A (en) * | 1998-05-13 | 1999-11-30 | Murata Mfg Co Ltd | Solid electrolytic fuel cell |
| JP3149849B2 (en) * | 1998-06-04 | 2001-03-26 | 株式会社村田製作所 | Solid oxide fuel cell |
| DE19850203C1 (en) * | 1998-10-23 | 2000-05-31 | Eurotope Entwicklungsgesellsch | Medical radioactive iodine-125 miniature source comprises a radioactive carrier matrix enclosed in a corrosion resistant and body-compatible material |
| JP2000180595A (en) * | 1998-12-12 | 2000-06-30 | Eurotope Entwicklungs G Fuer Isotopentechnologien Mbh | Small radiation source of radioactive palladium 103 for medical use and method for manufacturing it |
| JP2004362913A (en) * | 2003-06-04 | 2004-12-24 | Nissan Motor Co Ltd | Electrolyte for solid oxide fuel cell, and manufacturing method of the same |
| JP4580729B2 (en) * | 2004-10-29 | 2010-11-17 | 株式会社ノリタケカンパニーリミテド | Zirconia porous body and method for producing the same |
| JP2006202667A (en) * | 2005-01-24 | 2006-08-03 | Chubu Electric Power Co Inc | Manufacturing method of solid electrolyte membrane |
| JP4871567B2 (en) * | 2005-10-07 | 2012-02-08 | 株式会社ニッカトー | Porous conductive zirconia sintered body and vacuum chuck member comprising the same |
| JP4523924B2 (en) * | 2006-03-23 | 2010-08-11 | 株式会社ノリタケカンパニーリミテド | Ceramic straight tube hole cylindrical support and oxygen separation membrane |
| JP4824050B2 (en) * | 2008-02-25 | 2011-11-24 | 株式会社ノリタケカンパニーリミテド | Porous support for oxygen separation membrane and oxygen separation membrane element provided with the support |
| EP2277228B1 (en) * | 2008-04-18 | 2012-05-16 | The Regents of the University of California | Integrated seal for high-temperature electrochemical device |
| FR2968000B1 (en) * | 2010-11-29 | 2013-03-08 | Saint Gobain Ct Recherches | YTTRIED ZIRCONY POWDER FONDUE |
| JP5571648B2 (en) * | 2011-12-12 | 2014-08-13 | 株式会社日本触媒 | Zirconia sheet |
| DE102017207560A1 (en) * | 2017-05-05 | 2018-11-08 | Robert Bosch Gmbh | Method for producing a functional layer device |
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