JP3417495B2 - Air electrode slurry for solid oxide fuel cells - Google Patents
Air electrode slurry for solid oxide fuel cellsInfo
- Publication number
- JP3417495B2 JP3417495B2 JP28608493A JP28608493A JP3417495B2 JP 3417495 B2 JP3417495 B2 JP 3417495B2 JP 28608493 A JP28608493 A JP 28608493A JP 28608493 A JP28608493 A JP 28608493A JP 3417495 B2 JP3417495 B2 JP 3417495B2
- Authority
- JP
- Japan
- Prior art keywords
- air electrode
- earth metal
- electrode slurry
- solid oxide
- slurry
- 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
-
- 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
Landscapes
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
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用
空気極スラリーに関するもので、さらに詳しく言えば、
その成形を容易に行い、成形体の強度を高めることがで
きる固体電解質型燃料電池用空気極スラリーに関するも
のである。FIELD OF THE INVENTION The present invention relates to an air electrode slurry for a solid oxide fuel cell, and more specifically,
The present invention relates to an air electrode slurry for a solid oxide fuel cell, which can be easily molded to enhance the strength of the molded body.
【０００２】[0002]
【従来の技術】固体電解質型燃料電池は、作動温度が約
１０００℃であるため、高温の排熱を利用できるといっ
た付加価値やエネルギーの変換効率が高いといった利点
があるため、精力的な研究開発が進められている。2. Description of the Related Art A solid oxide fuel cell has an operating temperature of about 1000 ° C., and therefore has advantages such as high added value such as use of high temperature exhaust heat and high energy conversion efficiency. Is being promoted.
【０００３】このような固体電解質型燃料電池の構造と
しては、平板型や円筒型などが知られているが、電池を
構成する電解質の材料としては酸素イオンや水素イオン
に対する導電性が大きく、酸化雰囲気や還元雰囲気中の
いずれにおいても化学的に安定であり、空気極の材料と
しては電子電導性が大きく、酸化雰囲気中において化学
的に安定であり、燃料極の材料としては電子電導性が大
きく、還元雰囲気中において化学的に安定であるといっ
た条件を満足することが求められている。As a structure of such a solid oxide fuel cell, a flat plate type and a cylindrical type are known, but as a material of an electrolyte constituting the cell, there is great conductivity with respect to oxygen ions and hydrogen ions, and oxidation is caused. It is chemically stable in both atmosphere and reducing atmosphere, has a large electron conductivity as an air electrode material, and is chemically stable in an oxidizing atmosphere, has a large electron conductivity as a fuel electrode material. It is required to satisfy the condition that it is chemically stable in a reducing atmosphere.
【０００４】すなわち、上記した電解質としてはイット
リアなどの安定化剤を添加したジルコニア（ＹＳＺ）が
用いられ、空気極としては酸化カルシウムまたは酸化ス
トロンチウムを添加したＬａＭｎＯ3やＬａＣｒＯ3など
の複合酸化物を主体としたものが用いられ、燃料極とし
ては酸化ニッケルを主体としたものが用いられている。That is, zirconia (YSZ) added with a stabilizer such as yttria is used as the electrolyte, and composite oxides such as LaMnO 3 and LaCrO 3 added with calcium oxide or strontium oxide are used as the air electrode. The main component is used, and the main component of the fuel electrode is nickel oxide.
【０００５】上記した材料からなる固体電解質型燃料電
池の燃料極に約１０００℃の作動温度に昇温した燃料と
しての水素や一酸化炭素を供給すると、酸化ニッケルが
還元されて抵抗の小さいＮｉ−ＹＳＺサーメットとなっ
て負極としての作用をし、同温度に昇温した酸素や空気
を空気極に供給すると、空気極が正極の作用をして電池
として作動する。When hydrogen or carbon monoxide as a fuel heated to an operating temperature of about 1000 ° C. is supplied to the fuel electrode of a solid oxide fuel cell made of the above-mentioned materials, nickel oxide is reduced and Ni− having a small resistance is supplied. The YSZ cermet acts as a negative electrode, and when oxygen or air heated to the same temperature is supplied to the air electrode, the air electrode acts as a positive electrode and operates as a battery.
【０００６】一方、上記した電解質は、その抵抗を小さ
くする必要性から数十〜数百μｍの膜体に加工され、し
かもガスを通さない緻密性を必要とするため、平板型の
固体電解質型燃料電池ではテープキャスト法、カレンダ
ロール法、スラリーキャスト法といった湿式法によって
作製され、円筒型の固体電解質型燃料電池では溶射法、
ＥＶＤ法などによって作製され、上記した空気極、燃料
極も、その形状に応じて電解質と同様の方法で作製され
る。On the other hand, the above-mentioned electrolyte is processed into a film having a thickness of several tens to several hundreds of μm due to the necessity of reducing the resistance thereof, and further, it is required to have a gas-tight denseness. The fuel cell is manufactured by a wet method such as a tape casting method, a calendar roll method, and a slurry casting method, and a cylindrical solid oxide fuel cell is manufactured by a thermal spraying method.
It is produced by the EVD method or the like, and the air electrode and the fuel electrode described above are also produced by the same method as that for the electrolyte depending on their shapes.
【０００７】ところで、近年、固体電解質型燃料電池と
しては円筒型のものが注目され、高価な溶射法、ＥＶＤ
法に代わる電解質などの作製方法が研究され、特願平２
−４０９９９７号や特願平３−２９５３９号に開示され
たような、スラリーを連続して吸水性を有する型に流し
込んで成形する方法が開発されている。By the way, in recent years, a cylindrical type solid electrolyte fuel cell has been attracting attention, and an expensive thermal spraying method, EVD
Japanese Patent Application No. 2
As disclosed in Japanese Patent Application No. 409997 and Japanese Patent Application No. 3-29539, there has been developed a method of continuously pouring a slurry into a mold having water absorbency and molding.
【０００８】[0008]
【発明が解決しようとする課題】上記した、スラリーを
連続して吸水性を有する型に流し込んで成形して空気極
を作製する場合、最初に空気極を作製するスラリーを吸
水性を有する型に流し込むと、前記スラリー中のＬａＭ
ｎＯ3 やＬａＣｒＯ3 などの複合酸化物が溶解してスラ
リーの分散性が低下し、型から成形体を取り出すのが困
難になったり、取り出した成形体の強度が小さくなると
いう問題があった。When an air electrode is produced by continuously casting the slurry into a mold having water absorption, the slurry for producing the air electrode is first changed to a mold having water absorption. When poured, LaM in the slurry
There are problems that the complex oxides such as nO 3 and LaCrO 3 are dissolved and the dispersibility of the slurry is lowered, making it difficult to take out the molded body from the mold, and the strength of the molded body taken out is reduced.
【０００９】[0009]
【課題を解決するための手段】上記課題を解決するた
め、本発明の固体電解質型燃料電池用空気極スラリー
は、希土類金属元素またはアルカリ土類金属元素を含む
複合酸化物と、前記希土類金属イオンまたはアルカリ土
類金属イオンと反応して不溶性の塩を生成する添加物と
を主体として構成されることを特徴とするものであ
る。。In order to solve the above problems, an air electrode slurry for a solid oxide fuel cell according to the present invention is a composite oxide containing a rare earth metal element or an alkaline earth metal element, and the rare earth metal ion. Alternatively, it is mainly composed of an additive which reacts with an alkaline earth metal ion to form an insoluble salt. .
【００１０】[0010]
【作用】従って、本発明は、酸化カルシウムまたは酸化
ストロンチウムを添加したＬａＭｎＯ3 やＬａＣｒＯ3
などの複合酸化物は、スラリーにすることによってその
一部がイオン化するが、このイオンと反応して不溶性の
塩を生成する添加物によってスラリー中の多価イオンの
濃度を低下させることができるので、型から成形体を容
易に取り出すことができ、成形体の強度も高めることが
できる。Therefore, according to the present invention, LaMnO 3 or LaCrO 3 to which calcium oxide or strontium oxide is added is added.
A part of the composite oxide such as is ionized by making it into a slurry, but the concentration of polyvalent ions in the slurry can be lowered by an additive that reacts with this ion to form an insoluble salt. The molded body can be easily taken out from the mold, and the strength of the molded body can be increased.
【００１１】[0011]
【実施例】以下実施例により説明する。EXAMPLES Examples will be described below.
【００１２】図１は、本発明の固体電解質型燃料電池用
空気極スラリーとして、（Ｌａ0.8Ｓｒ0.2 ）0.9 Ｍｎ
Ｏ3 粉末と、０〜０．７５重量％のシュウ酸アンモニウ
ムとに炭素粉末、分散剤、消泡剤、バインダーを水中で
混合してなるものを調製し、この空気極スラリー中に溶
解したＬａイオン、Ｓｒイオン、Ｍｎイオンの量を調査
したものである。FIG. 1 shows (La 0.8 Sr 0.2 ) 0.9 Mn as an air electrode slurry for a solid oxide fuel cell of the present invention.
An O 3 powder and 0 to 0.75% by weight of ammonium oxalate were mixed with a carbon powder, a dispersant, an antifoaming agent and a binder in water to prepare La, which was dissolved in the air electrode slurry. The amount of ions, Sr ions, and Mn ions was investigated.
【００１３】図１から、シュウ酸アンモニウムを添加す
ることにより、Ｍｎイオンの空気極スラリー中への溶解
量は微増したものの、Ｌａイオン、Ｓｒイオンの空気極
スラリー中への溶解量は減少することがわかり、シュウ
酸アンモニウムを添加することによってスラリー中のＬ
ａイオン、Ｓｒイオンの濃度を抑制できることがわか
る。From FIG. 1, by adding ammonium oxalate, the amount of Mn ions dissolved in the air electrode slurry slightly increased, but the amount of La ions and Sr ions dissolved in the air electrode slurry decreased. And the ammonium in the slurry was added by adding ammonium oxalate.
It can be seen that the concentrations of a-ions and Sr-ions can be suppressed.
【００１４】また、前記シュウ酸アンモニウムに代えて
炭酸アンモニウムを添加しても同様の効果が得られるこ
とが考えられる。It is considered that the same effect can be obtained by adding ammonium carbonate instead of ammonium oxalate.
【００１５】次に、前記空気極スラリーを石膏型に流し
込んで一定時間放置した後余剰の空気極スラリーを除去
して空気極成形体を形成した後、この空気極成形体の平
均気孔径、最大気孔径および比表面積を水銀圧入法によ
って分析するとともに、シュウ酸アンモニウムの添加量
と石膏型から前記空気極成形体の離型性の難易を調査し
た結果を表１に示す。Next, after pouring the air electrode slurry into a plaster mold and allowing it to stand for a certain period of time, excess air electrode slurry is removed to form an air electrode formed body, and the average pore diameter of the air electrode formed body Table 1 shows the results of an analysis of the pore diameter and the specific surface area by the mercury porosimetry method, and an examination of the ease of releasability of the air electrode molded body from the amount of ammonium oxalate added and the gypsum mold.
【００１６】[0016]
【表１】 [Table 1]
【００１７】表１から、シュウ酸アンモニウムを添加し
た本発明の空気極成形体は平均気孔径、最大気孔径が小
さくなり、比表面積が増加することがわかる。From Table 1, it can be seen that the air electrode molded body of the present invention to which ammonium oxalate is added has a smaller average pore diameter and maximum pore diameter and an increased specific surface area.
【００１８】また、表１から、シュウ酸アンモニウムを
０．２５〜０．５０重量％添加した本発明の空気極成形
体は石膏型からの離型性が良好になることがわかる。Further, it can be seen from Table 1 that the air electrode molding of the present invention containing ammonium oxalate in an amount of 0.25 to 0.50% by weight has a good releasability from the gypsum mold.
【００１９】なお、前記シュウ酸アンモニウムが無添加
の場合は空気極成形体が柔軟すぎて空気極成形体を型か
ら除去するのが困難になり、０．７５重量％添加した場
合は空気極成形体が型に密着しすぎて空気極成形体を型
から除去するのが困難になることがわかった。When the above-mentioned ammonium oxalate was not added, the air electrode formed body was too soft and it was difficult to remove the air electrode formed body from the mold. When 0.75% by weight was added, the air electrode formed body was formed. It has been found that the body adheres too closely to the mold making it difficult to remove the cathode molding from the mold.
【００２０】また、前記シュウ酸アンモニウムに代えて
炭酸アンモニウムを添加しても、同様に空気極成形体の
平均気孔径、最大気孔径が小さくなり、比表面積が増加
することが考えられる。Further, even if ammonium carbonate is added instead of the ammonium oxalate, it is considered that the average pore diameter and the maximum pore diameter of the air electrode molded article are similarly reduced and the specific surface area is increased.
【００２１】上記した実施例は空気極スラリーについて
述べているが、インターコネクターも前記空気極スラリ
ーと類似の材料から作製することができるので、このイ
ンターコネクターをスラリーで形成する場合についても
適用できることは言うまでもない。Although the above-mentioned embodiments describe the cathode slurry, the interconnector can also be made of a material similar to the cathode slurry, so that it can be applied to the case where the interconnector is formed by the slurry. Needless to say.
【発明の効果】上記した如く、本発明の固体電解質型燃
料電池用空気極スラリーは、空気極成形体を型から容易
に取り出すことができ、その成形体の強度を高めること
ができるので、固体電解質型燃料電池を安価に製造する
ことができる湿式法の改善に寄与することができる。As described above, since the air electrode slurry for a solid oxide fuel cell of the present invention can easily take out the air electrode formed body from the mold and enhance the strength of the formed body, It can contribute to the improvement of the wet method that can manufacture the electrolyte fuel cell at low cost.
【図１】本発明の固体電解質型燃料電池用空気極スラリ
ーとして、（Ｌａ0.8 Ｓｒ0.2）0.9 ＭｎＯ3 粉末と、
０〜０．７５重量％のシュウ酸アンモニウムとに炭素粉
末、分散剤、消泡剤、バインダーを水中で混合してなる
ものを調製し、この空気極スラリー中に溶解したＬａイ
オン、Ｓｒイオン、Ｍｎイオンの量を調査した図であ
る。FIG. 1 shows (La 0.8 Sr 0.2 ) 0.9 MnO 3 powder as an air electrode slurry for a solid oxide fuel cell of the present invention,
A mixture of 0 to 0.75% by weight of ammonium oxalate with carbon powder, a dispersant, a defoaming agent, and a binder was prepared, and La ions and Sr ions dissolved in the air electrode slurry were prepared. It is the figure which investigated the quantity of Mn ion.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭60−159185（ＪＰ，Ａ) 特開 平４−74721（ＪＰ，Ａ) 特開 昭51−90435（ＪＰ，Ａ) 特開 昭64−14872（ＪＰ，Ａ) 特開 平３−17959（ＪＰ，Ａ) 特開 平４−149024（ＪＰ，Ａ) 特開 平４−215259（ＪＰ，Ａ) 特開 平４−267068（ＪＰ，Ａ) 特開 平４−289665（ＪＰ，Ａ) 特開 平４−357163（ＪＰ，Ａ) 特開 平５−101841（ＪＰ，Ａ) 特公 昭40−7695（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/86 - 4/98 H01M 8/12 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-60-159185 (JP, A) JP-A-4-74721 (JP, A) JP-A 51-90435 (JP, A) JP-A 64-- 14872 (JP, A) JP 3-17959 (JP, A) JP 4-149024 (JP, A) JP 4-215259 (JP, A) JP 4-267068 (JP, A) JP-A-4-289665 (JP, A) JP-A-4-357163 (JP, A) JP-A-5-101841 (JP, A) JP-B-40-7695 (JP, B1) (58) Fields investigated (Int.Cl. 7 , DB name) H01M 4/86-4/98 H01M 8/12 CA (STN) REGISTRY (STN)
Claims (3)
元素を含む複合酸化物と、前記希土類金属イオンまたは
アルカリ土類金属イオンと反応して不溶性の塩を生成す
る添加物とを主体として構成されることを特徴とする固
体電解質型燃料電池用空気極スラリー。1. A composite oxide mainly containing a rare earth metal element or an alkaline earth metal element, and an additive which reacts with the rare earth metal ion or the alkaline earth metal ion to form an insoluble salt. An air electrode slurry for a solid oxide fuel cell, which is characterized in that:
属イオンと反応して不溶性の塩を生成する添加物はシュ
ウ酸アンモニウムまたは炭酸アンモニウムであることを
特徴とする請求項第１項記載の固体電解質型燃料電池用
空気極スラリー。2. The solid electrolyte type according to claim 1, wherein the additive that reacts with the rare earth metal ion or the alkaline earth metal ion to form an insoluble salt is ammonium oxalate or ammonium carbonate. Air electrode slurry for fuel cells.
元素を含む複合酸化物は、（Ｌａ1-X ＡX ）Y ＭｎＯ3
または（Ｌａ1-X ＡX ）Y ＣｒＯ3 （Ｘ＝０〜０．９，
Ｙ＝１〜０．８５，Ａ＝Ｃａ，Ｓｒ，Ｂａ）であること
を特徴とする請求項第１項記載の固体電解質型燃料電池
用空気極スラリー。3. A composite oxide containing a rare earth metal element or an alkaline earth metal element is (La 1 -X A X ) Y MnO 3
Or (La 1-X A X) Y CrO 3 (X = 0~0.9,
Y = 1 to 0.85, A = Ca, Sr, Ba), The air electrode slurry for a solid oxide fuel cell according to claim 1, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28608493A JP3417495B2 (en) | 1993-10-19 | 1993-10-19 | Air electrode slurry for solid oxide fuel cells |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28608493A JP3417495B2 (en) | 1993-10-19 | 1993-10-19 | Air electrode slurry for solid oxide fuel cells |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07114926A JPH07114926A (en) | 1995-05-02 |
| JP3417495B2 true JP3417495B2 (en) | 2003-06-16 |
Family
ID=17699737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28608493A Expired - Fee Related JP3417495B2 (en) | 1993-10-19 | 1993-10-19 | Air electrode slurry for solid oxide fuel cells |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3417495B2 (en) |
-
1993
- 1993-10-19 JP JP28608493A patent/JP3417495B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07114926A (en) | 1995-05-02 |
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