JP2001283877A - Unit cell for solid electrolytic fuel battery and its manufacturing method - Google Patents
Unit cell for solid electrolytic fuel battery and its manufacturing methodInfo
- Publication number
- JP2001283877A JP2001283877A JP2000101471A JP2000101471A JP2001283877A JP 2001283877 A JP2001283877 A JP 2001283877A JP 2000101471 A JP2000101471 A JP 2000101471A JP 2000101471 A JP2000101471 A JP 2000101471A JP 2001283877 A JP2001283877 A JP 2001283877A
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- fuel electrode
- unit cell
- electrode
- electrolyte membrane
- 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
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
-
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、燃料極を支持体と
して構成した支持膜型の固体電解質型燃料電池の単電池
に関し、特に発電性能を向上させた固体電解質型燃料電
池の単電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a unit cell of a solid oxide fuel cell of a support membrane type having a fuel electrode as a support, and more particularly to a solid electrolyte fuel cell unit having improved power generation performance.
【０００２】[0002]
【従来の技術】固体電解質型燃料電池の単電池は、電解
質の一方の面に空気極を設け、他方の面に燃料極を設け
てあり、固体電解質型燃料電池はこのような単電池を複
数積層し、空気極に酸化剤ガスを、燃料極に燃料ガスを
供給して起電力を発生させている。2. Description of the Related Art A cell of a solid oxide fuel cell has an air electrode provided on one side of an electrolyte and a fuel electrode provided on the other side. A solid oxide fuel cell comprises a plurality of such cells. The layers are stacked, and an oxidizing gas is supplied to the air electrode and a fuel gas is supplied to the fuel electrode to generate an electromotive force.
【０００３】次に、ディップ法を用いた支持膜式の単電
池の製造方法について、図１２に示す流れ図を用いて説
明する。Next, a method for manufacturing a single cell of a supporting film type using a dip method will be described with reference to a flowchart shown in FIG.
【０００４】まず粉末状の燃料極の原料をプレスにより
所定の形状に押し固め成形し（Ｔ１）、成形した燃料極
（グリーン）を電気炉等により約１００時間仮焼し、多
孔体とする（Ｔ２）。次に、仮焼した燃料極を、電解質
の原料をスラリ状にした電解質スラリの中に浸し（Ｔ
３）、燃料極の表面全体に薄く電解質原料を付着させ
る。電解質スラリを付着させたなら、電解質スラリを適
度に乾燥させ（Ｔ４）、再び燃料極を電解質スラリの中
に浸し、電解質原料を表面に付着させ、再度乾燥を行な
う。このような電解質原料の付着・乾燥作業を電解質原
料が所定の厚みとなるまで（７回程度）繰り返し、電解
質膜が燃料極の表面に所定の厚みに形成されたなら炉に
入れ焼成（Ｔ５）する。[0004] First, the raw material of the powdery fuel electrode is pressed and formed into a predetermined shape by a press (T1), and the formed fuel electrode (green) is calcined for about 100 hours in an electric furnace or the like to obtain a porous body ( T2). Next, the calcined fuel electrode is immersed in an electrolyte slurry in which the raw material of the electrolyte is formed into a slurry (T
3) A thin electrolyte material is attached to the entire surface of the fuel electrode. After the electrolyte slurry is attached, the electrolyte slurry is dried appropriately (T4), the fuel electrode is immersed in the electrolyte slurry again, the electrolyte material is attached to the surface, and drying is performed again. Such an operation of depositing and drying the electrolyte material is repeated until the electrolyte material has a predetermined thickness (about 7 times). When the electrolyte membrane is formed to a predetermined thickness on the surface of the fuel electrode, it is placed in a furnace and fired (T5). I do.
【０００５】次に電解質膜を研磨し、燃料極の周囲に形
成された不要な電解質膜を除去して、所定の形状に仕上
げる（Ｔ６）。そして、電解質膜の上に空気極を設け
（Ｔ７）、焼成を行なっていた（Ｔ８）。[0005] Next, the electrolyte membrane is polished to remove unnecessary electrolyte membranes formed around the fuel electrode, thereby completing a predetermined shape (T6). Then, an air electrode was provided on the electrolyte membrane (T7), and firing was performed (T8).
【０００６】このようにして従来は、電気的抵抗が高い
電解質膜を１０〜数１０μｍの薄膜として抵抗を低減さ
せ、単電池の作動温度を低くして、固体電解質型燃料電
池の単電池のコストや熱機械的信頼性等を向上させてい
た。As described above, conventionally, an electrolyte membrane having a high electric resistance is formed as a thin film having a thickness of 10 to several tens of μm to reduce the resistance, lower the operating temperature of the cell, and reduce the cost of the cell of the solid oxide fuel cell. And improved thermomechanical reliability.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、近年固
体電解質型燃料電池は小型化、高出力化を図る必要があ
り、より高い発電性能が単電池に求められている。例え
ば、電解質膜と空気極、あるいは電解質膜と燃料極との
間の電気抵抗をより低減させ、より高い発電性能を実現
することが求められている。However, in recent years, it has been necessary to reduce the size and output of a solid oxide fuel cell, and a higher power generation performance is required for a unit cell. For example, it is required to further reduce the electric resistance between the electrolyte membrane and the air electrode or between the electrolyte membrane and the fuel electrode to realize higher power generation performance.
【０００８】[0008]
【課題を解決するための手段】本発明では、上記課題を
解決するため、単電池を次のようにして構成した。According to the present invention, in order to solve the above problems, a unit cell is constituted as follows.
【０００９】すなわち、電解質膜と空気極との間にＳＤ
Ｃ（サマリアをドープしたセリア）の層（膜）などＣｅ
1-X ＦX Ｏ(2-δ)の膜（ＦはＣａ、Ｙ、Ｓｍ、Ｇｄ、Ｌ
ａ、Ｍｇ、Ｓｃ、Ｎｄ、Ｙｂ、Ｐｒ、Ｐｂ、Ｓｒ、Ｅ
ｕ、Ｄｙ、Ｂａ、Ｂｅのいずれか１つ又は２つ以上の組
合せであり、０≦ｘ≦０．５０）を形成して単電池を構
成した。That is, SD between the electrolyte membrane and the air electrode
Ce (Camarium doped ceria) layer (film) such as Ce
1-X F X O ( 2- δ) film (F is Ca, Y, Sm, Gd, L
a, Mg, Sc, Nd, Yb, Pr, Pb, Sr, E
u, Dy, Ba, and Be are one or a combination of two or more, and 0 ≦ x ≦ 0.50) was formed to constitute a unit cell.
【００１０】その塗布方法は例えば、燃料極の上に電解
質膜を形成した段階で、電解質膜の上にＳＤＣのスラリ
等を塗布し、そののち空気極を電解質膜の上に形成する
こととした。これにより、電解質膜と空気極との間の電
気抵抗を低減でき、発電性能の高い単電池を得ることが
できる。ＳＤＣ膜等は、少なくとも電解質膜側の面に塗
布すればよいが、電解質膜を形成した面の裏面の燃料極
表面に塗布してもよい。[0010] For example, at the stage of forming an electrolyte membrane on the fuel electrode, SDC slurry or the like is applied on the electrolyte membrane, and then the air electrode is formed on the electrolyte membrane. . Thereby, the electric resistance between the electrolyte membrane and the air electrode can be reduced, and a unit cell having high power generation performance can be obtained. The SDC film or the like may be applied on at least the surface on the electrolyte membrane side, but may be applied on the fuel electrode surface on the back surface of the surface on which the electrolyte film is formed.
【００１１】[0011]
【発明の実施の形態】本発明にかかる単電池の一実施例
について説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of a unit cell according to the present invention will be described.
【００１２】図１に単電池２を示す。単電池２は、支持
体としての燃料極４の表面に電解質膜６が形成してあ
り、さらに電解質膜６の表面にＳＤＣ膜７を介在させて
空気極８が形成してある。この単電池２を図１０に示す
ように合金セパレータ３０とセラミックマニホールド３
２からなるセパレータ３４で挟持し、セパレータ３４と
単電池２とを適宜積層して固体電解質型燃料電池１が構
成してある。固体電解質型燃料電池１は、所定の条件
（例えば温度７５０℃等）において燃料極４に燃料ガス
を、また空気極８に酸化剤ガスを供給することにより起
電力を発生する。FIG. 1 shows a cell 2. In the unit cell 2, an electrolyte membrane 6 is formed on the surface of the fuel electrode 4 as a support, and an air electrode 8 is formed on the surface of the electrolyte membrane 6 with an SDC film 7 interposed. As shown in FIG. 10, the cell 2 was divided into an alloy separator 30 and a ceramic manifold 3.
The solid oxide fuel cell 1 is configured by sandwiching the separator 34 and the unit cell 2 as appropriate, while sandwiching the separator 34 made of the fuel cell 2. The solid oxide fuel cell 1 generates an electromotive force by supplying a fuel gas to the fuel electrode 4 and an oxidant gas to the air electrode 8 under predetermined conditions (for example, a temperature of 750 ° C.).
【００１３】次に、単電池２の製造方法について図７の
流れ図を用いて説明する。まず、粉末状の原料を所定の
形状に成形し、支持体としての燃料極４を形成する（Ｓ
１）。燃料極４の原料は、例えばニッケルとイットリア
安定化ジルコニア（ＹＳＺ）のサーメットであり、原料
を水溶性のバインダ、例えばポリビニルアルコールと混
練し、プレス装置（図示せず）等により押し固め、成形
する。所定の形状に成形した燃料極４を図３に示す。燃
料極４の原料には、造孔剤（図示せず）が所定量含有し
てあり、後述する焼成により造孔剤が焼失されると燃料
極４の内部に多数の孔が形成される。Next, a method of manufacturing the unit cell 2 will be described with reference to a flowchart of FIG. First, a powdery raw material is formed into a predetermined shape to form a fuel electrode 4 as a support (S4).
1). The raw material of the fuel electrode 4 is, for example, a cermet of nickel and yttria-stabilized zirconia (YSZ). The raw material is kneaded with a water-soluble binder, for example, polyvinyl alcohol, and is compacted by a press device (not shown) and molded. . FIG. 3 shows the fuel electrode 4 formed into a predetermined shape. The raw material of the fuel electrode 4 contains a predetermined amount of a pore-forming agent (not shown), and when the pore-forming agent is burned out by firing described later, a large number of holes are formed inside the fuel electrode 4.
【００１４】プレス装置により成形された未焼成の燃料
極４は、そのままの状態で塗布装置１８（図２参照）に
配置され、電解質スラリ２４が表面に塗布される（Ｓ
２）。電解質スラリ２４は、ＹＳＺからなる電解質（電
解質膜６）の原料と非水溶性のバインダ、例えばポリビ
ニルブチラールとを混練したものであり、所定の粘度に
設定してある。尚、バインダとしては、上記以外に、メ
チルセルロース、ポリエチレン、ポリアクリル酸ソー
ダ、アラビアゴムなどがある。The unfired fuel electrode 4 formed by the pressing device is placed as it is in the coating device 18 (see FIG. 2), and the electrolyte slurry 24 is coated on the surface (S).
2). The electrolyte slurry 24 is obtained by kneading a raw material of an electrolyte (electrolyte membrane 6) made of YSZ and a water-insoluble binder, for example, polyvinyl butyral, and has a predetermined viscosity. As the binder, other than the above, there are methylcellulose, polyethylene, sodium polyacrylate, gum arabic and the like.
【００１５】図２に示すように塗布装置１８は、いわゆ
るスクリーン印刷法で印刷を行なう印刷機であり、スク
リーン版２０には電解質膜６に等しい形状の型が形成さ
れている。燃料極４を、塗布装置１８の所定の位置に配
置したなら、スクリーン版２０に沿ってスキージ２２を
移動させることにより、型を通して電解質スラリ２４が
燃料極４の上面に塗布（Ｓ２）される。電解質スラリ２
４が所定の形状に塗布されたなら、電解質の表面を適宜
乾燥させる。乾燥作業は、電解質スラリ２４を完全に乾
燥させる必要はなく、塗布した電解質スラリ２４上に重
ねて電解質スラリ２４が塗布できる程度であればよい。
電解質膜６が表面に形成された燃料極４を図４に示す。As shown in FIG. 2, the coating device 18 is a printing machine for performing printing by a so-called screen printing method, and a screen plate 20 is formed with a mold having the same shape as the electrolyte membrane 6. When the fuel electrode 4 is disposed at a predetermined position of the coating device 18, the squeegee 22 is moved along the screen plate 20, so that the electrolyte slurry 24 is coated on the upper surface of the fuel electrode 4 through the mold (S2). Electrolyte slurry 2
When 4 is applied in a predetermined shape, the surface of the electrolyte is appropriately dried. It is not necessary to completely dry the electrolyte slurry 24, and the drying operation may be performed as long as the electrolyte slurry 24 can be applied over the applied electrolyte slurry 24.
FIG. 4 shows the fuel electrode 4 on which the electrolyte membrane 6 is formed.
【００１６】電解質スラリ２４を適度に乾燥させたな
ら、上記と同様にして重ねて電解質スラリ２４を塗布
し、乾燥させる。そして電解質スラリ２４が所定の厚さ
になるまで電解質スラリ２４の塗布を繰り返す。電解質
スラリ２４が所定の厚みに積層されたなら、燃料極４と
ともに共焼結（電解質膜６と燃料極４とを一緒に焼成す
ること）する（Ｓ３）。After the electrolyte slurry 24 has been properly dried, the electrolyte slurry 24 is applied and dried in the same manner as described above. Then, the application of the electrolyte slurry 24 is repeated until the electrolyte slurry 24 has a predetermined thickness. When the electrolyte slurry 24 is laminated to a predetermined thickness, it is co-sintered with the fuel electrode 4 (the electrolyte film 6 and the fuel electrode 4 are fired together) (S3).
【００１７】そして、電解質膜６にＳＤＣを塗布して、
ＳＤＣ膜７を形成する。ＳＤＣは、サマリアをドープし
たセリア（Ｃｅ１−ｘＳｍｘＯ（２−δ））であり、粒
径が０．１〜５μｍ程度で、ｘ＝０．３である。ＳＤＣ
は、その粉末をＣｅゾルに分散、混合してＳＤＣスラリ
を形成し、ディップ法等により電解質膜６の表面全体に
４μｍの厚さに塗布する（Ｓ４）。ＳＤＣ膜７が塗布さ
れた状態を図５に示す。次に塗布したＳＤＣ膜７を所定
の温度で焼成する（Ｓ５）。焼成したなら、空気極８を
ＳＤＣ膜７を介して電解質膜６の上に塗布し（Ｓ６）、
全体を焼成して完成させる（Ｓ７）。空気極８は、平均
粒径が０．６０μｍのＬａ0.6Ｓｒ0.4Ｃｏ0.8Ｆｅ0.2Ｏ
3と、この粒子の周囲を取り囲む粒径が０．１μｍのＣ
ｅ0.8 Ｓｍ0.2Ｏ1.9の組成を有する粒子（ＬＳＣＦ−Ｓ
ＤＣ）からなり、Ｃｅ0.8 Ｓｍ0. 2Ｏ1.9は０．５〜６０
ｗｔ％含まれている。空気極８を電解質膜６の上に形成
した単電池２の全体を図６に示す。Then, SDC is applied to the electrolyte membrane 6,
An SDC film 7 is formed. SDC is a doped ceria Samaritan (Ce 1-x Sm x O (2- δ)), particle size of about 0.1 to 5 [mu] m, a x = 0.3. SDC
The SDC slurry is formed by dispersing and mixing the powder in a Ce sol, and applied to the entire surface of the electrolyte membrane 6 to a thickness of 4 μm by a dipping method or the like (S4). FIG. 5 shows a state where the SDC film 7 is applied. Next, the applied SDC film 7 is fired at a predetermined temperature (S5). After firing, the air electrode 8 is applied on the electrolyte membrane 6 via the SDC membrane 7 (S6),
The whole is fired and completed (S7). The air electrode 8 is made of La 0.6 Sr 0.4 Co 0.8 Fe 0.2 O having an average particle size of 0.60 μm.
3 and C having a particle diameter of 0.1 μm surrounding the particle.
Particles having a composition of e 0.8 Sm 0.2 O 1.9 (LSCF-S
Consists of DC), Ce 0.8 Sm 0. 2 O 1.9 0.5 to 60
wt%. FIG. 6 shows the entire unit cell 2 in which the air electrode 8 is formed on the electrolyte membrane 6.
【００１８】尚、空気極８は、（Ａ1-x Ｂx）（Ｃ1-y
Ｄy）Ｏ(3+δ) の組成を有する粒子と、Ｃｅ1-X ＥX Ｏ
(2-δ)の組成を有する粒子（ＡはＬａ、Ｙ、Ｓｍ、Ｇ
ｄ、Ｐｒ、Ｃａのいずれか１つ又は２つ以上の組合せ、
ＢはＳｒ、Ｂａ、Ｃａのいずれか１つ又は２つ以上の組
合せ、ＣはＭｎ、Ｃｏ、Ｃｅのいずれか１つ又は２つ以
上の組合せ、ＤはＣｒ、Ｎｉ、Ｍｇ、Ｚｒ、Ｃｅ、Ｆ
ｅ、Ａｌのいずれか１つ又は２つ以上の組合せ、ＥはＣ
ａ、Ｙ、Ｓｍ、Ｇｄ、Ｌａ、Ｍｇ、Ｓｃ、Ｎｄ、Ｙｂ、
Ｐｒ、Ｐｂ、Ｓｒ、Ｅｕ、Ｄｙ、Ｂａ、Ｂｅのいずれか
１つ又は２つ以上の組合せであり、０≦ｘ≦０．５０、
０≦ｙ≦０．５０）とから構成すればよく、また（Ａ
1-x Ｂx）（Ｃ1-y Ｄy）Ｏ(3+δ) の組成を有する粒子
は、径が０．１〜２０μｍ、Ｃｅ1-X ＥX Ｏ(2-δ)の組
成を有する粒子は、径が０．１〜５μｍであればよい。The air electrode 8 is (A 1 -xB x ) (C 1 -y
And particles having a composition of D y) O (3+ δ) , Ce 1-X E X O
Particles having the composition of ( 2- δ) (A is La, Y, Sm, G
d, Pr, one or a combination of two or more of Ca,
B is any one or a combination of two or more of Sr, Ba, Ca, C is a combination of any one or two or more of Mn, Co, Ce, D is Cr, Ni, Mg, Zr, Ce, F
e, any combination of two or more of Al, E is C
a, Y, Sm, Gd, La, Mg, Sc, Nd, Yb,
Any one or a combination of two or more of Pr, Pb, Sr, Eu, Dy, Ba, Be, and 0 ≦ x ≦ 0.50;
0 ≦ y ≦ 0.50), and (A
1-x B x) (C 1-y D y) O ( particles having a composition of 3+ [delta]) has a diameter 0.1 to 20 [mu] m, a composition of Ce 1-X E X O ( 2- δ) The particles may have a diameter of 0.1 to 5 μm.
【００１９】更に電解質膜６と空気極８との間にはＳＤ
Ｃ膜７でなく、Ｃｅ1-X ＦX Ｏ(2-δ)の膜（ＦはＣａ、
Ｙ、Ｓｍ、Ｇｄ、Ｌａ、Ｍｇ、Ｓｃ、Ｎｄ、Ｙｂ、Ｐ
ｒ、Ｐｂ、Ｓｒ、Ｅｕ、Ｄｙ、Ｂａ、Ｂｅのいずれか１
つ又は２つ以上の組合せであり、０≦ｘ≦０．５０）を
形成してもよい。またその粒径は０．１〜２μｍ程度で
あればよい。更に、酸素分圧やそれぞれの膜の熱膨張の
差などの観点から、電解質膜６とＳＤＣ膜７等との膜厚
の比率は、実質的に１０以上であればよい。Further, an SD is provided between the electrolyte membrane 6 and the air electrode 8.
Instead of the C film 7, a film of Ce 1-x F x O ( 2- δ) (F is Ca,
Y, Sm, Gd, La, Mg, Sc, Nd, Yb, P
any one of r, Pb, Sr, Eu, Dy, Ba, Be
Or a combination of two or more, and 0 ≦ x ≦ 0.50) may be formed. The particle size may be about 0.1 to 2 μm. Further, from the viewpoint of the oxygen partial pressure and the difference in thermal expansion between the respective films, the ratio of the film thickness between the electrolyte film 6 and the SDC film 7 or the like may be substantially 10 or more.
【００２０】このように、電解質膜６と空気極８との間
に導電性の高いＳＤＣ膜７を設けたことにより、空気極
８と電解質膜６との界面の電気抵抗が低減され、高い発
電性能を得ることができる。また、スクリーン印刷法を
用いて電解質膜６を形成したことにより表面に凹凸が形
成され、電解質膜６と空気極８との間の接触面積が増大
し、密着性が向上する。As described above, by providing the highly conductive SDC film 7 between the electrolyte membrane 6 and the air electrode 8, the electric resistance at the interface between the air electrode 8 and the electrolyte membrane 6 is reduced, and high power generation is achieved. Performance can be obtained. In addition, since the electrolyte membrane 6 is formed by using the screen printing method, irregularities are formed on the surface, the contact area between the electrolyte membrane 6 and the air electrode 8 is increased, and the adhesion is improved.
【００２１】さらに、支持体である燃料極４に所定の形
状、厚みの電解質膜６を簡易、迅速に塗布、形成するこ
とができ、また、燃料極４を仮焼することなく、燃料極
４の原料を成形した後直接電解質スラリ２４を燃料極４
に塗布できることから、手間とコストを大幅に削減する
ことができる。また、スクリーン版２０を通過させて電
解質スラリ２４を塗布することから、適度な凹凸が形成
され、良好な電解質膜６を形成することができる。Further, the electrolyte membrane 6 having a predetermined shape and thickness can be easily and quickly applied and formed on the fuel electrode 4 as a support, and the fuel electrode 4 can be formed without calcining the fuel electrode 4. The electrolyte slurry 24 is directly applied to the fuel electrode 4
, The labor and cost can be greatly reduced. Further, since the electrolyte slurry 24 is applied by passing through the screen plate 20, moderate unevenness is formed, and a good electrolyte membrane 6 can be formed.
【００２２】また、燃料極４と電解質スラリ２４それぞ
れのバインダの性質、すなわちバインダが水溶性か非水
溶性かの組み合わせを適宜選択することにより、燃料極
４に電解質スラリ２４を塗布した際の両者間に形成され
る界面の状態を調整でき、焼成した後緻密で、不純物の
少ない良好な電解質膜６を形成できる。更に、両者のバ
インダを水溶性か非水溶性か等の組み合わせ以外の組み
あわせで適宜選択することにより電解質膜６の表面や電
解質膜６と燃料極４の界面を所望の構造にすることがで
きる。The properties of the binder of the fuel electrode 4 and the electrolyte slurry 24, that is, the combination of the binder being water-soluble and the water-insoluble, are appropriately selected so that both the properties when the electrolyte slurry 24 is coated on the fuel electrode 4 can be improved. The state of the interface formed therebetween can be adjusted, and after baking, it is possible to form a dense and favorable electrolyte membrane 6 with few impurities. Furthermore, the surface of the electrolyte membrane 6 and the interface between the electrolyte membrane 6 and the fuel electrode 4 can have a desired structure by appropriately selecting a binder other than a combination of water-soluble and water-insoluble. .
【００２３】尚、ＳＤＣ膜７は、電解質膜６の全体表面
でなく、図８および図９に示すように、燃料極４と電解
質膜６の外表面全体に塗布してもよい。また空気極８は
従来の空気極でよく、空気極８を電解質膜６の上に形成
する製造方法も従来どおりでよい。The SDC film 7 may be applied not to the entire surface of the electrolyte membrane 6 but to the entire outer surfaces of the fuel electrode 4 and the electrolyte membrane 6 as shown in FIGS. The air electrode 8 may be a conventional air electrode, and the manufacturing method for forming the air electrode 8 on the electrolyte membrane 6 may be the same as the conventional method.
【００２４】尚、上記例ではスクリーン印刷法によって
電解質スラリを塗布して電解質膜を形成することとした
が、本発明では、スクリーン印刷に限らず、他の印刷法
でもよく、更にディップ法により電解質膜を形成しても
よい。In the above-described example, the electrolyte slurry is applied by the screen printing method to form the electrolyte membrane. However, the present invention is not limited to the screen printing, but may be another printing method. A film may be formed.
【００２５】またバインダの性質は、上記例に限らず他
の種類の組み合わせでもよい。The nature of the binder is not limited to the above example, but may be other types of combinations.
【００２６】実験例 図１１に本件発明にかかる実験結果を示す。実験に用い
た単電池は、燃料極をＮｉとＹＳＺのサーメット、電解
質をＹＳＺ、空気極を平均０．６μｍの（Ｌａ １−ｘＳ
ｒｘ）（Ｃｏ１−ｙＦｅｙ）Ｏ（３＋δ）粒子（ｘ＝
０．４、ｙ＝０．２）と、０．１μｍのＣｅ１−ｘＳｍ
ｘＯ（２−δ）粒子（ｘ＝０．２）から構成し、燃料極
に電解質膜を形成した状態で、一方は全体に、他方は電
解質膜と空気極の間にのみＳＤＣ（Ｃｅ０．７Ｓｍ
０．３Ｏ（２−δ））膜を設け、それぞれ空気極をＳＤ
Ｃ膜の上に形成した。Experimental Example FIG. 11 shows an experimental result according to the present invention. Used for experiment
The cell has a fuel electrode of Ni and YSZ cermet, electrolytic
The quality is YSZ and the cathode is 0.6 μm on average (La 1-xS
rx) (Co1-yFey) O(3+δ)Particles (x =
0.4, y = 0.2) and 0.1 μm Ce1-xSm
xO(2-δ)Composed of particles (x = 0.2)
With the electrolyte membrane formed on one side, one is the whole and the other is the
The SDC (Ce0.7Sm
0.3O(2-δ)) A membrane is provided and the air electrode is set to SD
It was formed on the C film.
【００２７】これら単電池を、７５０℃の作動温度で、
燃料ガスと酸化剤ガスとを供給し、発電を開始させ、電
流密度に対する電圧を計測した。これにより、電流密度
が上昇しても電圧の降下が少なく、高い発電性能が得ら
れ、しかもＳＤＣ膜を燃料極と電解質膜との間のみでな
く電解質膜の逆側、すなわち燃料極の表面側にも形成し
た方が良い結果が得られることがわかる。These cells were operated at an operating temperature of 750 ° C.
The fuel gas and the oxidizing gas were supplied, power generation was started, and the voltage with respect to the current density was measured. As a result, even if the current density increases, the voltage drop is small and high power generation performance can be obtained. In addition, the SDC film is formed not only between the fuel electrode and the electrolyte film but also on the opposite side of the electrolyte film, that is, on the surface side of the fuel electrode. It can be seen that better results can be obtained by forming them.
【００２８】[0028]
【発明の効果】本発明の単電池によれば、少なくとも電
解質膜と空気極との間にＳＤＣ膜などＣｅ1-X ＦX Ｏ(
2-δ)の膜（ＦはＣａ、Ｙ、Ｓｍ、Ｇｄ、Ｌａ、Ｍｇ、
Ｓｃ、Ｎｄ、Ｙｂ、Ｐｒ、Ｐｂ、Ｓｒ、Ｅｕ、Ｄｙ、Ｂ
ａ、Ｂｅのいずれか１つ又は２つ以上の組合せであり、
０≦ｘ≦０．５０）を形成したことにより、電解質膜と
空気極との電気抵抗を低減し、高い発電性能の単電池を
得ることができる。According to the unit cell of the present invention, Ce 1-X F X O (SDC film or the like) is provided at least between the electrolyte membrane and the air electrode.
2- δ) film (F is Ca, Y, Sm, Gd, La, Mg,
Sc, Nd, Yb, Pr, Pb, Sr, Eu, Dy, B
a, Be or a combination of two or more of Be,
(0 ≦ x ≦ 0.50), the electric resistance between the electrolyte membrane and the air electrode is reduced, and a unit cell with high power generation performance can be obtained.
【図１】本発明にかかる単電池を示す図である。FIG. 1 is a diagram showing a unit cell according to the present invention.
【図２】塗布装置を示す図である。FIG. 2 is a view showing a coating apparatus.
【図３】燃料極を示す図である。FIG. 3 is a diagram showing a fuel electrode.
【図４】電解質膜を形成した燃料極を示す図である。FIG. 4 is a view showing a fuel electrode on which an electrolyte membrane is formed.
【図５】ＳＤＣ膜を形成した燃料極を示す図である。FIG. 5 is a view showing a fuel electrode on which an SDC film is formed.
【図６】単電池を示す図である。FIG. 6 is a diagram showing a unit cell.
【図７】本発明にかかる製造方法の手順を示す図であ
る。FIG. 7 is a diagram showing a procedure of a manufacturing method according to the present invention.
【図８】ＳＤＣ膜を形成した電解質膜と燃料極の断面図
である。FIG. 8 is a sectional view of an electrolyte membrane on which an SDC membrane is formed and a fuel electrode.
【図９】ＳＤＣ膜を形成した単電池を示す断面図であ
る。FIG. 9 is a cross-sectional view showing a unit cell on which an SDC film is formed.
【図１０】固体電解質型燃料電池を示す図である。FIG. 10 is a diagram showing a solid oxide fuel cell.
【図１１】実験結果を示す図である。FIG. 11 is a view showing an experimental result.
【図１２】従来の製造方法の手順を示す図である。FIG. 12 is a diagram showing a procedure of a conventional manufacturing method.
２ 単電池 ４ 燃料極 ６ 電解質膜 ７ ＳＤＣ膜 ８ 空気極 １８ 塗布装置 ２０ スクリーン版 ２２ スキージ ２４ 電解質スラリ ３０ 合金セパレータ ３２ セラミックマニホールド ３４ セパレータ Reference Signs List 2 cell 4 fuel electrode 6 electrolyte membrane 7 SDC membrane 8 air electrode 18 coating device 20 screen plate 22 squeegee 24 electrolyte slurry 30 alloy separator 32 ceramic manifold 34 separator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 浦谷 美由紀 東京都港区海岸一丁目５番20号 東京瓦斯 株式会社内 Ｆターム(参考） 5H018 AA06 AS02 AS03 BB08 EE13 HH05 5H026 AA06 BB04 EE13 HH05 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Miyuki Uraya 1-5-20 Kaigan, Minato-ku, Tokyo Tokyo Gas Co., Ltd. F-term (reference) 5H018 AA06 AS02 AS03 BB08 EE13 HH05 5H026 AA06 BB04 EE13 HH05
Claims (5)
質膜を形成し、該電解質膜の上に空気極を形成し、前記
空気極に酸化剤ガス、前記燃料極に燃料ガスを供給し、
両者間で起電力を発生させて電力を得る固体電解質型燃
料電池の単電池において、 前記電解質膜と前記空気極との間にＣｅ1-X ＦX Ｏ(2-
δ)の膜（ＦはＣａ、Ｙ、Ｓｍ、Ｇｄ、Ｌａ、Ｍｇ、Ｓ
ｃ、Ｎｄ、Ｙｂ、Ｐｒ、Ｐｂ、Ｓｒ、Ｅｕ、Ｄｙ、Ｂ
ａ、Ｂｅのいずれか１つ又は２つ以上の組合せであり、
０≦ｘ≦０．５０）を形成したことを特徴とした固体電
解質型燃料電池の単電池。A fuel electrode is used as a substrate, an electrolyte film is formed on the fuel electrode, an air electrode is formed on the electrolyte film, an oxidant gas is supplied to the air electrode, and a fuel gas is supplied to the fuel electrode. Supply,
In a unit cell of a solid oxide fuel cell that obtains electric power by generating electromotive force between the two, a Ce 1-X F X O ( 2−) is provided between the electrolyte membrane and the air electrode.
δ) film (F is Ca, Y, Sm, Gd, La, Mg, S
c, Nd, Yb, Pr, Pb, Sr, Eu, Dy, B
a, Be or a combination of two or more of Be,
0 ≦ x ≦ 0.50). A solid electrolyte fuel cell unit cell.
燃料極の表面全体に形成したことを特徴とする請求項１
記載の固体電解質型燃料電池の単電池。2. A method according to claim membrane of the Ce 1-X F X O ( 2- δ), characterized in that formed on the entire surface of the fuel electrode 1
A unit cell of the solid oxide fuel cell according to the above.
リアをドープしたセリア膜であることを特徴とする請求
項１または２記載の固体電解質型燃料電池の単電池。Wherein membrane of the Ce 1-X F X O ( 2- δ) is a single cell of the solid oxide fuel cell according to claim 1 or 2, wherein the ceria film doped with samaria .
料極に形成したことを特徴とする請求項１〜３のいずれ
か１項に記載の固体電解質型燃料電池の単電池の製造方
法。4. The method for manufacturing a unit cell of a solid oxide fuel cell according to claim 1, wherein said electrolyte membrane is formed on said fuel electrode by a printing method. .
請求項４に記載の固体電解質型燃料電池の単電池の製造
方法。5. The method of manufacturing a solid oxide fuel cell according to claim 4, wherein the printing method is a screen printing method.
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|---|---|---|---|
| JP2000101471A JP2001283877A (en) | 2000-04-03 | 2000-04-03 | Unit cell for solid electrolytic fuel battery and its manufacturing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000101471A JP2001283877A (en) | 2000-04-03 | 2000-04-03 | Unit cell for solid electrolytic fuel battery and its manufacturing method |
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|---|---|
| JP2001283877A true JP2001283877A (en) | 2001-10-12 |
Family
ID=18615516
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|---|---|---|---|
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004055326A (en) * | 2002-07-19 | 2004-02-19 | Toho Gas Co Ltd | Unit cell of solid oxide fuel cell and solid oxide fuel cell using the unit cell |
| JP2004119161A (en) * | 2002-09-25 | 2004-04-15 | Ngk Spark Plug Co Ltd | Unit cell for solid electrolyte fuel battery, fuel battery therewith and manufacturing method thereof |
| JP2005196981A (en) * | 2003-12-26 | 2005-07-21 | Ngk Spark Plug Co Ltd | Intermediate body of fuel electrode supporting film type fuel cell, and manufacturing method of the same |
| JP2005216761A (en) * | 2004-01-30 | 2005-08-11 | Kyocera Corp | Fuel battery cell and fuel battery |
| JP2005327637A (en) * | 2004-05-14 | 2005-11-24 | Ngk Spark Plug Co Ltd | Solid electrolyte fuel cell |
| JP2006134597A (en) * | 2004-11-02 | 2006-05-25 | Honda Motor Co Ltd | Fuel cell |
| JP2006278089A (en) * | 2005-03-29 | 2006-10-12 | Kyocera Corp | Fuel battery cell and fuel battery |
| JP2007005186A (en) * | 2005-06-24 | 2007-01-11 | Honda Motor Co Ltd | Fuel cell and fuel cell stack |
| WO2007061043A1 (en) * | 2005-11-25 | 2007-05-31 | Nippon Telegraph And Telephone Corporation | Solid oxide fuel cell |
| CN100456544C (en) * | 2006-08-18 | 2009-01-28 | 中国科学院上海硅酸盐研究所 | Anode supporting solid electrolyte compound film for solid oxide fuel battery and its preparing method |
| JP2009140694A (en) * | 2007-12-05 | 2009-06-25 | Nippon Telegr & Teleph Corp <Ntt> | Solid oxide fuel cell |
| JP2009245603A (en) * | 2008-03-28 | 2009-10-22 | Dainippon Printing Co Ltd | Manufacturing method for solid oxide fuel cell, and the solid oxide fuel cell manufactured by the manufacturing method |
| JP2009295521A (en) * | 2008-06-09 | 2009-12-17 | Nippon Telegr & Teleph Corp <Ntt> | Solid oxide fuel cell |
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|---|---|---|---|---|
| JP2004055326A (en) * | 2002-07-19 | 2004-02-19 | Toho Gas Co Ltd | Unit cell of solid oxide fuel cell and solid oxide fuel cell using the unit cell |
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| JP2006278089A (en) * | 2005-03-29 | 2006-10-12 | Kyocera Corp | Fuel battery cell and fuel battery |
| JP2007005186A (en) * | 2005-06-24 | 2007-01-11 | Honda Motor Co Ltd | Fuel cell and fuel cell stack |
| JP4555173B2 (en) * | 2005-06-24 | 2010-09-29 | 本田技研工業株式会社 | Fuel cell and fuel cell stack |
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| JP5065046B2 (en) * | 2005-11-25 | 2012-10-31 | 日本電信電話株式会社 | Solid oxide fuel cell |
| CN100456544C (en) * | 2006-08-18 | 2009-01-28 | 中国科学院上海硅酸盐研究所 | Anode supporting solid electrolyte compound film for solid oxide fuel battery and its preparing method |
| JP2009140694A (en) * | 2007-12-05 | 2009-06-25 | Nippon Telegr & Teleph Corp <Ntt> | Solid oxide fuel cell |
| JP2009245603A (en) * | 2008-03-28 | 2009-10-22 | Dainippon Printing Co Ltd | Manufacturing method for solid oxide fuel cell, and the solid oxide fuel cell manufactured by the manufacturing method |
| JP2009295521A (en) * | 2008-06-09 | 2009-12-17 | Nippon Telegr & Teleph Corp <Ntt> | Solid oxide fuel cell |
| JP2010177096A (en) * | 2009-01-30 | 2010-08-12 | Nippon Telegr & Teleph Corp <Ntt> | Method for manufacturing air electrode for solid oxide fuel cell and solid oxide fuel cell |
| JP2014123520A (en) * | 2012-12-21 | 2014-07-03 | Agc Seimi Chemical Co Ltd | Gallate complex oxide, and solid oxide fuel cell using the same |
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