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JP2006139955A - Solid oxide fuel cell - Google Patents

Solid oxide fuel cell Download PDF

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JP2006139955A
JP2006139955A JP2004326806A JP2004326806A JP2006139955A JP 2006139955 A JP2006139955 A JP 2006139955A JP 2004326806 A JP2004326806 A JP 2004326806A JP 2004326806 A JP2004326806 A JP 2004326806A JP 2006139955 A JP2006139955 A JP 2006139955A
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electrode
solid oxide
current collector
fuel cell
air electrode
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JP4867155B2 (en
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Kuniaki Yoshikata
邦聡 芳片
Hirotoshi Sakamoto
宏年 坂元
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Dai Nippon Printing Co Ltd
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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

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid oxide fuel cell suppressing increase in the resistance value due to increase in the contact resistance of a fuel electrode and an air electrode with a current collector, and preventing damages to cell performance. <P>SOLUTION: The solid oxide fuel cell has structure arranging a fuel electrode 3 on one side and an air electrode 4 on the other side via an electrolyte 2, and a current collector 5 is formed by printing, while leaving an exposure region exposing the fuel electrode 3 and the air electrode 4 on at least one electrode of the fuel electrode 3 and the air electrode 4. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、燃料ガスと酸化剤ガスを利用して安定的に発電する固体酸化物形燃料電池に関する。   The present invention relates to a solid oxide fuel cell that generates power stably using fuel gas and oxidant gas.

従来の固体酸化物形燃料電池（SOFC）は、電解質を介して燃料極及び空気極からなる電極を配置した構造であり、電解質が隔壁になり、一方の電極室に燃料ガス、他方の電極室に酸化剤ガスを供給する二室型ＳＯＦＣを用いていた。   A conventional solid oxide fuel cell (SOFC) has a structure in which an electrode composed of a fuel electrode and an air electrode is arranged through an electrolyte. The electrolyte serves as a partition, fuel gas in one electrode chamber, and the other electrode chamber. A two-chamber SOFC that supplies an oxidant gas was used.

また、近年、燃料ガス及び酸化剤ガスを混合して供給することでセパレーターやガスシール材を必要とせず、ガス供給ラインの簡略化が出来、簡単なシステム構造になる単室型ＳＯＦＣが提案されている。この単室型ＳＯＦＣで採用される燃料電池としては、燃料極と空気極の二つの電極が、燃料ガスと酸化剤ガスとの混合ガスにさらされながらも、ガス選択性を持ち、それらの間に電圧が発生する特徴があり、電池構造としては、電解質の基板を用い、電解質の一方面に燃料極と空気極を向かい合うように配置した構造（例えば特許文献１参照）と電解質の基板の一方面に燃料極、他方面に空気極を配置した構造（例えば特許文献２参照）がある。   In recent years, a single-chamber SOFC has been proposed in which fuel gas and oxidant gas are mixed and supplied without the need for a separator or gas seal material, and the gas supply line can be simplified and the system structure can be simplified. ing. As a fuel cell employed in this single-chamber SOFC, two electrodes, a fuel electrode and an air electrode, are exposed to a mixed gas of a fuel gas and an oxidant gas, and have gas selectivity between them. In the battery structure, an electrolyte substrate is used, and a structure in which a fuel electrode and an air electrode are arranged to face each other on one side of the electrolyte (see, for example, Patent Document 1) and one of the electrolyte substrates. There is a structure in which a fuel electrode is disposed in the direction and an air electrode is disposed on the other surface (see, for example, Patent Document 2).

しかしながら、上記燃料電池では、従来、例えば、集電体としてメッシュ状の白金や導電性を有する板状の多孔質体（特許文献３）などを用い、そのような集電体を燃料極或いは空気極上に圧接させる等しているが、割れが発生したり、メッシュや板状の多孔質体と電極との接触抵抗が大きくなりやすく、接触抵抗値の増加等により、電圧が不安定になり、電池性能が低下することがある。
特許２８１０９７７号公報 特開２０００−２４３４１２号公報 特開２００２−５０３７０号公報 However, in the above fuel cell, conventionally, for example, mesh-like platinum or a plate-like porous body having electrical conductivity (Patent Document 3) is used as a current collector, and such a current collector is used as a fuel electrode or air. Although it is pressed to the extreme, etc., cracking occurs, the contact resistance between the mesh or plate-like porous body and the electrode tends to increase, the voltage becomes unstable due to the increase in the contact resistance value, etc. Battery performance may be reduced.
Japanese Patent No. 2810977 Japanese Unexamined Patent Publication No. 2000-243412 JP 2002-50370 A

本発明は、燃料極及び空気極と集電体との接触抵抗の増加等による抵抗値の増加を抑え、電池性能が損なわれることを防止可能な固体酸化物形燃料電池を提供することを課題とする。   It is an object of the present invention to provide a solid oxide fuel cell capable of suppressing an increase in resistance value due to an increase in contact resistance between a fuel electrode and an air electrode and a current collector, and preventing cell performance from being impaired. And

上記課題を解決するために、本発明に係る固体酸化物形燃料電池は、電解質を介して、一方面に燃料極、他方面に空気極を配置した構造を持つ電池構造を有し、燃料極上及び空気極上の少なくとも一方に、各々の燃料極及び空気極が露出する露出領域を残しつつ集電体を印刷形成したことを特徴とする。   In order to solve the above problems, a solid oxide fuel cell according to the present invention has a battery structure having a structure in which a fuel electrode is disposed on one surface and an air electrode on the other surface via an electrolyte, In addition, the current collector is printed and formed on at least one of the air electrode while leaving an exposed region where the fuel electrode and the air electrode are exposed.

前記集電体は、規則性を持つパターンで印刷形成されていることが好ましく、前記パターンは、円形若しくは多角形を一単位としてその複数個が規則的に離隔配置するか、又は、連続する格子状パターンとしても良い。   The current collector is preferably printed and formed with a regular pattern, and a plurality of the patterns are regularly spaced apart from each other in a circular or polygonal unit, or a continuous lattice. It is good also as a pattern.

また、前記露出領域上における任意の点と集電体との最短距離が１０ｍｍ以下となるように集電体を形成することが好ましい。   The current collector is preferably formed such that the shortest distance between an arbitrary point on the exposed region and the current collector is 10 mm or less.

更に、前記電解質を基板とし、前記燃料極及び空気極も印刷形成されていることが好ましい。   Furthermore, it is preferable that the electrolyte is a substrate and the fuel electrode and the air electrode are also printed.

また、前記燃料極を基板とし、該燃料極の一方面に前記電解質を印刷形成し、該電解質上に空気極を印刷形成しても良い。   Alternatively, the fuel electrode may be used as a substrate, the electrolyte may be printed on one surface of the fuel electrode, and the air electrode may be printed on the electrolyte.

本発明に係る固体酸化物形燃料電池によれば、電解質を介して燃料極及び空気極を配置し、燃料極上及び空気極上の少なくとも一方に、各々の燃料極及び空気極が露出する露出領域を残しつつ集電体を印刷形成し、焼結させることで、電極と集電体を一体化することが出来、また、露出領域を反応ガスが通り、所望の固体酸化物形燃料電池が得られることを見出した。   According to the solid oxide fuel cell of the present invention, the fuel electrode and the air electrode are disposed via the electrolyte, and at least one of the fuel electrode and the air electrode has an exposed region where each of the fuel electrode and the air electrode is exposed. The current collector can be formed by printing and sintering while leaving the electrode and the current collector integrated, and the reaction gas can pass through the exposed region to obtain a desired solid oxide fuel cell. I found out.

本発明に係る固体酸化物形燃料電池の好適な実施形態について、以下に図１〜６参照しつつ説明する。なお、全図を通し、同様の構成部分には同符号を付した。   A preferred embodiment of a solid oxide fuel cell according to the present invention will be described below with reference to FIGS. In addition, the same code | symbol was attached | subjected to the same component through the whole figure.

まず、本発明に係る固体酸化物形燃料電池の第１実施形態について、図１及び図２を参照しつつ説明する。図１は縦断面図、図２は平面図である。   First, a first embodiment of a solid oxide fuel cell according to the present invention will be described with reference to FIGS. 1 and 2. 1 is a longitudinal sectional view, and FIG. 2 is a plan view.

固体酸化物形燃料電池１は、固体電解質２を基板とし、固体電解質２介して燃料極３及び空気極４を配置し、燃料極３及び空気極４の上に、発電に必要な反応ガス（燃料ガス、酸化剤ガス、或いはそれらの混合ガス）が接触可能なように、燃料極３及び空気極４が露出する露出領域を残しつつ集電体５を印刷で形成し、焼結させることで、燃料極３及び空気極４と集電体５とを一体化させている。即ち、集電体５が形成されていない領域が、反応ガスが電極と直接接触する露出領域となる。   In the solid oxide fuel cell 1, a solid electrolyte 2 is used as a substrate, a fuel electrode 3 and an air electrode 4 are arranged via the solid electrolyte 2, and a reaction gas (for generating power) (on the fuel electrode 3 and the air electrode 4) By forming the current collector 5 by printing and sintering it, leaving an exposed region where the fuel electrode 3 and the air electrode 4 are exposed so that the fuel gas, the oxidant gas, or a mixed gas thereof can be contacted. The fuel electrode 3 and the air electrode 4 and the current collector 5 are integrated. That is, the region where the current collector 5 is not formed becomes an exposed region where the reactive gas directly contacts the electrode.

固体電解質２の材料としては、固体酸化物形燃料電池の電解質として公知のものを使用することができ、例えば、サマリウムやガドリニウム等をドープしたセリア系酸化物、ストロンチウムやマグネシウムをドープしたランタン・ガレード系酸化物、スカンジウムやイットリウムを含むジルコニア系酸化物などの酸素イオン伝導性セラミックス材料を用いることができる。固体電解質２を基板とする場合、一般的に乾式加圧成形が用いられるが、これに特定する必要は無く、押し出し成形、射出成形、鋳込み成形、キャスティング法（シート成形）を用いて作製することができる。   As the material of the solid electrolyte 2, those known as electrolytes for solid oxide fuel cells can be used. For example, ceria-based oxides doped with samarium or gadolinium, lanthanum galade doped with strontium or magnesium An oxygen ion conductive ceramic material such as a zirconia oxide or a zirconia oxide containing scandium or yttrium can be used. When the solid electrolyte 2 is used as a substrate, dry pressure molding is generally used, but it is not necessary to specify this. Extrusion molding, injection molding, casting molding, casting method (sheet molding) should be used. Can do.

燃料極３は、例えば、金属触媒と酸化物イオン導電体からなるセラミックス粉末材料との混合物を用いることができる。このとき用いられる金属触媒としては、ニッケル、鉄、コバルトや、貴金属（白金、ルテニウム、パラジウム等）等の還元性雰囲気中で安定で、水素酸化活性を有する材料を用いることができる。また、酸化物イオン導電体としては、蛍石型構造又はペロブスカイト型構造を有するものを好ましく用いることができる。蛍石型構造を有するものとしては、例えばサマリウムやガドリニウム等をドープしたセリア系酸化物、スカンジウムやイットリウムを含むジルコニア系酸化物などを挙げることができる。また、ペロブスカイト型構造を有するものとしてはストロンチウムやマグネシウムをドープしたランタン・ガレード系酸化物を挙げることができる。上記材料の中では、酸化物イオン導電体とニッケルとの混合物で、燃料極を形成することが好ましい。なお、酸化物イオン導電体からなるセラミックス材料とニッケルとの混合形態は、物理的な混合形態であってもよいし、ニッケルへの粉末修飾などの形態であってもよい。また、上述したセラミックス材料は、１種類を単独で、或いは２種類以上を混合して使用することができる。また、燃料極は、金属触媒を単体で用いて構成することもできる。   As the fuel electrode 3, for example, a mixture of a metal catalyst and a ceramic powder material made of an oxide ion conductor can be used. As the metal catalyst used at this time, a material that is stable in a reducing atmosphere, such as nickel, iron, cobalt, or a noble metal (platinum, ruthenium, palladium, etc.) and has hydrogen oxidation activity can be used. In addition, as the oxide ion conductor, one having a fluorite structure or a perovskite structure can be preferably used. Examples of those having a fluorite structure include ceria-based oxides doped with samarium, gadolinium, and the like, and zirconia-based oxides containing scandium and yttrium. In addition, examples of those having a perovskite structure include lanthanum galide oxides doped with strontium and magnesium. Among the above materials, it is preferable to form the fuel electrode with a mixture of an oxide ion conductor and nickel. The mixed form of the ceramic material made of the oxide ion conductor and nickel may be a physical mixed form or a form of powder modification to nickel. Moreover, the ceramic material mentioned above can be used individually by 1 type or in mixture of 2 or more types. The fuel electrode can also be configured using a metal catalyst alone.

空気極４を形成するセラミックス粉末材料としては、例えば、ペロブスカイト型構造等を有するＣｏ，Ｆｅ，Ｎｉ，Ｃｒ又はＭｎ等からなる金属酸化物を用いることができる。具体的には（Ｓｍ，Ｓｒ）ＣｏＯ３，（Ｌａ，Ｓｒ）ＭｎＯ３，（Ｌａ，Ｓｒ）ＣｏＯ３，（Ｌａ，Ｓｒ）（Ｆｅ，Ｃｏ）Ｏ３，（Ｌａ，Ｓｒ）（Ｆｅ，Ｃｏ，Ｎｉ）Ｏ３などの酸化物が挙げられ、好ましくは、（Ｌａ，Ｓｒ）ＭｎＯ３である。上述したセラミックス材料は、１種を単独で、或いは２種以上を混合して使用することができる。 As the ceramic powder material forming the air electrode 4, for example, a metal oxide made of Co, Fe, Ni, Cr, Mn or the like having a perovskite structure or the like can be used. Specifically, (Sm, Sr) CoO 3 , (La, Sr) MnO 3 , (La, Sr) CoO 3 , (La, Sr) (Fe, Co) O 3 , (La, Sr) (Fe, Co , Ni) O 3 and the like, and (La, Sr) MnO 3 is preferable. The ceramic material mentioned above can be used individually by 1 type or in mixture of 2 or more types.

また、集電体５は、Ｐｔ，Ａｕ，Ｐｄ，Ａｇ，Ｎｉ，Ｃｕ，ＳＵＳ等の導電性金属、或いは金属系材料，又はＬａ（Ｃｒ，Ｍｇ）Ｏ３，（Ｌａ，Ｃａ）ＣｒＯ３，（Ｌａ，Ｓｒ）ＣｒＯ３などのランタン・クロマイト系等の導電性セラミックス材料によって形成することができ、これらのうちの１種を単独で使用してもよいし、２種以上を混合して使用してもよい。 The current collector 5 is made of a conductive metal such as Pt, Au, Pd, Ag, Ni, Cu, SUS, or a metal-based material, or La (Cr, Mg) O 3 , (La, Ca) CrO 3 , (La, Sr) CrO 3 and other lanthanum chromite-based conductive ceramic materials can be used. One of these may be used alone, or two or more may be used in combination. May be.

固体電解質２、燃料極３、空気極４及び集電体５の原材料となるセラミック粉末の平均粒径は、好ましくは１０ｎｍ〜１００μｍであり、さらに好ましくは５０ｎｍ〜５０μｍであり、特に好ましくは１００ｎｍ〜１０μｍである。なお、平均粒径は、例えば、ＪＩＳＺ８９０１にしたがって計測することができる。   The average particle size of the ceramic powder as a raw material for the solid electrolyte 2, the fuel electrode 3, the air electrode 4 and the current collector 5 is preferably 10 nm to 100 μm, more preferably 50 nm to 50 μm, and particularly preferably 100 nm to 10 μm. In addition, an average particle diameter can be measured according to JISZ8901, for example.

燃料極、空気極を印刷形成する際に、先ず、燃料極及び空気極のペーストを作製する。上述した材料を主成分として、さらにバインダー樹脂、有機溶媒などが適量加えられることにより形成される。より詳細には、上記主成分とバインダー樹脂との混合において、上記主成分が５０〜９５重量％となるように、バインダー樹脂等を加えることが好ましい。また、電解質も印刷形成する際に、上記燃料極及び空気極と同様に、上述した材料を主成分として、バインダー樹脂、有機溶媒などが適量加えられることにより形成されるが、上記主成分とバインダーとの混合において、上記主成分の割合が８０重量％以上となるように混合されることが好ましい。   When printing the fuel electrode and the air electrode, first, a paste of the fuel electrode and the air electrode is prepared. It is formed by adding an appropriate amount of a binder resin, an organic solvent, etc. with the above-described material as a main component. More specifically, it is preferable to add a binder resin or the like so that the main component is 50 to 95% by weight in the mixing of the main component and the binder resin. In addition, when the electrolyte is also formed by printing, as in the case of the fuel electrode and the air electrode, it is formed by adding an appropriate amount of a binder resin, an organic solvent, etc. with the above-mentioned material as the main component. Is preferably mixed so that the ratio of the main component is 80% by weight or more.

また、集電体用ペーストも上述したように、バインダー樹脂、有機溶媒などが適量加えられることにより形成される。   Further, as described above, the current collector paste is also formed by adding an appropriate amount of a binder resin, an organic solvent, or the like.

前記バインダーは、有機樹脂と溶媒とを含む。バインダーに含まれる有機樹脂は焼成過程にて低温で燃焼／分解／気化することが必要であり、アクリル系樹脂、スチレン系樹脂、エチルセルロース誘導体、或いはスチレンアクリル共重合体等の熱可塑性樹脂を、単独または混合して使用することができる。   The binder includes an organic resin and a solvent. The organic resin contained in the binder needs to be combusted / decomposed / vaporized at a low temperature during the baking process, and a thermoplastic resin such as an acrylic resin, a styrene resin, an ethyl cellulose derivative, or a styrene acrylic copolymer is used alone. Or it can be mixed and used.

また、前記有機溶媒としては、ケトン類、エステル類、エーテル類、アミド類等を、単独又は混合して使用することができ、具体的には、イソプロパノール、ノルマルプロパノール、ジアセトンアルコール、グリコール・ジアセテート、メチルセルソルブ、カルビトール、シクロヘキサン、テルピネオールなどが使用できる。また、溶媒としては、グリセリン、ジブチルフタレート、ジオクチルフタレートなどの化合物を使用できる。   In addition, as the organic solvent, ketones, esters, ethers, amides and the like can be used alone or in combination, and specifically, isopropanol, normal propanol, diacetone alcohol, glycol diester. Acetate, methyl cellosolve, carbitol, cyclohexane, terpineol and the like can be used. As the solvent, compounds such as glycerin, dibutyl phthalate and dioctyl phthalate can be used.

電解質、燃料極、空気極及び集電体の形成方法として印刷法を用い、例えばスクリーン印刷法やナイフコ−ト法、ドクターブレード法、スプレーコート等の印刷方法を用いることができる。   A printing method is used as a method for forming the electrolyte, fuel electrode, air electrode, and current collector. For example, a printing method such as a screen printing method, a knife coating method, a doctor blade method, or a spray coating method can be used.

集電体５は、規則性を持つパターンで印刷形成することができる。このパターンは、図２に示されているように、個々の集電体要素を形成したマトリックス状としたものが好ましく、またそのパターンを構成する一単位は、如何なる形態でも良いが、例えば四角形等の多角形、円形などを単独あるいは組み合わせても良い。この場合、個々の集電体５から電流を取り出すようにしても良いし、図３に示すように、各々の集電体を導電接続し、１箇所から電流を取り出し可能とすることもできる。また、図４に示すような連続する格子状パターンとしても良い。   The current collector 5 can be printed and formed with a regular pattern. As shown in FIG. 2, this pattern is preferably in the form of a matrix in which individual current collector elements are formed, and one unit constituting the pattern may take any form. These polygons and circles may be used alone or in combination. In this case, currents may be taken out from the individual current collectors 5, or as shown in FIG. 3, the current collectors can be conductively connected so that the current can be taken out from one place. Moreover, it is good also as a continuous grid | lattice pattern as shown in FIG.

電極３、４中の抵抗による電子伝導ロスを極力防ぐため、電極３，４上の反応ガスに直接晒される露出領域（即ち、集電体５が形成されていない領域）上における任意の点と集電体とを結ぶ最短距離が、１０ｍｍ以下であることが好ましい。   In order to prevent electron conduction loss due to resistance in the electrodes 3 and 4 as much as possible, any point on an exposed region (that is, a region where the current collector 5 is not formed) directly exposed to the reaction gas on the electrodes 3 and 4; The shortest distance connecting the current collector is preferably 10 mm or less.

電解質２の厚みを例えば２００〜１０００μｍ程度、燃料極３及び空気極４の印刷厚みを例えば１０〜５０μｍ程度とすることができる。電解質２の一方面に、上記の燃料極ペーストを所定厚みに印刷し、５０〜１５０℃で５〜６０分間乾燥した後、１０００〜１５００℃で１〜４８時間焼結させる。次に、電解質２を反転して他方面を上方に向けた後、空気極ペーストを所定厚みとなるように印刷し、５０〜１５０℃で５〜６０分間乾燥した後、９００〜１４００℃で１〜４８時間焼結する。焼結させた燃料極３及び空気極４に集電体ペーストを所定厚みとなるように印刷し、５０〜１５０℃で５〜６０分間乾燥した後、８００〜１５００℃で１〜４８時間焼結させる。こうして電解質を支持基板とした固体酸化物形燃料電池を製造することができる。   The thickness of the electrolyte 2 can be about 200 to 1000 μm, for example, and the printing thickness of the fuel electrode 3 and the air electrode 4 can be about 10 to 50 μm, for example. The fuel electrode paste is printed on one surface of the electrolyte 2 to a predetermined thickness, dried at 50 to 150 ° C. for 5 to 60 minutes, and then sintered at 1000 to 1500 ° C. for 1 to 48 hours. Next, the electrolyte 2 is reversed and the other surface is directed upward, and then the air electrode paste is printed to a predetermined thickness, dried at 50 to 150 ° C. for 5 to 60 minutes, and then 1 to 900 to 1400 ° C. Sinter for ~ 48 hours. The current collector paste is printed on the sintered fuel electrode 3 and air electrode 4 so as to have a predetermined thickness, dried at 50 to 150 ° C. for 5 to 60 minutes, and then sintered at 800 to 1500 ° C. for 1 to 48 hours. Let Thus, a solid oxide fuel cell using the electrolyte as a supporting substrate can be manufactured.

また、支持基板として、図５に示すように、燃料極３を基板とし、この燃料極３の基板の一方面に集電体５を印刷形成し、他方面に電解質２及び空気極４を印刷により積層させて形成することもできる。このように燃料極３を基板化する方法は、上記した固体電解質を基板とする場合と同様であり、乾式加圧成形のほか、押し出し成形、射出成形、鋳込み成形、キャスティング法（シート成形）を用いて作製することができる。なお、この場合も、図６に示すように集電体５を四角形のパターンで印刷形成し、或いは、図７に示すように、集電体５を格子状パターンで印刷形成することもできる。   Further, as shown in FIG. 5, the fuel electrode 3 is used as a substrate as a support substrate, the current collector 5 is printed on one surface of the substrate of the fuel electrode 3, and the electrolyte 2 and the air electrode 4 are printed on the other surface. It can also be formed by laminating. Thus, the method of forming the fuel electrode 3 as a substrate is the same as that in the case where the solid electrolyte is used as a substrate. Extrusion molding, injection molding, casting molding, casting method (sheet molding) is used in addition to dry pressure molding. Can be used. In this case as well, the current collector 5 can be printed and formed in a square pattern as shown in FIG. 6, or the current collector 5 can be printed and formed in a grid pattern as shown in FIG.

この場合、燃料極３の厚みを例えば２００〜１０００μｍ程度、電解質２及び空気極４の印刷厚みを例えば１０〜５０μｍ程度とすることができる。この場合、基板となる燃料極３の一方面に、電解質ペーストを所定厚みとなるように印刷し、５０〜１５０℃で５〜６０分間乾燥した後、１０００〜１５００℃で１〜４８時間焼結する。次に、焼結させた電解質２上に、空気極ペーストを所定厚みとなるように印刷し、５０〜１５０℃で５〜６０分間乾燥し、７００〜１４００℃で１〜４８時間焼結させる。次に、上記集電体ペ−ストを燃料極３及び空気極４上に印刷し、５０〜１５０℃で５〜６０分間乾燥した後、８００〜１５００℃で１〜４８時間焼結させる。こうして燃料極３を支持基板とした固体酸化物形燃料電池を得ることができる。
以上の説明から明らかなように、本発明に係る固体酸化物形燃料電池によれば、集電体と電極との接触抵抗の増加等により電池性能が低下する虞れのない固体酸化物形燃料電池を提供することが可能となり、移動体、据置き用途への搭載が期待できる。
なお、上記実施形態は、燃料極と空気極の両極に集電体を印刷形成したものを示したが、それに限られることはなく、例えば、燃料極側にニッケルフェルトを用いる等とする構成とすることもできる。 In this case, the thickness of the fuel electrode 3 can be about 200 to 1000 μm, for example, and the printing thickness of the electrolyte 2 and the air electrode 4 can be about 10 to 50 μm, for example. In this case, the electrolyte paste is printed on one surface of the fuel electrode 3 serving as a substrate to have a predetermined thickness, dried at 50 to 150 ° C. for 5 to 60 minutes, and then sintered at 1000 to 1500 ° C. for 1 to 48 hours. To do. Next, the air electrode paste is printed on the sintered electrolyte 2 so as to have a predetermined thickness, dried at 50 to 150 ° C. for 5 to 60 minutes, and sintered at 700 to 1400 ° C. for 1 to 48 hours. Next, the current collector paste is printed on the fuel electrode 3 and the air electrode 4, dried at 50 to 150 ° C. for 5 to 60 minutes, and then sintered at 800 to 1500 ° C. for 1 to 48 hours. Thus, a solid oxide fuel cell using the fuel electrode 3 as a support substrate can be obtained.
As is apparent from the above description, according to the solid oxide fuel cell according to the present invention, the solid oxide fuel that does not have a risk of deterioration in battery performance due to an increase in contact resistance between the current collector and the electrode, etc. Batteries can be provided and can be expected to be mounted on mobile objects and stationary applications.
In the above embodiment, the current collector is printed on both the fuel electrode and the air electrode. However, the present invention is not limited to this. For example, nickel felt is used on the fuel electrode side. You can also

実施例１、２
以下に実施例を挙げて、本発明をさらに詳細に説明する。なお、本発明は以下の実施例に限定されるものではない。 Examples 1 and 2
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to a following example.

ここでは、実施例１として図１、２に示した構造を有する固体酸化物形燃料電池を作成し、実施例２として図１，３に示すような構造を有する固体酸化物形燃料電池を作成した。固体電解質材料としてはＧＤＣ（Ｃｅ0.9Ｇｄ0.1Ｏ1.9）からなる厚さ０．８ｍｍのプレス成形基板９ｍｍ□を使用した。また、燃料極材料としてＮｉＯ粉末（粒径０．０１〜１０μｍ、平均粒径１μｍ)、ＳＤＣ（Ｃｅ0.8Ｓｍ0.2Ｏ1.9）粉末（粒径１〜１０μｍ、平均粒径０．１μｍ）を重量比で７：３となるように混合して混合物を作成した後、セルロース系バインダー樹脂を添加して、上記混合物の割合が８０重量％となるように燃料極ペーストを作製した。つまり、上記混合物と、バインダー樹脂との重量比が８０：２０となるようにした。燃料極ペーストの粘度はスクリーン印刷に適した５×１０5ｍＰａ・ｓとした。続いて、空気極材料としてＳＳＣ（Ｓｍ0.5Ｓｒ0.5ＣｏＯ3）粉末（粒径０．１〜１０μｍ、平均粒径３μｍ)を使用し、セルロース系バインダー樹脂を添加して、上記粉末の割合が８０重量％となるように空気極ペーストを作製した。つまり、ＳＳＣ粉末と、バインダー樹脂との重量比が８０：２０となるようにした。空気極ペーストの粘度は、燃料極と同様にスクリーン印刷に適した５×１０5ｍＰａ・ｓとした。また、集電体の材料として、Ｐｔ及びＡｕ粉末（粒径０．１〜５μｍ、平均粒径２．５μｍ）を使用し、上述のように、セルロース系バインダーを混合し、その粘度をスクリーン印刷に適した５×１０5ｍＰａ・ｓとした。 Here, a solid oxide fuel cell having the structure shown in FIGS. 1 and 2 is prepared as Example 1, and a solid oxide fuel cell having the structure shown in FIGS. did. As the solid electrolyte material, a press molded substrate 9 mm □ made of GDC (Ce 0.9 Gd 0.1 O 1.9 ) and having a thickness of 0.8 mm was used. Further, NiO powder (particle size 0.01 to 10 μm, average particle size 1 μm) and SDC (Ce 0.8 Sm 0.2 O 1.9 ) powder (particle size 1 to 10 μm, average particle size 0.1 μm) as a fuel electrode material are in a weight ratio. The mixture was prepared so as to be 7: 3, and then a cellulosic binder resin was added to prepare a fuel electrode paste so that the ratio of the mixture was 80% by weight. That is, the weight ratio of the mixture to the binder resin was set to 80:20. The viscosity of the fuel electrode paste was 5 × 10 5 mPa · s suitable for screen printing. Subsequently, SSC (Sm 0.5 Sr 0.5 CoO 3 ) powder (particle size 0.1 to 10 μm, average particle size 3 μm) is used as an air electrode material, and a cellulose-based binder resin is added. An air electrode paste was prepared so as to have a weight%. That is, the weight ratio of the SSC powder to the binder resin was set to 80:20. The viscosity of the air electrode paste was 5 × 10 5 mPa · s suitable for screen printing as in the fuel electrode. In addition, Pt and Au powder (particle size 0.1 to 5 μm, average particle size 2.5 μm) is used as a current collector material, and as described above, a cellulose binder is mixed and the viscosity is screen printed. 5 × 10 5 mPa · s suitable for the above.

続いて、電解質の一方面に、燃料極ペーストをスクリーン印刷法により塗布厚み５０μｍとなるように印刷し、１３０℃で１５分間乾燥し、１４５０℃で１時間焼結した。次に、電解質を反転して他方面を上方に向けた後、空気極ペーストをスクリーン印刷法により塗布厚み５０μｍとなるように印刷し、１３０℃で１５分間乾燥し、１２００℃で１時間焼結した。
次に、上記集電体ペーストとして、燃料極にはＰｔペースト、空気極上にはＡｕペ−ストをスクリーン印刷法により塗布厚み１０μｍとなるようにパターン印刷する。その際のパタ−ン形状は、集電体を四角状（図２）と格子状パターン（図４）とし配置する。その後、１３０℃で１５分間乾燥し、１０００℃で１時間焼結し、電解質を支持基板とした単室型固体酸化物形燃料電池を作製した。集電体は２．０ｍｍ□とし、隣り合う集電体の間隔は２．５ｍｍとした。 Subsequently, the fuel electrode paste was printed on one surface of the electrolyte by screen printing so as to have a coating thickness of 50 μm, dried at 130 ° C. for 15 minutes, and sintered at 1450 ° C. for 1 hour. Next, the electrolyte is reversed and the other surface is directed upward, and then the air electrode paste is printed by screen printing to a coating thickness of 50 μm, dried at 130 ° C. for 15 minutes, and sintered at 1200 ° C. for 1 hour. did.
Next, as the current collector paste, Pt paste is applied to the fuel electrode and Au paste is applied to the air electrode by pattern printing so as to have a coating thickness of 10 μm by screen printing. The pattern shape at that time is arranged such that the current collector is a square shape (FIG. 2) and a lattice pattern (FIG. 4). Then, it dried for 15 minutes at 130 degreeC, and sintered for 1 hour at 1000 degreeC, and produced the single chamber type solid oxide fuel cell which used the electrolyte as the support substrate. The current collector was 2.0 mm □, and the distance between adjacent current collectors was 2.5 mm.

実施例１、２では、図８に示すように、燃料極側の集電体上にＰｔメッシュＭ１を圧接させ、空気極側の集電体上にＡｕメッシュＭ２を圧接させた。Ｐｔメッシュ及びＡｕメッシュは、線幅100μm×開口200μm□のものを使用した。   In Examples 1 and 2, as shown in FIG. 8, the Pt mesh M1 was pressure-contacted on the fuel electrode-side current collector, and the Au mesh M2 was pressure-contacted on the air electrode-side current collector. As the Pt mesh and Au mesh, those having a line width of 100 μm and an opening of 200 μm □ were used.

比較例
比較例１として、実施例１で示した集電体の印刷していない単セルを準備し、図９、１０に示すように、各電極上にＰｔ及びＡｕのメッシュＭ（線幅100um×開口200um□）を圧接させて集電を行った。 Comparative Example As Comparative Example 1, a single cell of the current collector shown in Example 1 which was not printed was prepared. As shown in FIGS. 9 and 10, a mesh M of Pt and Au (line width of 100 μm) was formed on each electrode. × Opening 200um □) was pressed to collect current.

こうして製造された実施例および比較例に対して、次のような評価実験を行った。すなわち、メタンと酸素との混合ガス（ＣＨ４：Ｏ２＝２：１）を８００℃で流速３００ｍｌ／ｍｉｎで導入し、ＣＨ４＋（１／２）Ｏ２→２Ｈ２＋ＣＯの反応を起こさせることで、燃料極である酸化ニッケルを還元処理し、電流−電圧特性の評価を行った。 The following evaluation experiments were performed on the examples and comparative examples thus manufactured. That is, a mixed gas of methane and oxygen (CH 4 : O 2 = 2: 1) was introduced at a flow rate of 300 ml / min at 800 ° C. to cause a reaction of CH 4 + (1/2) O 2 → 2H 2 + CO. As a result, nickel oxide as a fuel electrode was subjected to reduction treatment, and current-voltage characteristics were evaluated.

その結果、図１１のように、最大出力密度については、比較例が28ｍW/ｃｍ2であるのに対して、同じセル構造である実施例１では116ｍW/ｃｍ2、実施例２では130ｍW/ｃｍ2、セル抵抗については、比較例では4.1Ωであるのに対して、実施例１では0.9Ω、実施例２では0.8Ωとなり、電池性能の向上が確認された。 As a result, as shown in FIG. 11, for the maximum power density, Comparative examples 28 mW / cm, whereas the a 2, 116 mW / cm 2 in the first embodiment have the same cell structure, in Example 2 130 mW / cm 2 , cell resistance was 4.1Ω in the comparative example, 0.9Ω in Example 1 and 0.8Ω in Example 2, confirming the improvement in battery performance.

本発明に係る固体酸化物形燃料電池の一実施形態を示す縦断面図である。1 is a longitudinal sectional view showing an embodiment of a solid oxide fuel cell according to the present invention. 図１に示す固体酸化物形燃料電池の平面図である。FIG. 2 is a plan view of the solid oxide fuel cell shown in FIG. 1. 図１に示す固体酸化物形燃料電池の変更態様を示す平面図である。It is a top view which shows the change aspect of the solid oxide fuel cell shown in FIG. 図１に示す固体酸化物形燃料電池の集電体のパターンを変更した例を示す平面図である。It is a top view which shows the example which changed the pattern of the electrical power collector of the solid oxide fuel cell shown in FIG. 本発明に係る固体酸化物形燃料電池の他の実施形態を示す縦断面図である。It is a longitudinal cross-sectional view which shows other embodiment of the solid oxide fuel cell which concerns on this invention. 図５に示す固体酸化物形燃料電池の平面図である。FIG. 6 is a plan view of the solid oxide fuel cell shown in FIG. 5. 図５に示す固体酸化物形燃料電池の集電体のパターンを変更した例を示す平面図である。It is a top view which shows the example which changed the pattern of the electrical power collector of the solid oxide fuel cell shown in FIG. 実施例の固体酸化物形燃料電池を示す縦断面図である。It is a longitudinal cross-sectional view which shows the solid oxide fuel cell of an Example. 比較例の固体酸化物形燃料電池を示す縦断面図である。It is a longitudinal cross-sectional view which shows the solid oxide fuel cell of a comparative example. 図９に示す固体酸化物形燃料電池の平面図である。FIG. 10 is a plan view of the solid oxide fuel cell shown in FIG. 9. 実施例と比較例の電流−電圧特性を示すグラフである。It is a graph which shows the current-voltage characteristic of an Example and a comparative example.

符号の説明Explanation of symbols

１ 固体酸化物形燃料電池
２ 電解質
３ 燃料極
４ 空気極
５ 集電体 1 Solid Oxide Fuel Cell 2 Electrolyte 3 Fuel Electrode 4 Air Electrode 5 Current Collector

Claims (6)

電解質を介して、一方面に燃料極、他方面に空気極を配置した構造を持つ電池構造を有し、燃料極上及び空気極上の少なくとも一方に、各々の燃料極及び空気極が露出する露出領域を残しつつ集電体を印刷形成したことを特徴とする固体酸化物形燃料電池。   An exposed region in which each of the fuel electrode and the air electrode is exposed to at least one of the fuel electrode and the air electrode, with a battery structure having a fuel electrode on one surface and an air electrode on the other surface via an electrolyte. A solid oxide fuel cell, wherein the current collector is printed and formed while leaving 前記集電体が、規則性を持つパターンで印刷形成されていることを特徴とする請求項１に記載の固体酸化物形燃料電池。   2. The solid oxide fuel cell according to claim 1, wherein the current collector is printed and formed with a regular pattern. 前記パターンは、円形若しくは多角形を一単位としてその複数個が規則的に離隔配置されているか、又は、連続する格子状パターンであることを特徴とする請求項２に記載の固体酸化物形燃料電池。   3. The solid oxide fuel according to claim 2, wherein the pattern has a circular or polygonal unit and a plurality of the patterns are regularly spaced apart or a continuous lattice pattern. 4. battery. 前記露出領域上における任意の点と集電体との最短距離が、１０ｍｍ以下となるように集電体を配置したことを特徴とする請求項１に記載の固体酸化物形燃料電池。   2. The solid oxide fuel cell according to claim 1, wherein the current collector is arranged so that a shortest distance between an arbitrary point on the exposed region and the current collector is 10 mm or less. 前記電解質を基板とし、前記燃料極及び空気極が印刷形成されていることを特徴とする請求項１に記載の固体酸化物形燃料電池。   2. The solid oxide fuel cell according to claim 1, wherein the electrolyte is used as a substrate, and the fuel electrode and the air electrode are printed. 前記燃料極を基板とし、該燃料極の一方面に前記電解質が印刷形成され、該電解質上に空気極が印刷形成されていることを特徴とする請求項１に記載の固体酸化物形燃料電池。   2. The solid oxide fuel cell according to claim 1, wherein the fuel electrode is used as a substrate, the electrolyte is printed on one surface of the fuel electrode, and the air electrode is printed on the electrolyte. .
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JP2009099308A (en) * 2007-10-15 2009-05-07 Ngk Spark Plug Co Ltd Solid oxide fuel cell
JP2012146459A (en) * 2011-01-11 2012-08-02 Toshiba Corp Solid oxide electrochemical cell and method of manufacturing the same
JP2015028887A (en) * 2013-07-30 2015-02-12 日本特殊陶業株式会社 Fuel battery cell and fuel battery cell stack
JP2015028890A (en) * 2013-07-30 2015-02-12 日本特殊陶業株式会社 Fuel battery cell and fuel battery cell stack
JP2015028889A (en) * 2013-07-30 2015-02-12 日本特殊陶業株式会社 Fuel battery cell and fuel battery cell stack
JP2015028888A (en) * 2013-07-30 2015-02-12 日本特殊陶業株式会社 Fuel battery cell and fuel battery cell stack
KR102585572B1 (en) * 2022-11-04 2023-10-06 한국세라믹기술원 Membrane electrode assembly having metal ball grid array type current collecting and pressurized structure and frel cell stack including the same

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JP2015028887A (en) * 2013-07-30 2015-02-12 日本特殊陶業株式会社 Fuel battery cell and fuel battery cell stack
JP2015028890A (en) * 2013-07-30 2015-02-12 日本特殊陶業株式会社 Fuel battery cell and fuel battery cell stack
JP2015028889A (en) * 2013-07-30 2015-02-12 日本特殊陶業株式会社 Fuel battery cell and fuel battery cell stack
JP2015028888A (en) * 2013-07-30 2015-02-12 日本特殊陶業株式会社 Fuel battery cell and fuel battery cell stack
KR102585572B1 (en) * 2022-11-04 2023-10-06 한국세라믹기술원 Membrane electrode assembly having metal ball grid array type current collecting and pressurized structure and frel cell stack including the same

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