JP5184450B2 - Manufacturing method of membrane electrode assembly for fuel cell - Google Patents
Manufacturing method of membrane electrode assembly for fuel cell Download PDFInfo
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- JP5184450B2 JP5184450B2 JP2009152021A JP2009152021A JP5184450B2 JP 5184450 B2 JP5184450 B2 JP 5184450B2 JP 2009152021 A JP2009152021 A JP 2009152021A JP 2009152021 A JP2009152021 A JP 2009152021A JP 5184450 B2 JP5184450 B2 JP 5184450B2
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- 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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
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- 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
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
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- 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
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Description
本発明は、燃料電池用膜電極接合体の製造方法に関する。 The present invention relates to a method for producing a membrane electrode assembly for a fuel cell.
固体酸化物燃料電池の膜電極接合体は、化学エネルギーを電気エネルギーに変換する役割を担う、燃料電池の核心である。図１は燃料電池用膜電極接合体（Ｍｅｍｂｒａｎｅ Ｅｌｅｃｔｒｏｄｅ ａｓｓｅｍｂｌｙ、ＭＥＡ）の断面図であって、電解質層２、燃料極３、及び空気極４が示されている。 The membrane electrode assembly of a solid oxide fuel cell is the core of the fuel cell that plays a role in converting chemical energy into electrical energy. FIG. 1 is a sectional view of a membrane electrode assembly (MEA) for a fuel cell, in which an electrolyte layer 2, a fuel electrode 3, and an air electrode 4 are shown.
水素を燃料として用いる燃料電池を例に挙げて、各電極での化学反応を説明すると、次の通りである。
［反応式１］
燃料極３：Ｈ２→２Ｈ＋＋２ｅ−
空気極４：（１／２）Ｏ２＋２Ｈ＋＋２ｅ−→Ｈ２Ｏ
全反応：Ｈ２＋（１／２）Ｏ２→Ｈ２Ｏ
電解質層２の主な機能は、空気極４と燃料極３との間のイオンを伝達することである。電解質層２は燃料極にて生成されたイオンを空気極に移動させることにより、燃料電池の電荷バランスを維持し、電流の流れを発生させる。
Taking a fuel cell using hydrogen as a fuel as an example, the chemical reaction at each electrode will be described as follows.
[Reaction Formula 1]
Fuel electrode 3: H 2 → 2H + + 2e −
Air electrode 4: (1/2) O 2 + 2H + + 2e − → H 2 O
Total reaction: H 2 + (1/2) O 2 → H 2 O
The main function of the electrolyte layer 2 is to transmit ions between the air electrode 4 and the fuel electrode 3. The electrolyte layer 2 moves the ions generated at the fuel electrode to the air electrode, thereby maintaining the charge balance of the fuel cell and generating a current flow.
電解質層２は、還元、酸化雰囲気に安定し、反応ガスが透過されることなく、作動条件で充分なイオン伝導度を有しなければならない。固体酸化物燃料電池は高温（６００〜１０００℃）で作動するため、電解質層２は室温から作動温度、及び燃料電池が製造されるさらに高い温度でも、他の電極材料との間で化学的・熱的に安定性が要求される。 The electrolyte layer 2 must be stable in a reducing and oxidizing atmosphere, and must have sufficient ionic conductivity under operating conditions without allowing reaction gas to permeate. Since the solid oxide fuel cell operates at a high temperature (600 to 1000 ° C.), the electrolyte layer 2 can be chemically treated with other electrode materials even from the room temperature to the operating temperature and even higher temperature at which the fuel cell is manufactured. Thermal stability is required.
したがって、固体酸化物燃料電池の電解質層２は電子伝導性はなく、酸素イオンだけを伝導する酸素イオン伝導体である必要があり、電解質層の空気極側は酸化雰囲気に露出され、電解質層の燃料極側は還元雰囲気に露出されるため、１０〜１８気圧の極めて広い酸素分圧範囲での化学的安定性を有し、ガスが透過されないように緻密な構造であることが求められる。 Therefore, the electrolyte layer 2 of the solid oxide fuel cell is not electronically conductive and needs to be an oxygen ion conductor that conducts only oxygen ions. The air electrode side of the electrolyte layer is exposed to an oxidizing atmosphere, and the electrolyte layer Since the fuel electrode side is exposed to a reducing atmosphere, the fuel electrode side is required to have a chemical structure in an extremely wide oxygen partial pressure range of 10 to 18 atm, and to have a dense structure so that gas is not permeated.
こうした従来技術の問題点に鑑み、本発明は、燃料電池用膜電極接合体の製造方法を提供することを目的とする。 In view of the problems of the prior art, an object of the present invention is to provide a method for producing a membrane electrode assembly for a fuel cell.
本発明の一実施形態によれば、固体酸化物燃料電池用膜電極接合体を製造する方法であって、炉（ｆｕｒｎａｃｅ）にランタンガレート系の複合酸化物層を投入する工程と、炉に酸素または窒素を含む雰囲気ガスを供給する工程と、複合酸化物層を熱処理して電解質層を形成する工程と、電解質層の一面に燃料極を形成する工程と、電解質層の他面に空気極を形成する工程と、を含む燃料電池用膜電極接合体の製造方法が提供される。 According to one embodiment of the present invention, there is provided a method for manufacturing a membrane electrode assembly for a solid oxide fuel cell, the step of introducing a lanthanum gallate-based composite oxide layer into a furnace, and the step of introducing oxygen into the furnace. Alternatively, a step of supplying an atmospheric gas containing nitrogen, a step of heat-treating the composite oxide layer to form an electrolyte layer, a step of forming a fuel electrode on one surface of the electrolyte layer, and an air electrode on the other surface of the electrolyte layer And a process for forming the membrane electrode assembly for a fuel cell.
ここで、複合酸化物層の組成は、下記一般式（１）を満たすことを特徴とし、式中、ｘ及びｙは０以上１以下の値を有する。 Here, the composition of the composite oxide layer is characterized by satisfying the following general formula (1), wherein x and y have a value of 0 or more and 1 or less.
［化１］
（ＬａｘＳｒ１−ｘ）（ＧａｙＭｇ１−ｙ）Ｏ３ （１）
一方、熱処理工程は、１０００℃以上１３５０℃以下で行われることができ、複合酸化物層を炉に投入する前に、複合酸化物層の一面に金属層を形成する工程をさらに含むことができ、電解質層の一面に燃料極を形成する工程は、電解質層を形成する工程と同時に金属層を熱処理することにより行われることができる。
ここで、金属層は遷移金属を含む材質からなることができる。
[Chemical 1]
(La x Sr 1-x) (Ga y Mg 1-y) O 3 (1)
Meanwhile, the heat treatment process may be performed at 1000 ° C. or more and 1350 ° C. or less, and may further include a step of forming a metal layer on one surface of the composite oxide layer before putting the composite oxide layer into the furnace. The step of forming the fuel electrode on one surface of the electrolyte layer can be performed by heat-treating the metal layer simultaneously with the step of forming the electrolyte layer.
Here, the metal layer may be made of a material including a transition metal.
本発明の好ましい実施例によれば、中低温の固体酸化物燃料電池の電解質材料である、ドーピングされたランタンガレートの焼結温度を低め、加熱時間を短くすることにより、生産性を向上させ、特に、燃料極と電解質を同時に焼結する場合に発生し得る燃料極内の遷移金属の焼結加速化及び粗大化を防止して、電池の反応が活発に起こる三相界面の面積の減少を防止することができる。
なお、上記の発明の概要は、本発明の必要な特徴の全てを列挙したものではない。また、これらの特徴群のサブコンビネーションもまた、発明となりうる。
According to a preferred embodiment of the present invention, the sintering temperature of the doped lanthanum gallate, which is an electrolyte material of a low-temperature solid oxide fuel cell, is lowered, and the heating time is shortened, thereby improving productivity, In particular, it prevents the acceleration and coarsening of the transition metal in the fuel electrode, which can occur when the fuel electrode and the electrolyte are sintered at the same time, and reduces the area of the three-phase interface where the cell reaction occurs actively. Can be prevented.
It should be noted that the above summary of the invention does not enumerate all the necessary features of the present invention. In addition, a sub-combination of these feature groups can also be an invention.
以下、発明の実施の形態を通じて本発明を説明するが、以下の実施形態は特許請求の範囲にかかる発明を限定するものではない。また、実施形態の中で説明されている特徴の組み合わせの全てが発明の解決手段に必須であるとは限らない。 Hereinafter, the present invention will be described through embodiments of the invention, but the following embodiments do not limit the invention according to the claims. In addition, not all the combinations of features described in the embodiments are essential for the solving means of the invention.
本発明は多様な変換を加えることができ、様々な実施例を有することができるため、本願では特定実施例を図面に例示し、詳細に説明する。しかし、これは本発明を特定の実施形態に限定するものではなく、本発明の思想及び技術範囲に含まれるあらゆる変換、均等物及び代替物を含むものとして理解されるべきである。本発明を説明するに当たって、係る公知技術に対する具体的な説明が本発明の要旨をかえって不明にすると判断される場合、その詳細な説明を省略する。 Since the present invention can be modified in various ways and can have various embodiments, specific embodiments are illustrated in the drawings and described in detail herein. However, this is not to be construed as limiting the invention to the specific embodiments, but is to be understood as including all transformations, equivalents, and alternatives falling within the spirit and scope of the invention. In describing the present invention, when it is determined that the specific description of the known technology is not clear, the detailed description thereof will be omitted.
本願で用いた用語は、ただ特定の実施例を説明するために用いたものであって、本発明を限定するものではない。単数の表現は、文の中で明らかに表現しない限り、複数の表現を含む。本願において、「含む」または「有する」などの用語は明細書上に記載された特徴、数字、段階、動作、構成要素、部品、またはこれらを組合せたものの存在を指定するものであって、一つまたはそれ以上の他の特徴や数字、段階、動作、構成要素、部品、またはこれらを組合せたものの存在または付加可能性を予め排除するものではないと理解しなくてはならない。 The terms used in the present application are merely used to describe particular embodiments, and are not intended to limit the present invention. A singular expression includes the plural expression unless it is explicitly expressed in a sentence. In this application, terms such as “comprising” or “having” specify the presence of a feature, number, step, action, component, part, or combination thereof described in the specification, and It should be understood that the existence or additional possibilities of one or more other features or numbers, steps, operations, components, parts, or combinations thereof are not excluded in advance.
以下、本発明による燃料電池用膜電極接合体の製造方法の好ましい実施例を添付図面を参照して詳しく説明し、添付図面を参照して説明するに当たって、同一または対応する構成要素は同一の図面番号を付し、これに対する重複説明は省略する。 Hereinafter, preferred embodiments of a method for manufacturing a membrane electrode assembly for a fuel cell according to the present invention will be described in detail with reference to the accompanying drawings, and the same or corresponding components will be described with reference to the accompanying drawings. A number will be assigned, and repeated explanation thereof will be omitted.
図２は本発明の好ましい一実施例による燃料電池用膜電極接合体の製造方法を示す順序図であり、図３は本発明の一実施例による燃料電池用膜電極接合体の製造装置を示す概念図である。図３を参照すると、複合酸化物層１０、酸素タンク１１、窒素タンク１２、加湿器１３、炉１４、及びバルブ１５が示されている。 FIG. 2 is a flow chart illustrating a method of manufacturing a fuel cell membrane electrode assembly according to a preferred embodiment of the present invention, and FIG. 3 illustrates a fuel cell membrane electrode assembly manufacturing apparatus according to an embodiment of the present invention. It is a conceptual diagram. Referring to FIG. 3, a composite oxide layer 10, an oxygen tank 11, a nitrogen tank 12, a humidifier 13, a furnace 14, and a valve 15 are shown.
先ず、ステップＳ１００で、炉１４にランタンガレート系の複合酸化物層１０を投入する。 First, in step S100, the lanthanum gallate-based composite oxide layer 10 is charged into the furnace.
炉１４は、ものを加熱したり、溶解したりする目的で所定の閉鎖空間を形成し、加熱装置を備えたチャンバであって、内部空間で複合酸化物層１０を加熱することにより、電解質層の焼結工程を行うことができる。 The furnace 14 forms a predetermined closed space for the purpose of heating or melting the object, and is a chamber equipped with a heating device, and the electrolyte layer 10 is heated by heating the composite oxide layer 10 in the internal space. The sintering process can be performed.
酸素タンク１１及び窒素タンク１２は、炉１４に供給される酸素または窒素ガスを貯留するタンクであって、供給される量を調節するために、ＭＦＣ（Ｍａｓｓ Ｆｌｏｗ Ｃｏｎｔｒｏｌｌｅｒ）のようなバルブ１５を用いることができる。また、ガスに適切な湿気を供給するために加湿器１３を備えることができる。 The oxygen tank 11 and the nitrogen tank 12 are tanks for storing oxygen or nitrogen gas supplied to the furnace 14, and a valve 15 such as an MFC (Mass Flow Controller) is used to adjust the supplied amount. be able to. Further, a humidifier 13 can be provided to supply appropriate moisture to the gas.
複合酸化物層１０は焼結工程により膜電極接合体の電解質層となる部分であって、本実施例で電解質層の材料として用いられる、ドーピングされたランタンガレート系の複合酸化物は、既存のジルコニア電解質に比べてイオン伝導度が高いため、次世代の電解質層材料として注目されている。 The composite oxide layer 10 is a portion that becomes an electrolyte layer of a membrane electrode assembly by a sintering process, and a doped lanthanum gallate-based composite oxide used as a material of the electrolyte layer in this embodiment is an existing one. Because of its higher ionic conductivity than zirconia electrolytes, it is attracting attention as a next-generation electrolyte layer material.
ドーピングされたランタンガレート系の複合酸化物は、ランタンガレート酸化物（ＬａＧａＯ３）にストロンチウム（Ｓｒ）とガリウム（Ｇａ）が添加（ｄｏｐｉｎｇ）されたものであって、一般式（１）の組成を有する。式中、ｘ及びｙは０以上１以下の値を有することができる。
［化１］
（ＬａｘＳｒ１−ｘ）（ＧａｙＭｇ１−ｙ）Ｏ３ （１）
次に、ステップＳ２００で、炉１４に酸素または窒素を含む雰囲気ガスを供給し、ステップＳ３００で、雰囲気ガス下で複合酸化物層１０を熱処理して電解質層を形成する。
The doped lanthanum gallate-based composite oxide is obtained by adding strontium (Sr) and gallium (Ga) to a lanthanum gallate oxide (LaGaO 3 ), and has a composition of the general formula (1). Have. In the formula, x and y may have a value of 0 or more and 1 or less.
[Chemical 1]
(La x Sr 1-x) (Ga y Mg 1-y) O 3 (1)
Next, in step S200, an atmosphere gas containing oxygen or nitrogen is supplied to the furnace 14, and in step S300, the composite oxide layer 10 is heat-treated under the atmosphere gas to form an electrolyte layer.
ドーピングされたランタンガレート系の複合酸化物層１０を焼結して優れた電気的特性及び緻密な微細組織を有する電解質層を得るためには、１４７０〜１５５０℃の高温で６時間以上加熱することになるため、製造工程にかかる時間及び高温維持という負担から実用化が困難とされていた。 In order to sinter the doped lanthanum gallate-based composite oxide layer 10 to obtain an electrolyte layer having excellent electrical characteristics and a fine microstructure, it is heated at a high temperature of 1470 to 1550 ° C. for 6 hours or more. Therefore, it has been difficult to put it to practical use due to the time required for the manufacturing process and the burden of maintaining a high temperature.
空気中で複合酸化物層１０を１３５０℃程度の比較的低い温度で３０分間加熱すると、図４に示すように、焼結粒子のサイズが不均一であり、９０％程度の焼結密度を有する電解質層が形成される。このような低い焼結密度を有する電解質層は、電気伝導度が低く、燃料電池の作動時に燃料と空気が直接接触することになって燃料電池の効率を低下させる。 When the composite oxide layer 10 is heated in air at a relatively low temperature of about 1350 ° C. for 30 minutes, as shown in FIG. 4, the size of the sintered particles is non-uniform and the sintered density is about 90%. An electrolyte layer is formed. The electrolyte layer having such a low sintered density has low electrical conductivity, and the fuel and air are in direct contact with each other when the fuel cell is operated, thereby reducing the efficiency of the fuel cell.
一方、空気の代りに酸素または窒素雰囲気で焼結する場合、より高い焼結密度を有する電解質層を得ることができる。図５は本発明の一実施例による燃料電池用膜電極接合体の製造方法により焼結された複合酸化物の表面を示す微細組織写真であり、図６は本発明の他の実施例による燃料電池用膜電極接合体の製造方法により焼結された電解質層の表面を示す微細組織写真である。図４と比較すると、焼結密度が９７〜９８％であって、１３５０℃程度の比較的低い温度で約３０分だけ加熱しても２〜３％の気孔率を有する電解質層が形成されたことが分かる。 On the other hand, when sintering is performed in an oxygen or nitrogen atmosphere instead of air, an electrolyte layer having a higher sintering density can be obtained. FIG. 5 is a microstructural photograph showing the surface of a composite oxide sintered by a method of manufacturing a membrane electrode assembly for a fuel cell according to one embodiment of the present invention, and FIG. 6 is a fuel according to another embodiment of the present invention. It is a micro structure photograph which shows the surface of the electrolyte layer sintered by the manufacturing method of the membrane electrode assembly for batteries. Compared with FIG. 4, the sintered density was 97 to 98%, and an electrolyte layer having a porosity of 2 to 3% was formed even when heated at a relatively low temperature of about 1350 ° C. for about 30 minutes. I understand that.
本実施例では、開放された空間ではなく、炉１４で熱処理を行うため、酸素タンク１１または窒素タンク１２に貯留されていた酸素または窒素を炉１４の内部に注入して雰囲気ガス下で焼結工程を行うことができる。 In this embodiment, since heat treatment is performed in the furnace 14 instead of the open space, oxygen or nitrogen stored in the oxygen tank 11 or the nitrogen tank 12 is injected into the furnace 14 and sintered in an atmosphere gas. A process can be performed.
図７は炉内部の雰囲気ガスによる電解質層の電気伝導度を示すグラフであって、６００℃での電気伝導度は、酸素雰囲気で焼結した電解質層が２．７ＳＫ／ｃｍ以上であり、窒素雰囲気で焼結した電解質層が２．５ＳＫ／ｃｍであった。これは、空気中で焼結した電解質層の電気伝導度に比べると、０．５ＳＫ／ｃｍ以上高いので、燃料電池の効率を向上させることができる。 FIG. 7 is a graph showing the electrical conductivity of the electrolyte layer by the atmospheric gas inside the furnace. The electrical conductivity at 600 ° C. is 2.7 SK / cm or more for the electrolyte layer sintered in an oxygen atmosphere. The electrolyte layer sintered in the atmosphere was 2.5 SK / cm. This is higher by 0.5 SK / cm or more than the electric conductivity of the electrolyte layer sintered in the air, so that the efficiency of the fuel cell can be improved.
本発明の他の実施例によれば、複合酸化物層の一面に金属層をさらに形成し、炉に投入して焼結することができる。複合酸化物層は加熱後に電解質層に焼結され、金属層は燃料極となる。金属層は、水素が水素イオンになる際に触媒の役割をするニッケル（Ｎｉ）、コバルト（Ｃｏ）、鉄（Ｆｅ）などの遷移金属を含むことができる。 According to another embodiment of the present invention, a metal layer may be further formed on one surface of the composite oxide layer, which may be charged into a furnace and sintered. The composite oxide layer is sintered to the electrolyte layer after heating, and the metal layer becomes the fuel electrode. The metal layer can include a transition metal such as nickel (Ni), cobalt (Co), or iron (Fe) that acts as a catalyst when hydrogen becomes hydrogen ions.
燃料電池の場合、燃料極と電解質層との間の界面で、燃料極から投入された水素が燃料極内の遷移金属（Ｎｉ、Ｃｏ、Ｆｅなど）のような触媒と反応して水素イオンとなり、このような反応サイトを三相界面と言う。三相界面が多いほど反応量が増加して電子の発生も増加し、燃料電池の発電出力も向上することになるが、過焼結により燃料極の粒子が過成長すると、これにより、三相界面が減少する。 In the case of a fuel cell, hydrogen introduced from the fuel electrode reacts with a catalyst such as a transition metal (Ni, Co, Fe, etc.) in the fuel electrode at the interface between the fuel electrode and the electrolyte layer to form hydrogen ions. Such a reaction site is called a three-phase interface. As the number of three-phase interfaces increases, the amount of reaction increases, the generation of electrons increases, and the power generation output of the fuel cell also improves. The interface is reduced.
したがって、燃料極の焼結は低い温度で焼結する必要があり、既存の電解質層の焼結は高温で長期間加熱したため、燃料極と同時に焼結することが困難であった。しかし、本実施例によれば、電解質層の焼結は、窒素または酸素の雰囲気ガス下では低い温度で加熱しても充分な焼結密度を得ることができるため、電解質層と燃料極を同時に焼結することができ、低コストで電解質−燃料極半電池を製造することができる。 Therefore, it is necessary to sinter the fuel electrode at a low temperature, and since the existing electrolyte layer is heated at a high temperature for a long time, it is difficult to sinter at the same time as the fuel electrode. However, according to the present embodiment, since the electrolyte layer can be sintered at a low temperature under a nitrogen or oxygen atmosphere gas, a sufficient sintered density can be obtained. It can be sintered, and an electrolyte-fuel electrode half-cell can be manufactured at low cost.
以上、本発明を実施の形態を用いて説明したが、本発明の技術的範囲は上記実施の形態に記載の範囲には限定されない。上記実施の形態に、多様な変更または改良を加えることが可能であることが当業者に明らかである。その様な変更または改良を加えた形態も本発明の技術的範囲に含まれ得ることが、特許請求の範囲の記載から明らかである。 As mentioned above, although this invention was demonstrated using embodiment, the technical scope of this invention is not limited to the range as described in the said embodiment. It will be apparent to those skilled in the art that various modifications or improvements can be added to the above-described embodiment. It is apparent from the scope of the claims that the embodiments added with such changes or improvements can be included in the technical scope of the present invention.
特許請求の範囲、明細書、および図面中において示した装置、方法における動作、手順、ステップ、および工程等の各処理の実行順序は、特段「より前に」、「先立って」等と明示しておらず、また、前の処理の出力を後の処理で用いるのでない限り、任意の順序で実現しうることに留意すべきである。特許請求の範囲、明細書、および図面中の動作フローに関して、便宜上「先ず、」、「次に、」等を用いて説明したとしても、この順で実施することが必須であることを意味するものではない。 The execution order of each process such as operation, procedure, step, and process in the apparatus and method shown in the claims, the description, and the drawings is clearly indicated as “before”, “prior”, etc. It should be noted that, unless the output of the previous process is used in the subsequent process, it can be realized in any order. Even if the operation flow in the claims, the description, and the drawings is described using “first,” “next,” etc. for the sake of convenience, it means that it is essential to carry out in this order. It is not a thing.
２ 電解質層
３ 燃料極
４ 空気極
１０ 複合酸化物層
１１ 酸素タンク
１２ 窒素タンク
１３ 加湿器
１４ 炉
１５ バルブ
2 Electrolyte layer 3 Fuel electrode 4 Air electrode 10 Composite oxide layer 11 Oxygen tank 12 Nitrogen tank 13 Humidifier 14 Furnace 15 Valve
Claims (4)
ランタンガレート系の複合酸化物層の一面に金属層を形成する工程と、
炉に上記ランタンガレート系の複合酸化物層を投入する工程と、
前記炉に酸素または窒素を含む雰囲気ガスを供給し、加湿器により前記ガスに湿気を供給する工程と、
前記複合酸化物層を熱処理して電解質層を形成する工程と、
前記電解質層の一面に燃料極を形成する工程と、
前記電解質層の他面に空気極を形成する工程と、を含み、
前記電解質層の一面に燃料極を形成する工程は、前記金属層を前記熱処理することにより行われることを特徴とする燃料電池用膜電極接合体の製造方法。 A method for producing a membrane electrode assembly for a solid oxide fuel cell, comprising:
Forming a metal layer on one surface of the lanthanum gallate-based composite oxide layer;
A step of turning on the composite oxide layer of the lanthanum gallate-based furnace,
Supplying an atmospheric gas containing oxygen or nitrogen to the furnace, and supplying moisture to the gas by a humidifier ;
Heat-treating the composite oxide layer to form an electrolyte layer;
Forming a fuel electrode on one surface of the electrolyte layer;
See containing and forming a cathode on the other surface of the electrolyte layer,
The process for forming a fuel electrode on one surface of the electrolyte layer is performed by performing the heat treatment on the metal layer .
［化１］
（ＬａｘＳｒ１−ｘ）（ＧａｙＭｇ１−ｙ）Ｏ３ （１）
（式中、ｘ及びｙは０以上１以下の値を有する。） The method for producing a membrane electrode assembly for a fuel cell according to claim 1, wherein the composition of the composite oxide layer satisfies the following general formula (1).
[Chemical 1]
(La x Sr 1-x) (Ga y Mg 1-y) O 3 (1)
(In the formula, x and y have values of 0 or more and 1 or less.)
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| JP3564535B2 (en) | 2000-12-22 | 2004-09-15 | 独立行政法人産業技術総合研究所 | Method for producing high-density sintered lanthanum-based composite oxide having perovskite-type crystal structure |
| KR100462950B1 (en) | 2002-03-27 | 2004-12-23 | 요업기술원 | Solid oxide fuel cell |
| JP2004339035A (en) | 2003-05-19 | 2004-12-02 | Nissan Motor Co Ltd | Lanthanum gallate sintered compact, method for producing the same, and use of the same |
| JP4670228B2 (en) * | 2003-05-22 | 2011-04-13 | 東京電力株式会社 | Fuel cell plant |
| JP2006228587A (en) * | 2005-02-18 | 2006-08-31 | Mitsubishi Materials Corp | Fuel electrode of power generation cell for solid electrolyte fuel cell |
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