JP5198908B2 - A method for producing a completely dense electrolyte layer laminated on a high performance solid oxide fuel cell membrane electrode assembly (SOFC-MEA). - Google Patents

A method for producing a completely dense electrolyte layer laminated on a high performance solid oxide fuel cell membrane electrode assembly (SOFC-MEA). Download PDF

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JP5198908B2
JP5198908B2 JP2008061916A JP2008061916A JP5198908B2 JP 5198908 B2 JP5198908 B2 JP 5198908B2 JP 2008061916 A JP2008061916 A JP 2008061916A JP 2008061916 A JP2008061916 A JP 2008061916A JP 5198908 B2 JP5198908 B2 JP 5198908B2
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高維欣
李茂傳
林泰男
王俊修
張揚状
林立夫
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行政院原子能委員會核能研究所
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Description

本発明は、高性能固体酸化物形燃料電池接合体に積層する電解質層の製造方法に関し、特にテープキャスティング法と、シルクスクリーン印刷法（Screen printing）、スパッタリングコーティング法（Sputtering coating）、スピンコーティング法（Spin coating）、プラズマ・スプレーコーティング法(Plasma spray Coating)などの薄膜塗布工程を組み合わせて行う薄膜製作方法に関する。   The present invention relates to a method for manufacturing an electrolyte layer to be laminated on a high performance solid oxide fuel cell assembly, and more particularly, a tape casting method, a silk screen printing method, a sputtering coating method, and a spin coating method. The present invention relates to a thin film manufacturing method in which thin film coating processes such as (Spin coating) and plasma spray coating are combined.

原油価格の高騰と環境保護意識の抬頭につれて、再生可能エネルギー技術も本世紀で最も重要な発展技術の一つとなっている。高性能固体酸化物燃料電池は高效率、低汚染及びエネルギー多元化を備えたエネルギー発電システムであり、かつ材料組成は簡単で、構造のモジュール化によって持続的安定な発電を提供できるなどの特色に基き、最も発展潜在力のある発電システムである。   Renewable energy technology has become one of the most important development technologies of this century as the price of crude oil has soared and the awareness of environmental protection has increased. The high-performance solid oxide fuel cell is an energy power generation system with high efficiency, low pollution and energy diversification, and the material composition is simple, and it can provide sustainable and stable power generation by modularizing the structure. Based on this, it is the power generation system with the most potential for development.

Ｙ2Ｏ3をドープしたイットリア安定化ジルコニア（YSZ）を電解質材料にする電解質支持形基板電池(Electrolyte Supported Cell:略称ESC)の作動温度は800〜1000℃であり、その電解質層基板の厚さは150〜300μｍであり、これは第一世代の固体酸化物形燃料電池電極接合体（SOFC-MEA）に属する。NiO+YSZを陽極材料にする陽極支持基板電池セル(Anode Supported Cell:略称ASC) の作動温度は650〜800℃であり、その電解質層(主にYSZを材料とし)の厚さは大よそ10μｍであり、これは第二世代のSOFC-MEAに属する。NiO＋8YSZはASC/ESCの陽極材料で、陰極材料は主にＬａ0.8Ｓｒ0.2ＭｎＯ3（LSM）およびLa-Sr-Co-Fe-O系ペロブスカイト型酸化物（LSCF）であり、その厚さは30〜60μｍである。これと同時に全世界の各研究室において新しい電解質材料および陰極材料の研究開発が進行しており、これら新材料が登場することによりSOFC-MEAの作動温度を500〜700 ℃に下げられることが望まれる。作動温度を下げることによってSOFCのスタック(Stack)に用いられる組立て部品、例えばインターコネクター(Inter-connector)などの構成材料を金属材料からセラミック材料に変えることができる。こうして電池の製造が容易になる上、その機械的強度/安定性/耐久性も向上し、SOFC全体のコストダウン(Cost down)も見込める。この技術の発展について、大学および国家の研究室では材料の研究開発に重点を置き、新世代の材料の開発によって電気抵抗を減少させ、イオン伝導/電気伝導性を増加することによりSOFCの発電能力を向上させることを目指している。
特開２００５−１４９７９７号公報 特開２００７−２００６６４号公報 特開２００７−３１３６５０号公報 Y 2 O 3 doped with yttria-stabilized zirconia (YSZ) electrolyte support type substrate batteries to electrolyte material: operating temperature (Electrolyte the Supported Cell abbreviated ESC) is 800 to 1000 ° C., the thickness of the electrolyte layer substrate Is 150-300 μm, which belongs to the first generation solid oxide fuel cell electrode assembly (SOFC-MEA). The operating temperature of the anode supported cell battery cell (Anode Supported Cell: ASC) using NiO + YSZ as the anode material is 650 to 800 ° C, and the thickness of the electrolyte layer (mainly YSZ is used as material) is approximately 10μm. This belongs to the second generation SOFC-MEA. NiO + 8YSZ is an anode material of ASC / ESC, and the cathode material is mainly La 0.8 Sr 0.2 MnO 3 (LSM) and La—Sr—Co—Fe—O based perovskite oxide (LSCF), and its thickness is 30 ~ 60 μm. At the same time, research and development of new electrolyte materials and cathode materials are progressing in laboratories around the world, and it is hoped that the operating temperature of SOFC-MEA can be lowered to 500-700 ° C by the appearance of these new materials. It is. By lowering the operating temperature, it is possible to change the construction material used in the SOFC stack, such as an inter-connector, from a metal material to a ceramic material. This makes it easier to manufacture the battery, improves its mechanical strength / stability / durability, and can reduce the cost of the SOFC as a whole. With regard to the development of this technology, the university and national laboratories will focus on material research and development, reduce the electrical resistance by developing a new generation of materials, increase the ionic conduction / conductivity, SOFC power generation capacity It aims to improve.
JP 2005-149797 A JP 2007-200634 A JP 2007-313650 A

本発明は、SOFC-MEAの電解質層を完全緻密な特性とすることにより、電池の作動性・耐久性・安定性を高めることを目標とする。その発明の効果は電池セルの性能試験(Performance test of SOFC-MEA)によって検証できる。   The present invention aims to improve the operability, durability, and stability of the battery by making the SOFC-MEA electrolyte layer completely dense. The effect of the invention can be verified by a battery cell performance test (Performance test of SOFC-MEA).

上記の目的を達成するために、本発明はテープキャスティング法に加えて、スパッタリングコーティング法(Sputtering coating)、シルクスクリーン印刷法(Screen printing)、スピンコーティング法(Spin coating)またはプラズマスプレーコーティング法(Plasma spray/Coating)などの薄膜製作工程を適用し、かつ1500℃の温度で５時間焼結を行い、温度昇降の速度率は0.1〜3℃/minという焼結条件をコントロールして、完全緻密な電解質を製作する方法である。   In order to achieve the above object, in addition to the tape casting method, the present invention provides a sputtering coating method, a screen printing method, a screen coating method, a spin coating method, or a plasma spray coating method (Plasma coating method). Applying a thin film manufacturing process such as spray / coating), sintering at 1500 ° C for 5 hours, and controlling the sintering condition of 0.1-3 ° C / min. This is a method of manufacturing an electrolyte.

陽極支持基板電池セル(Anode Supported Cell:略称ASC)を製造する場合、例えば、テープキャスティング法(tape casting)によって電解質のグリーンテープを成形して、ラミネート処理によりこの電解質グリーンテープを陽極と密着させる。この陽極/電解質の複合グリーンテープを高温焼結工程によって半電池（Half cell）とし、シルクスクリーン印刷法によって陰極層を半電池の電解質層上に塗布して、完全緻密な電解質層を有する陽極支持型固体酸化物燃料電池の電池セルを完成した。
こうして作られたSOFC-MEAは完全緻密/気密な特性を備えているから、燃料（例えばH2）や酸化剤気体（例えばAir）を完全に遮断して、酸素イオンだけ電解質層を通らせて電化学の発電反応を進行させ、その他の化学反応を一切起こらないようにする。これによって発電過程において電池セルの成分及び構造は化学反応によって破壊されることを免れ、理論値の開放電圧（OVC）の運転を維持することができる。この電池セルは、電気性能試験(Performance test of SOFC-MEA)によって高操作性、耐久性、安定性を検証できる。 When manufacturing an anode-supported substrate battery cell (Anode Supported Cell: abbreviated as ASC), for example, an electrolyte green tape is formed by a tape casting method, and the electrolyte green tape is brought into close contact with the anode by a laminating process. This anode / electrolyte composite green tape is made into a half cell by a high temperature sintering process, and a cathode layer is coated on the electrolyte layer of the half cell by a silk screen printing method, and an anode support having a completely dense electrolyte layer Type solid oxide fuel cell was completed.
The SOFC-MEA produced in this way has fully dense / airtight properties, so it completely shuts off the fuel (eg H 2 ) and oxidant gas (eg Air) and passes only oxygen ions through the electrolyte layer. Proceed with the electrochemical power generation reaction and prevent any other chemical reaction. As a result, the components and structure of the battery cell are prevented from being destroyed by a chemical reaction in the power generation process, and the operation of the theoretical open circuit voltage (OVC) can be maintained. This battery cell can be verified for high operability, durability and stability by a performance test of SOFC-MEA.

完全緻密(Fully dense)且つ気体透過率ゼロ(Zero gas leakage rate)、あるいは気密性(Air tight)の電解質（電解質の材料は8YSZ/GDC/YDC/LSGMなど）を有する平板型固体酸化物形燃料電池膜電極接合体(SOFC- MEA)、即ち電池セル(Unit cell)を製造するステップは以下のとおりである。   A flat solid oxide fuel with a fully dense and zero gas leakage rate or air tight electrolyte (the electrolyte material is 8YSZ / GDC / YDC / LSGM, etc.) The steps of manufacturing a battery membrane electrode assembly (SOFC-MEA), that is, a battery cell (Unit cell), are as follows.

ステップ1：テープキャスティング法によって平板型SOFC-MEAの陽極および電解質（材料はYSZ、GDC、YDC、SmDC、LSGMなどがある）のグリーンテープ（Green tapes）を成形し、ラミネート処理により両者を積層して電解質グリーンテープの層厚が5〜300μｍ、及び陽極グリーンテープの層厚が600〜1200μｍのSOFCのグリーンテープ半電池(Half cell)を得る。この半電池を1200°C〜1600°Cの温度(1400℃〜1500°Cが最適)で数時間(3時間以上)の焼結を行い、第一段階のセラミック半電池が得られる。電子顕微鏡(SEM)で半電池のマイクロ構造(Microstructure)の解析を行い、電解質層のマイクロ構造が無孔質状態であって完全緻密(Fully dense)な状態に達したことを確認した。 Step 1: Flat tape SOFC-MEA anode and electrolyte (materials include YSZ, GDC, YDC, SmDC, LSGM, etc.) green tapes are formed by tape casting, and both are laminated by laminating. Thus, an SOFC green tape half cell having an electrolyte green tape layer thickness of 5 to 300 μm and an anode green tape layer thickness of 600 to 1200 μm is obtained. This half-cell is sintered for several hours (3 hours or more) at a temperature of 1200 ° C to 1600 ° C (optimally 1400 ° C to 1500 ° C) to obtain a first stage ceramic half-cell. An electron microscope (SEM) was used to analyze the microstructure of the half-cell, and it was confirmed that the microstructure of the electrolyte layer had reached a non-porous state and a fully dense state.

ステップ2: 完成した半電池の電解質層上に、シルクスクリーン印刷法によって多孔質(Porous)の陰極層(材料は一般的にLSMかLSCFなど)を形成して、1200°Cで3時間の仮焼を行い、SOFC-MEAを完成する。 Step 2: A porous cathode layer (generally LSM or LSCF, etc.) is formed on the electrolyte layer of the completed half-cell by silk screen printing, and is temporarily set at 1200 ° C for 3 hours. Bake and complete SOFC-MEA.

なお、上記方法は、完全緻密(Fully dense)/気密性(Air-tight)の電解質層を有するSOFC-MEAを製造する方法であり、ステップ1およびステップ2の概要を図一に示す。   The above method is a method for producing SOFC-MEA having a fully dense / air-tight electrolyte layer, and outlines of Step 1 and Step 2 are shown in FIG.

本発明の製法によって得られた平板型固体酸化物形燃料電池膜電極接合体(SOFC- MEA)は、その電解質層が完全緻密(Fully dense)/気密性(Air-tight)を具えているため、電気抵抗が小さく、イオン伝導/電気伝導性を向上することによりSOFCの発電能力を向上することができる。   The plate-type solid oxide fuel cell membrane / electrode assembly (SOFC-MEA) obtained by the production method of the present invention has a fully dense / air-tight electrolyte layer. The power generation capability of SOFC can be improved by reducing the electrical resistance and improving the ion conduction / electric conductivity.

本発明について代表的な例を示しさらに具体的に説明する。これらは説明のための単なる例示であって、本発明はこれらに何等制限されるものではない。   The present invention will be described more specifically with representative examples. These are merely illustrative examples, and the present invention is not limited thereto.

［実施例］
ステップ１：完全緻密/気密の電解質層（材料は8YSZ/ GDC/ LSGM）の固体酸化物型燃料電池接合体(SOFC-MEA)の電池セル（Unit Cell）を作るには、まず50wt% NiO＋50wt% 8YSZ（8mol.% Yttria-Stablized Zirconia）の粉末及び気孔形成剤(Pore former)として所要量の石墨（Graphite）などで基本材料スラリーを調整し、適当な比率の溶剤（アルコール/ブタノン）、分散剤（トリエタノールアミン）、可塑剤（ポリエチレングリコール/フタル酸ジブチル）、及び粘着剤（ポリエチレンブチラール）をボールミルによって混合させて均一化し、テープキャスティング法によって電極グリーンテープを作り、更にラミネート処理に通して厚さ1000μｍ、サイズ5×5 ｃｍ2〜10×10ｃｍ2の陽極基板グリーンテープ（Anode Green Substrate）を完成する。 [Example]
Step 1: To make a unit cell of a solid oxide fuel cell assembly (SOFC-MEA) with a fully dense / airtight electrolyte layer (material is 8YSZ / GDC / LSGM), first 50wt% NiO + 50wt% Prepare 8YSZ (8mol.% Yttria-Stablized Zirconia) powder and pore former (Pore former) with basic material slurry with the required amount of Graphite, etc., solvent (alcohol / butanone), dispersant in appropriate ratio (Triethanolamine), plasticizer (polyethylene glycol / dibutyl phthalate), and pressure-sensitive adhesive (polyethylene butyral) are mixed by a ball mill and homogenized, and an electrode green tape is made by a tape casting method. Anode Green Substrate having a thickness of 1000 μm and a size of 5 × 5 cm 2 to 10 × 10 cm 2 is completed.

ステップ２：電解質層の材料としてYSZ、GDC、LSGM、SDC、又はYDC粉末を上記ステップ1の陽極材料と同様に溶剤、分散剤、可塑剤及び粘着剤をボールミルによって均一に混合してスラリーを調整し、テープキャスティング法によって電解質グリーンテープの薄膜(5〜300μｍ)を作成し、ステップ1で作成した電極グリーンテープにラミネート処理によって密着して積層させ、SOFCのグリーンテープ半電池(Half cell)を構成し、1200°C〜 1600°C間(1400°C〜1500℃が最適)で数時間(3時間以上)の焼結を行うことによって、第一段階のセラミック半電池を得る。
このようにして形成した半電池を、走査型電子顕微鏡（SEM）でマイクロ構造(Microstructure) を解析し、電解質層が無孔質(Open pore free)のマイクロ構造状態であることを確認した。図二に示したように、電解質層の厚さは約20μｍで、すでに完全緻密な構造を達成して、気密性を備えており、SOFC-MEAの電解質層に必須の要求は満たされている。残存する極かな閉塞性の細孔は、気体透過率に影響を与えない。 Step 2: Prepare slurry by mixing YSZ, GDC, LSGM, SDC, or YDC powder as electrolyte layer material uniformly with ball mill in the same way as anode material in Step 1 above. Then, an electrolyte green tape thin film (5-300μm) is prepared by tape casting method, and the electrode green tape prepared in step 1 is adhered and laminated by laminating process to form a SOFC green tape half cell (Half cell) The first stage ceramic half-cell is obtained by sintering for several hours (3 hours or more) between 1200 ° C. and 1600 ° C. (1400 ° C. to 1500 ° C. is optimal).
The half-cell thus formed was analyzed for the microstructure by a scanning electron microscope (SEM), and it was confirmed that the electrolyte layer was in an open pore free microstructure. As shown in Fig. 2, the thickness of the electrolyte layer is about 20μm, has already achieved a completely dense structure, has airtightness, and the essential requirements for the SOFC-MEA electrolyte layer are satisfied . The remaining extremely obstructive pores do not affect the gas permeability.

ステップ3：電解質層が気密であることをさらに確認するため、ステップ２で得られた半電池の気体透過率を測定し、気体透過率は1×10-6 L/cm2/sec以下であって、この電解質層が完全緻密であることが確認された。この完全緻密な電解質層の半電池はHC-fdと称する。 Step 3: To further confirm that the electrolyte layer is airtight, the gas permeability of the half-cell obtained in Step 2 was measured, and the gas permeability was 1 × 10 −6 L / cm 2 / sec or less. Thus, it was confirmed that the electrolyte layer was completely dense. This fully dense electrolyte layer half-cell is called HC-fd.

ステップ4：HC-fd電解質層の上に、シルクスクリーン印刷法によって、LSM材料で多孔質の陰極層を形成し、更に1200 °C、/3 hrsの焼結工程を行った。焼結温度昇降の速度は3°C/minでよいが、これに限定されない。
以上により、高い作動性能のSOFC-MEA (Unit cell)を完成した。この電池セルのマイクロ構造のSEM像を図二に示す。完成したSOFC-MEAに対して電気性能試験を行った結果を図三に示す。この結果からOCV (1.037~1.016V)はすでに理論値に達しており、電力密度も150 mW/ cm2を上回っていることが分かる。
本発明は、支持基板となる陽極又は陰極層をテープキャスティング法によって形成することにより支持強度を得るために必要な厚さにし、
これに対して電解質層は、これらの支持強度を具えた電極層にラミネートして積層することにより、気密性を確保するために必要な厚さであって、かつ酸素イオンの透過に適した薄さとすることができる。
また、支持基板となる陽極又は陰極層に対する陰極又は陽極層はスクリーン印刷法などの薄膜形成法により形成することによって、通気性を得るに必要な薄い層とすることができる。 Step 4: A porous cathode layer was formed with an LSM material on the HC-fd electrolyte layer by a silk screen printing method, and a sintering process was further performed at 1200 ° C. for 3 hrs. The rate of raising and lowering the sintering temperature may be 3 ° C / min, but is not limited thereto.
As described above, SOFC-MEA (Unit cell) with high operating performance was completed. The SEM image of the microstructure of this battery cell is shown in FIG. Figure 3 shows the results of electrical performance tests on the completed SOFC-MEA. From this result, it can be seen that OCV (1.037 to 1.016V) has already reached the theoretical value, and the power density exceeds 150 mW / cm 2 .
In the present invention, the anode or cathode layer to be a support substrate is formed by a tape casting method to have a thickness necessary for obtaining a support strength,
On the other hand, the electrolyte layer is a thin layer suitable for the permeation of oxygen ions and having a thickness necessary for ensuring airtightness by laminating and laminating these electrode layers having supporting strength. It can be.
In addition, the cathode or anode layer corresponding to the anode or cathode layer serving as the support substrate can be formed as a thin layer necessary for obtaining air permeability by being formed by a thin film forming method such as a screen printing method.

本発明の高性能固体酸化物燃料電池接合体（電池セル）に完全緻密な電解質を製作する方法の一実施例の簡易説明図。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a simplified illustration of one embodiment of a method for producing a complete dense electrolyte in a high performance solid oxide fuel cell assembly (battery cell) of the present invention. 本発明の薄膜形成法と焼結条件によって得られた固体酸化物燃料電池の断面構造のSEMマイクロ構造分析図。(A)：全電池截面、(B)：プラス極截面、(C)：マイナス極截面、(D)：電解質表面。The SEM micro structure analysis figure of the section structure of the solid oxide fuel cell obtained by the thin film formation method and sintering conditions of the present invention. (A): All battery surfaces, (B): Positive electrode surface, (C): Negative electrode surface, (D): Electrolyte surface. 本発明の高性能固体酸化物燃料電池接合体（電池セル）を用いた固体酸化物燃料電池の電気性能試験結果。The electrical performance test result of the solid oxide fuel cell using the high performance solid oxide fuel cell assembly (battery cell) of this invention.

Claims (12)

平板型固体酸化物形燃料電池膜電極接合体を製造する方法であって、
（ａ） テープキャスティング法によってＳＯＦＣの電極及び電解質のグリーンテープをそれぞれ作製し、
（ｂ） 電極グリーンテープ上に電解質グリーンテープを重ねて、真空雰囲気中で加圧するラミネート処理によってＳＯＦＣのグリーンテープの半電池を作成し、
（ｃ） 上記ｂで形成した半電池グリーンテープを温度昇降速度０．１〜３℃／ｍｉｎ、１２００〜１６００℃で３〜６時間の仮焼を行う高温焼結によって半電池基板（ＨＣ−ｆｄ）とし、
（ｄ） 上記ＨＣ−ｆｄの電解質層上にシルクスクリーン印刷法によって上記電極に対する電極層を形成し、１２００℃で３時間、焼結の温度昇降速度３℃／ｍｉｎの焼結工程を経て電池セルを完成する、
（ａ）〜（ｄ）の各工程からなることを特徴とする高性能固体酸化物形燃料電池膜電極接合体（ＳＯＦＣ−ＭＥＡ）に積層する完全緻密な電解質層の製造方法。 A method for producing a flat plate solid oxide fuel cell membrane electrode assembly,
(A) An SOFC electrode and an electrolyte green tape were respectively produced by a tape casting method.
(B) An electrolyte green tape is stacked on the electrode green tape, and a SOFC green tape half-cell is produced by a laminating process in which pressure is applied in a vacuum atmosphere.
(C) The half-cell substrate (HC-fd) is subjected to high-temperature sintering in which the half-cell green tape formed in b is calcined at a temperature rise / fall rate of 0.1 to 3 ° C./min and 1200 to 1600 ° C. for 3 to 6 hours. )age,
(D) An electrode layer for the electrode is formed on the HC-fd electrolyte layer by a silk screen printing method, and the battery cell is subjected to a sintering process at 1200 ° C. for 3 hours and a sintering temperature increase / decrease rate of 3 ° C./min. To complete the
A method for producing a complete dense electrolyte layer to be laminated on a high performance solid oxide fuel cell membrane electrode assembly (SOFC-MEA), comprising the steps of (a) to (d). 上記電解質の材料としてＹＳＺ、ＧＤＣ、ＬＳＧＭ、ＳＤＣ、又はＹＤＣの内のいずれかであることを特徴とする請求項１記載の高性能固体酸化物形燃料電池膜電極接合体（ＳＯＦＣ−ＭＥＡ）に積層する完全緻密な電解質層の製造方法。 The high-performance solid oxide fuel cell membrane electrode assembly (SOFC-MEA) according to claim 1, wherein the electrolyte material is any one of YSZ, GDC, LSGM, SDC, and YDC. A method for producing a completely dense electrolyte layer to be laminated. 前記（ａ）工程のＳＯＦＣの電極としての陽極材料は、ＹＳＺ＋ＮｉＯ、ＧＤＣ＋ＮｉＯ、ＬＳＧＭ＋ＮｉＯ、ＳＤＣ＋ＮｉＯ、又はＹＤＣ＋ＮｉＯから選択した1種であり、電解質材料はＹＳＺ、ＧＤＣ、ＬＳＧＭ、ＳＤＣ、又はＹＤＣから選択した１種であることを特徴とする、請求項１記載の高性能固体酸化物形燃料形電池膜電極接合体（ＳＯＦＣ−ＭＥＡ）に積層する完全緻密な電解質層の製造方法。 The anode material as the SOFC electrode in the step (a) is one selected from YSZ + NiO, GDC + NiO, LSGM + NiO, SDC + NiO, or YDC + NiO, and the electrolyte material is selected from YSZ, GDC, LSGM, SDC, or YDC . The method for producing a complete dense electrolyte layer to be laminated on a high-performance solid oxide fuel cell membrane electrode assembly (SOFC-MEA) according to claim 1, wherein the electrolyte layer is a single type. 前記の（ａ）の工程において、SOFCの電極グリーンテープとしての陽極中の触媒作用をするＮｉＯと電解質との重量百分率は５０wt％であることを特徴とする請求項１記載の高性能固体酸化物形燃料電池膜電極接合体（ＳＯＦＣ−ＭＥＡ）に積層する完全緻密な電解質層の製造方法。 2. The high performance solid oxide according to claim 1, wherein in the step (a), the weight percentage of NiO having a catalytic action in an anode as an SOFC electrode green tape and an electrolyte is 50 wt% . Of a completely dense electrolyte layer laminated on a fuel cell membrane electrode assembly (SOFC-MEA). 前記の（ａ）の工程において、SOFCの電極グリーンテープとしての陽極中の触媒作用物質がＮｉＯであることを特徴とする請求項１記載の高性能固体酸化物形燃料電池膜電極接合体（ＳＯＦＣ−ＭＥＡ)に積層する完全緻密な電解質層の製造方法。 2. The high performance solid oxide fuel cell membrane electrode assembly (SOFC) according to claim 1, wherein in the step (a), the catalytic agent in the anode as the SOFC electrode green tape is NiO. -Manufacturing method of a completely dense electrolyte layer laminated on MEA). 前記の（ｂ）において、電極グリーンテープ上に電解質薄膜グリーンテープを積層又は電解質グリーンテープ上に電極薄膜グリーンテープ層を積層することを特徴とする請求項１記載の高性能固体酸化物形燃料電池膜電極接合体(ＳＯＦＣ−ＭＥＡ)に積層する完全緻密な電解質層の製造方法。 2. The high-performance solid oxide fuel cell according to claim 1, wherein an electrolyte thin film green tape is laminated on the electrode green tape or an electrode thin film green tape layer is laminated on the electrolyte green tape. A method for producing a completely dense electrolyte layer laminated on a membrane electrode assembly (SOFC-MEA). 前記の（ｃ）において、半電池の焼結条件は１５００℃、５時間とすることを特徴とする請求項１記載の高性能固体酸化物形燃料電池膜電極接合体(ＳＯＦＣ−ＭＥＡ)に積層する完全緻密な電解質層の製造方法。 2. The high-performance solid oxide fuel cell membrane electrode assembly (SOFC-MEA) is laminated on the high-performance solid oxide fuel cell membrane electrode assembly according to claim 1, wherein the sintering condition of the half-cell is 1500 ° C. for 5 hours. A method for producing a completely dense electrolyte layer. 前記の（ｄ）において、ＨＣ-ｆｄの電解質層上に陰極層を形成する薄膜製作工程としてシルクスクリーン印刷法、スパッタリングコーティング法、プラズマ・スプレーコーティング法、又はスピンコーティング法によることを特徴とする請求項１記載の高性能固体酸化物形燃料電池膜電極接合体(ＳＯＦＣ−ＭＥＡ)に積層する完全緻密な電解質層の製造方法。 In the above (d), the thin film manufacturing process for forming the cathode layer on the HC-fd electrolyte layer is performed by a silk screen printing method, a sputtering coating method, a plasma spray coating method, or a spin coating method. A method for producing a completely dense electrolyte layer laminated on the high-performance solid oxide fuel cell membrane electrode assembly (SOFC-MEA) according to Item 1. 前記の（ｄ）において、焼結温度昇降速度は３℃／ｍｉｎ、焼結条件は１２００℃で３時間であることを特徴とする請求項１記載の高性能固体酸化物形燃料電池膜電極接合体(ＳＯＦＣ−ＭＥＡ)に積層する完全緻密な電解質層の製造方法。 2. The high performance solid oxide fuel cell membrane electrode joint according to claim 1, wherein in (d), the sintering temperature raising / lowering speed is 3 ° C./min, and the sintering condition is 1200 ° C. for 3 hours. Manufacturing method of complete dense electrolyte layer laminated on body (SOFC-MEA). 前記の（ｄ）において、ＨＣ-ｆｄの電解質層上にシルクスクリーン印刷法によって形成する陰極層の材料は、ＬＳＭ、又はＬＳＣＦであることを特徴とする請求項１記載の高性能固体酸化物形燃料電池膜電極接合体(ＳＯＦＣ−ＭＥＡ)に積層する完全緻密な電解質層の製造方法。 2. The high-performance solid oxide form according to claim 1, wherein the material of the cathode layer formed by silk screen printing on the HC-fd electrolyte layer in (d) is LSM or LSCF. A method for producing a completely dense electrolyte layer laminated on a fuel cell membrane electrode assembly (SOFC-MEA). 前記の（ｄ）において、ＨＣ-ｆｄの電解質層上にシルクスクリーン印刷法によって形成する陰極層の厚さは３０〜５０μmであることを特徴とする請求項１記載の高性能固体酸化物形燃料電池膜電極接合体(ＳＯＦＣ−ＭＥＡ)に積層する完全緻密な電解質層の製造方法。 2. The high-performance solid oxide fuel according to claim 1, wherein in (d), the thickness of the cathode layer formed on the HC-fd electrolyte layer by a silk screen printing method is 30 to 50 [mu] m. A method for producing a completely dense electrolyte layer laminated on a battery membrane electrode assembly (SOFC-MEA). 前記の（ｃ）において、走査型電子顕微鏡(ＳＥＭ)により半電池のマイクロ構造を検定して電解質層の緻密性を判定し、または気体透過率測定器によって気体透過率が１×１０-６ l／ｃｍ 2 ／ｓｅｃ以下であることを判断して、次の工程に進めることを特徴とする請求項１記載の高性能固体酸化物形燃料電池膜電極接合体(ＳＯＦＣ−ＭＥＡ)に積層する完全緻密な電解質層の製造方法。 In the above (c), the micro structure of the half-cell is examined by a scanning electron microscope (SEM) to determine the denseness of the electrolyte layer, or the gas permeability is 1 × 10 −6 l by a gas permeability meter. The complete stacking on the high performance solid oxide fuel cell membrane electrode assembly (SOFC-MEA) according to claim 1, characterized in that it is determined to be / cm 2 / sec or less and proceeds to the next step. A method for producing a dense electrolyte layer.
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