JP2009266765A - Method for manufacturing electrolyte layer of high performance solid oxide fuel cell membrane-electrode assembly (sofc-mea) by sputtering method - Google Patents
Method for manufacturing electrolyte layer of high performance solid oxide fuel cell membrane-electrode assembly (sofc-mea) by sputtering method Download PDFInfo
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Abstract
Description
本発明は、固体酸化物形燃料電池電解質層の製造方法であり、特に、薄膜の製作方法に係り、シングルターゲットスパッタ(single-gun sputter)とマルチターゲットスパッタ(multi-gun co-sputter)を含み、直流(Direct Current)と高周波(Radio Frequency)の二つの電源供給タイプで分類される反応性マグネトロンスパッタリング法(Magnetron Sputtering)を以って、テープキャスティング法(Tape casting)・ラミネート法(Lamination)・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)・プラスマスプレーコーティング法(Plasma spray coating)などの燃料電池膜電極接合体(Membrane Electrode Assembly, MEA)の製造工程と合わせて、最適化された焼結技術によって完全緻密な電解質層を製作し、固体酸化物形燃料電池の気密電解質層を製造することを目的とする。 The present invention relates to a method for producing a solid oxide fuel cell electrolyte layer, and more particularly to a method for producing a thin film, and includes a single-target sputter and a multi-target co-sputter. The reactive magnetron sputtering method (Magnetron Sputtering), which is classified into two types of power supply, direct current and radio frequency, tape casting, laminating, Optimized together with the manufacturing process of fuel cell membrane assembly (MEA) such as screen printing, spin coating, and plasma spray coating. It is an object of the present invention to manufacture a completely dense electrolyte layer by using the sintered technique and to manufacture an airtight electrolyte layer of a solid oxide fuel cell.
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。固体酸化物形燃料電池は高效率、低汚染及びエネルギー多元化の特長を備えるエネルギー発電システムであり、かつ材料組成は簡単であって、構造のモジュール化により持続的に安定な発電を提供できたりする特色を備えていることから、最も発展潜在力のある発電システムとなる。 Renewable energy technology has become one of the most important development technologies of this century as the price of crude oil rises and the consciousness of environmental protection increases. A solid oxide fuel cell is an energy power generation system with the features of high efficiency, low pollution and energy diversification. The material composition is simple, and the modularization of the structure can provide sustainable and stable power generation. Because of this feature, it will be a power generation system with the most potential for development.
第一世代のSOFC-MEAに属する電解質支持基板電池セル(Electrolyte Supported Cell: 略称ESC)の作動温度は800 ~ 1000℃であり、その電解質基板の厚さは150〜300μmである。
第二世代のSOFC-MEAに属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、その電解質基板の厚さは10μmである。
これらASC/ESCにおいて、陽極材料は(NiO+8YSZ(yttrium stabilized zirconia))であり、陰極の主要材料はLSM及びLSCFであって、その厚さは30〜60μmである。新たな電解質材料及び陰極材料は、現在世界中の研究機関・研究室で開発が進められており、新たな材料の登場することによって、さらにSOFC-MEAの作動温度を500〜700 ℃に下げることが望まれる。
その時SOFCの電池スタック(Stack)の組立て部品、例えばインターコネクター(Inter-connector)などの構成材料として金属材料をセラミック材料の代わりとして使用でき、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。これらの技術的発展は大学および国家の研究室・研究機関において材料の研究開発に重点を置かれており、材料の開発により抵抗を減少させて、イオン伝導/電気伝導性を向上することによるSOFCの発電能力の向上が期待されている。
The operating temperature of the anode supported cell battery cell (Anode Supported Cell: abbreviated as ASC) belonging to the second generation SOFC-MEA is 650 to 800 ° C., and the thickness of the electrolyte substrate is 10 μm.
In these ASC / ESC, the anode material is (NiO + 8YSZ (yttrium stabilized zirconia)), the main materials of the cathode are LSM and LSCF, and the thickness thereof is 30-60 μm. New electrolyte materials and cathode materials are currently being developed in research institutes and laboratories around the world. By introducing new materials, the operating temperature of SOFC-MEA will be further reduced to 500-700 ° C. Is desired.
At that time, metal materials can be used instead of ceramic materials as assembly materials for SOFC battery stacks, for example, inter-connectors, etc., making it easy to manufacture and its mechanical strength / stability / Durability is also improved, and cost reduction of the entire SOFC can be expected. These technological developments are focused on materials research and development in universities and national laboratories and research institutes, and SOFC by reducing resistance and improving ion conduction / electric conductivity by developing materials. The power generation capacity is expected to improve.
本発明は、完全緻密なSOFC-MEA電解質層を有する固体酸化物形燃料電池を製造する方法を提供する。こうして作られるSOFC-MEAは、高操作性・耐久性・安定性を備え、電池セルの電気性能試験(Performance test of SOFC-MEA)によって検証できる。 The present invention provides a method of manufacturing a solid oxide fuel cell having a fully dense SOFC-MEA electrolyte layer. The SOFC-MEA produced in this way has high operability, durability and stability, and can be verified by a battery cell electrical performance test (Performance test of SOFC-MEA).
上記目標を達成するためには、マグネトロンスパッタリング法を中心とし、燃料電池膜電極接合体(Membrane Electrode Assembly, MEA)の製造に係わる膜形成方法のテープキャスティング法(Tape casting)・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)・プラスマスプレーコーティング法(Plasma spray coating)など及び膜を積層するラミネート法(Lamination)を併用して、焼結技術の設計やコントロールに合わせて、完全緻密/気密電解質層(材料は8YSZ・GDC (Gd doped ceria)・LSGM (strontium and magnesium doped lanthana gallat)などから選択する。) を製作する製造方法を提供する。 In order to achieve the above goal, the tape casting method and the silk screen printing method of the film formation method related to the manufacture of the fuel cell membrane electrode assembly (MEA), centering on the magnetron sputtering method ( Screen printing, spin coating, plasma spray coating, etc. and laminating methods for laminating films are used in combination with sintering technology design and control. / Provides a manufacturing method for manufacturing an airtight electrolyte layer (material is selected from 8YSZ, GDC (Gd doped ceria), LSGM (strontium and magnesium doped lanthana gallat), etc.).
本発明に示したマグネトロンスパッタリング法は(1)酸化物標的(oxide target)をスパッタリングするRFマグネトロンスパッタリング法(Radio frequency magnetron Sputtering)及び(2)直流(Direct Current)と高周波(Radio Frequency)の2タイプの反応性マグネトロンスパッタリング法で金属合金標的をスパッタリングする、という二種類がある。なお、酸化物標的の材料は、YSZ+NiO、GDC+NiO、LSGM+NiO、SDC+NiO、YDC+NiO、YSZ、GDC、LSGM、SDC、YDCであり、金属合金標的の材料は、Zrx-Y1-x、Zrx-Sc1-x、Cex-Gd1-x、Cex-Sm1-x、Cex-Y1-x (80<x<100 wt.%)、LSGMである。
例えば、陽極支持基板電池セル(Anode Supported Cell略称ASC)の場合は、本発明は、マグネトロンスパッタリング法により電解質の薄膜を陽極基板上に形成し、高温焼結過程を経て半電池の構造が得られる。更に、シルクスクリーン印刷法により陰極層を半電池構造に形成し、完全緻密な電解質層を有する陽極支持型固体酸化物形燃料電池を完成する。
The magnetron sputtering method shown in the present invention includes (1) RF magnetron sputtering method (Radio frequency magnetron sputtering) for sputtering an oxide target, and (2) two types of direct current and radio frequency. There are two types of sputtering of a metal alloy target by the reactive magnetron sputtering method. The oxide target materials are YSZ + NiO, GDC + NiO, LSGM + NiO, SDC + NiO, YDC + NiO, YSZ, GDC, LSGM, SDC, YDC, and the metal alloy target materials are Zr x -Y 1-x , Zr x -Sc 1-x, Ce x -Gd 1 -x, Ce x -Sm 1-x, Ce x -Y 1-x (80 <x <100 wt.%), a LSGM.
For example, in the case of an anode supported cell battery cell (ASC), the present invention forms a thin-cell electrolyte on the anode substrate by a magnetron sputtering method, and a half-cell structure is obtained through a high-temperature sintering process. . Further, a cathode layer is formed in a half-cell structure by a silk screen printing method, and an anode-supported solid oxide fuel cell having a completely dense electrolyte layer is completed.
本発明は、完全緻密(Full dense)並びに気体透過率ゼロ(Zero gas leakage rate)・或いは気密(Air tight)の電解質層を有する平板形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))を製作する方法である。電解質の材料は8YSZ・GDC・YDC・LSGMなどから選択する。本発明の完全緻密な電解質層を有する平板形固体酸化物形燃料電池膜電極接合体の作製方法を以下に説明する。 The present invention relates to a flat solid oxide fuel cell membrane electrode assembly (SOFC-MEA) having an electrolyte layer with full dense and zero gas leakage rate or air tight. That is, it is a method of manufacturing a battery cell (Unit cell). The electrolyte material is selected from 8YSZ, GDC, YDC, LSGM, etc. A method for producing a flat solid oxide fuel cell membrane electrode assembly having a completely dense electrolyte layer according to the present invention will be described below.
ステップ1:平板形SOFC-MEAの電極基板(Electrode Substrate)上に、マグネトロンスパッタリング(Magnetron Sputtering)法により電解質薄膜を形成する。電極基板上に5〜15μmの電解質薄膜を形成してSOFCの半電池(Half cell)を形成し、1200℃〜1600℃において数時間(3時間以上)の焼結を行い、第一段階の半電池が得られる。この段階の電解質の材料はYSZ・GDC・YDC・SmDC・LSGMなどから選択する。走査型電子顕微鏡(SEM)で半電池のマイクロ構造(Micro-structure)を解析して、無孔質(Open-pore free)のマイクロ構造及び完全緻密な状態を達成したことを確認する。 Step 1: An electrolyte thin film is formed on an electrode substrate (Electrode Substrate) of a flat plate SOFC-MEA by a magnetron sputtering method. A 5-15 μm electrolyte thin film is formed on the electrode substrate to form a SOFC half cell, and sintering is performed at 1200 ° C. to 1600 ° C. for several hours (over 3 hours). A battery is obtained. The electrolyte material at this stage is selected from YSZ, GDC, YDC, SmDC, and LSGM. Analyze the micro-structure of the half-cell with a scanning electron microscope (SEM) to confirm that an open-pore free microstructure and a fully dense state have been achieved.
ステップ2:半電池の電解質層の上にシルクスクリーン印刷法で多孔質(Porous)の陰極層を構築する。陰極層の材料は一般的にLSMかLSCFを適用する。1200℃において3時間の仮焼を行い、SOFC-MEAを完成する。 Step 2: A porous cathode layer is constructed on the half-cell electrolyte layer by silk screen printing. The material of the cathode layer is generally LSM or LSCF. Perform calcination for 3 hours at 1200 ℃ to complete SOFC-MEA.
本発明について代表的な例を挙げてさらに具体的に説明する。上記製作方法のステップ1およびステップ2の過程は図一に示す。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 typical examples. The process of Step 1 and Step 2 of the manufacturing method is shown in FIG. 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(Full dense)で気密性(Air tight)の電解質(材料は8YSZ/GDC/LSGMなどを採用。) 層を有する平板形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) を製作するためには、まず50 wt% のNiO+50 wt% の8YSZ及び特定量の造孔剤 (Pore former) と石墨(Graphite)で基本材料を構成し、テープキャスティング法によって5×5cm2〜 12×12 cm2のサイズに成形し、ラミネートにより1000μmの厚さに積層する。
〔Example〕
Step 1: Full dense and air tight electrolyte (material is 8YSZ / GDC / LSGM, etc.) Plate type solid oxide fuel cell membrane electrode assembly (SOFC-MEA) In order to manufacture a unit cell, the basic material is first composed of 50 wt% NiO + 50 wt% 8YSZ and a specific amount of pore former (Pore former) and graphite. It is formed into a size of 5 × 5 cm 2 to 12 × 12 cm 2 by a casting method and laminated to a thickness of 1000 μm by lamination.
ステップ2:RFマグネトロンスパッタリング法(標的物の材料は8YSZの酸化物)又はDCマグネトロンスパッタリング法(標的物の材料はZrxY1-x合金)によって電解質材料を電極基板上に堆積(deposit )させて、厚さ5〜10μmのSOFCの半電池(Half cell)を形成し、1200℃〜1600℃(1400℃が最適)において数時間(3時間以上)の焼結を行い、第一段階の半電池を得る。この半電池をSEM(走査型電子顕微鏡)でマイクロ構造を解析し、電解質層が無孔質(Open-pore free)のマイクロ構造になっていることを確認する。図二に示したように、電解質層の厚さは約5〜10μmで完全緻密な構造となり、気密性を備えていてSOFC-MEAの電解質層に対する要求を満たしている。残存する極くわずかな閉塞性の細孔は、気体透過率に影響を与えない。 Step 2: Deposit electrolyte material on the electrode substrate by RF magnetron sputtering method (target material is 8YSZ oxide) or DC magnetron sputtering method (target material is Zr x Y 1-x alloy) Then, form a SOFC half cell (Half cell) with a thickness of 5 to 10 μm, and sinter for several hours (3 hours or more) at 1200 ° C to 1600 ° C (1400 ° C is optimal). Get a battery. This half-cell is analyzed for microstructure by SEM (scanning electron microscope), and it is confirmed that the electrolyte layer has a non-porous (open-pore free) microstructure. As shown in FIG. 2, the thickness of the electrolyte layer is about 5 to 10 μm and has a completely dense structure, which is airtight and satisfies the requirements for the SOFC-MEA electrolyte layer. The very few obstructive pores that remain do not affect the gas permeability.
ステップ3:電解質の気密性能が完全であることを確認するため、ステップ2で得られた半電池の気体透過率を測定する。気体透過率が1×10-6 l/cm2/sec以下であれば、電解質は完全緻密性と認める。 Step 3: Measure the gas permeability of the half-cell obtained in Step 2 to confirm that the electrolyte's hermetic performance is complete. If the gas permeability is 1 × 10 −6 l / cm 2 / sec or less, the electrolyte is considered to be completely dense.
ステップ4:ステップ3で確認した完全緻密な半電池構造に対して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て、1100℃において3時間の焼結を行い、高動作性能のSOFC-MEA(Unit cell)を得る。この電池セルのマイクロ構造の横断面をSEMで解析した結果を図3に示す。完成したSOFC-MEAの電気性能試験を行った。
発電試験の温度は700/750/800℃で、試験気体は100%のH2/O2、流量は200/300/400 cc/minであった。試験中に電力は、減衰することなく120時間以上持続した。試験過程を、図4に示す。電池セルの開回路電圧(Open circuit voltage, OCV)は理論値に近く、最大数値は1.06 Vに達する。800℃における出力密度は最大限515 mW/cm2に達する(図5に示す)。これらの実験結果により、スパッタリング法によって製作した電解質層は緻密性を備え、作動が安定していて、電池セルの発電性能も優れていることが明らかとなった。
Step 4: Form a porous cathode layer with LSM material by silk screen printing on the fully dense half-cell structure confirmed in Step 3 and sinter at 1100 ° C for 3 hours. Obtain SOFC-MEA (Unit cell). FIG. 3 shows the result of SEM analysis of the cross section of the microstructure of the battery cell. The electrical performance test of the completed SOFC-MEA was conducted.
The temperature of the power generation test was 700/750/800 ° C., the test gas was 100% H 2 / O 2 , and the flow rate was 200/300/400 cc / min. During the test, power lasted over 120 hours without decay. The test process is shown in FIG. The open circuit voltage (OCV) of the battery cell is close to the theoretical value, and the maximum value reaches 1.06 V. The power density at 800 ° C reaches a maximum of 515 mW / cm 2 (shown in Figure 5). From these experimental results, it has been clarified that the electrolyte layer manufactured by the sputtering method has denseness, the operation is stable, and the power generation performance of the battery cell is excellent.
Claims (9)
(a) テープキャスティング法などにより、SOFCの陽極電極基板を形成する、
(b) 該電極基板上に酸化物標的をスパッタリングする高周波(RF)マグネトロンスパッタリング法又は金属合金標的をスパッタリングする反応性マグネトロンスパッタリング法により電解質薄膜層を形成する、
(c) 上記工程により作成した陽極/電解質の半電池構造体を1400℃において6時間の高温焼結を行って、電解質層の気体透過率が1×10-6 L/cm2 /sec以下の半電池基板を得る、
(d) 上記工程により得られた電解質層を有する半電池(略称HC-fd)の電解質層上に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)、或いはプラスマスプレーコーティング法(Plasma spray coating)によって陰極材料層を形成し、1000℃において3時間の焼結を行って全電池を得る、
工程からなることを特徴とする平板型固体酸化物形燃料電池膜電極接合体(SOFC-MEA) の製造方法。 A method for producing a flat plate solid oxide fuel cell membrane electrode assembly (SOFC-MEA), comprising:
(a) A SOFC anode electrode substrate is formed by a tape casting method or the like.
(b) forming an electrolyte thin film layer on the electrode substrate by a radio frequency (RF) magnetron sputtering method for sputtering an oxide target or a reactive magnetron sputtering method for sputtering a metal alloy target;
(c) The anode / electrolyte half-cell structure produced by the above process was sintered at 1400 ° C. for 6 hours at a high temperature, and the gas permeability of the electrolyte layer was 1 × 10 −6 L / cm 2 / sec or less. Get a half-cell board,
(d) On the electrolyte layer of a half-cell (abbreviated HC-fd) having an electrolyte layer obtained by the above process, a silk screen printing method, a spin coating method, or a plasma spray coating method (Plasma spray coating method) A cathode material layer is formed by spray coating), and sintering is performed at 1000 ° C. for 3 hours to obtain an entire battery.
A process for producing a plate-type solid oxide fuel cell membrane electrode assembly (SOFC-MEA), characterized by comprising steps.
上記ステップaの陽極基板材料はYSZ+NiO、GDC+NiO、LSGM+NiO、SDC+NiO、又はYDC+NiOであり、
電解質基板の材料は、YSZ(yttrium stabilized zirconia)、GDC(Gd doped ceria)、LSGM(strontium and magnesium doped lanthana gallat)、SDC(Sm doped ceria)、又はYDC(Y doped ceria)であって、電解質(例えばYSZ)と電極触媒材料NiOとの重量比の百分率は30〜65%であることを特徴とする請求項1記載の平板型固体酸化物形燃料電池膜電極接合体(SOFC-MEA) の製造方法。 In the method for producing an electrolyte layer of the flat plate type solid oxide fuel cell membrane electrode assembly (SOFC-MEA),
The anode substrate material of the above step a is YSZ + NiO, GDC + NiO, LSGM + NiO, SDC + NiO, or YDC + NiO,
The material of the electrolyte substrate is YSZ (yttrium stabilized zirconia), GDC (Gd doped ceria), LSGM (strontium and magnesium doped lanthana gallat), SDC (Sm doped ceria), or YDC (Y doped ceria). The percentage of the weight ratio of, for example, YSZ) to the electrode catalyst material NiO is 30 to 65%, and the production of a plate type solid oxide fuel cell membrane electrode assembly (SOFC-MEA) according to claim 1 Method.
陽極電極基板上に電解質層または機能界面層(functional interlayer)を積層したマルチターゲットスパッタリング法(multi-gun co-sputter)、又は電解質基板に電解質層或いは機能界面層を積層したマルチターゲットスパッタリング法(multi-gun co-sputter)によって行い、SOFC電解質層上に電極層を形成する方法は、スパッタリング法、シルクスクリーン印刷法、スピンコーティング法、又はプラスマスプレーコーティング法によることを特徴とする請求項1記載の平板型固体酸化物形燃料電池膜電極接合体(SOFC-MEA) の製造方法。 The magnetron sputtering method of step b above is
Multi-target sputtering method (multi-gun co-sputter) in which an electrolyte layer or functional interface layer is laminated on an anode electrode substrate, or multi-target sputtering method (multi-target sputtering method in which an electrolyte layer or functional interface layer is laminated on an electrolyte substrate) The method of forming an electrode layer on a SOFC electrolyte layer by using a -gun co-sputter) is based on a sputtering method, a silk screen printing method, a spin coating method, or a plasma spray coating method. A method for producing a plate-type solid oxide fuel cell membrane electrode assembly (SOFC-MEA).
金属合金標的をスパッタリングする反応性マグネトロンスパッタリング法に使う金属合金標的の材料は、Zrx-Y1-x、Zrx-Sc1-x、Cex-Gd1-x、Cex-Sm1-x、Cex-Y1-x (80<x<100 wt.%)、LSGMであることを特徴とする請求項1記載の平板型固体酸化物形燃料電池膜電極接合体(SOFC-MEA) の製造方法。 The oxide target materials used in the radio frequency magnetron sputtering method of the oxide target method in Step b above are YSZ + NiO, GDC + NiO, LSGM + NiO, SDC + NiO, YDC + NiO, YSZ, GDC, LSGM, SDC, YDC. ,
Reactive magnetron sputtering to sputter metal alloy targets The metal alloy target materials used in the sputtering method are Zr x -Y 1-x , Zr x -Sc 1-x , Ce x -Gd 1-x , Ce x -Sm 1- x, Ce x -Y 1-x (80 <x <100 wt.%), a flat plate type solid oxide fuel cell membrane electrode assembly according to claim 1, characterized in that the LSGM (SOFC-MEA) Manufacturing method.
ステップbの電解質層を製作する方法は、標的物の材料を8YSZの酸化物としたRFマグネトロンスパッタリング法、又は標的物の材料をZrxY1-x合金としたDCマグネトロンスパッタリング法によって電解質材料を電極基板上に堆積(deposit )させることを特徴とする請求項1記載の平板型固体酸化物形燃料電池膜電極接合体(SOFC-MEA) の製造方法。 In the method for producing an electrolyte layer of the high performance solid oxide fuel cell membrane electrode assembly (SOFC-MEA),
The electrolyte layer of step b is manufactured by RF magnetron sputtering using 8YSZ as the target material or DC magnetron sputtering using Zr x Y 1-x alloy as the target material. 2. The method for producing a flat plate type solid oxide fuel cell membrane electrode assembly (SOFC-MEA) according to claim 1, wherein the deposition is performed on an electrode substrate.
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