JPH084011B2 - Method for forming thin film of electrolyte in solid electrolyte fuel cell and solid electrolyte fuel cell - Google Patents
Method for forming thin film of electrolyte in solid electrolyte fuel cell and solid electrolyte fuel cellInfo
- Publication number
- JPH084011B2 JPH084011B2 JP1095426A JP9542689A JPH084011B2 JP H084011 B2 JPH084011 B2 JP H084011B2 JP 1095426 A JP1095426 A JP 1095426A JP 9542689 A JP9542689 A JP 9542689A JP H084011 B2 JPH084011 B2 JP H084011B2
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- fuel cell
- zirconium oxide
- thin film
- electrolyte fuel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
- H01M8/1253—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 the electrolyte containing zirconium oxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
- Coating By Spraying Or Casting (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、固体電解質燃料電池における電解質薄膜の
緻密度を向上させる薄膜形成方法および固体電解質燃料
電池に関する。Description: TECHNICAL FIELD The present invention relates to a thin film forming method and a solid electrolyte fuel cell for improving the density of an electrolyte thin film in a solid electrolyte fuel cell.
固体電解質燃料電池は、他の発電装置と比較して環境
の保全性がよく、効率が高く、しかもモジュラリティで
ある。近年、固体電解質燃料電池の上記利点が着目され
てきたので、固体電解質燃料電池に対する実用化の要望
が強くなってきた。The solid electrolyte fuel cell has good environmental conservation, high efficiency, and modularity as compared with other power generation devices. In recent years, attention has been paid to the above-mentioned advantages of the solid electrolyte fuel cell, and thus there has been a strong demand for practical application of the solid electrolyte fuel cell.
第４図ないし第６図を参照しつつ燃料電池の従来例を
説明する。第４図は単電池の原理説明図、第５図は従来
例における固体電解質燃料電池説明図、第６図は固体電
解質燃料電池構造説明図である。A conventional example of a fuel cell will be described with reference to FIGS. 4 to 6. FIG. 4 is an explanatory view of the principle of the unit cell, FIG. 5 is an explanatory view of a solid electrolyte fuel cell in a conventional example, and FIG. 6 is an explanatory view of a solid electrolyte fuel cell structure.
第５図において、20は基体管で、たとえば、酸化ジル
コニウムまたは酸化アルミニウムの円筒上に、マスクを
用いて後述する第６図の位置に固体電解質燃料電池を形
成する。基体管20は、ガスが厚さ方向に抜ける多孔質体
で、気孔率は30％程度のものである。21は前記基体管20
の上に形成された単電池で、ギャップ22を介して多数直
列に接続されて１個の集合電池を形成している。そし
て、燃料（H2、CO）および空気（O2）が基体管20の内外
に供給され、これらは前記各単電池21において電気と熱
に変換された後に、水（H2O）または炭素ガス（CO2）と
なって排出される。In FIG. 5, reference numeral 20 denotes a substrate tube, for example, a cylinder of zirconium oxide or aluminum oxide, which is used to form a solid electrolyte fuel cell at a position shown in FIG. The base tube 20 is a porous body through which gas escapes in the thickness direction and has a porosity of about 30%. 21 is the base tube 20
In the unit cell formed on the above, a plurality of cells are connected in series via the gap 22 to form one assembled battery. Then, fuel (H 2 , CO) and air (O 2 ) are supplied to the inside and outside of the base tube 20, and these are converted into electricity and heat in each of the unit cells 21, and then, water (H 2 O) or carbon. It is emitted as gas (CO 2 ).
ここで、単電池21の詳細な構成について第６図を参照
して説明する。Here, the detailed configuration of the unit cell 21 will be described with reference to FIG.
前記基体管20の上には、燃料極25たとえば、酸化ジル
コニウム（ZrO2）、酸化カルシウム（CaO）等が溶射に
よって形成される。この溶射方法は、先ず、酸化ジルコ
ニウム等の原料を５ないし15μｍの粉末にする。そし
て、この粉末をプラズマ・アークによって溶融し、不活
性ガスとともに基体管20に噴霧する。燃料極25の形成
は、燃料極25のギャップ30を設けるために、図示されて
いないマスクを使用して行われる。また、燃料極25の上
には、固体電解質26たとえば、酸化ジルコニウム（Zr
O2）、酸化カルシウム（CaO）等が、また、単電池を直
列接続するためのインターコネクタ・リード28たとえ
ば、コバルト・クロム・オキサイド（CoCr2O4）が第６
図図示のごとく上記と同様にして形成される。A fuel electrode 25, for example, zirconium oxide (ZrO 2 ), calcium oxide (CaO), or the like is formed on the base tube 20 by thermal spraying. In this thermal spraying method, a raw material such as zirconium oxide is first made into powder of 5 to 15 μm. Then, this powder is melted by a plasma arc and sprayed onto the base tube 20 together with an inert gas. The formation of the anode 25 is performed using a mask (not shown) to provide the gap 30 of the anode 25. Further, on the fuel electrode 25, a solid electrolyte 26 such as zirconium oxide (Zr
O 2 ), calcium oxide (CaO), etc., and an interconnector lead 28 for connecting cells in series, for example, cobalt chromium oxide (CoCr 2 O 4 ) is the sixth.
As shown in the figure, it is formed in the same manner as above.
さらに、固体電解質26とインターコネクタ・リード28
の上には、空気極27たとえば、酸化インジュウム（In2O
3）、酸化第２スズ（Sn2O3）等が空気極ギャップ22を設
けるようにして上記と同様に形成される。In addition, solid electrolyte 26 and interconnector lead 28
Above the air electrode 27, for example, indium oxide (In 2 O
3 ), stannous oxide (Sn 2 O 3 ) and the like are formed in the same manner as above with the air electrode gap 22 provided.
以上のような構成の固体電解質燃料電池において、第
６図図示符号21部分が単電池で、29が作動する電池部分
である。たとえば、基体管20上には、単電池21が多数直
列に接続されて集合電池を形成する。そして、多数の集
合電池はハウジング内に、一つの固体電解質燃料電池ユ
ニットとして組み立てられる。その他に、固体電解質燃
料電池ユニットには、図示されていないが、燃料（H2、
CO）、および空気（O2）供給用パイプ、および排ガス、
排熱等の回収用パイプ等が設けられている。In the solid oxide fuel cell having the above structure, reference numeral 21 in FIG. 6 is a single cell, and 29 is a cell portion which operates. For example, a large number of unit cells 21 are connected in series on the base tube 20 to form an assembled battery. Then, a large number of assembled cells are assembled into one solid electrolyte fuel cell unit in the housing. In addition, although not shown in the figure, the solid electrolyte fuel cell unit includes fuel (H 2 ,
CO) and air (O 2 ) supply pipes and exhaust gas,
A pipe for collecting exhaust heat and the like is provided.
このような構成の固体電解質燃料電池は、次のように
して動作する。すなわち、第４図図示のごとく、空気中
の酸素24は、空気極27で電子を受け取り、酸素イオンに
なって固体電解質26内を燃料極25へ移動する。The solid oxide fuel cell having such a structure operates as follows. That is, as shown in FIG. 4, oxygen 24 in the air receives electrons at the air electrode 27, becomes oxygen ions, and moves inside the solid electrolyte 26 to the fuel electrode 25.
一方、燃料極25では、前記酸素イオンと基体管20を通
過した水素または一酸化炭素23とが反応して電子を放出
する。この電子は、（−）極25′から負荷19を通って
（＋）極の空気極27′へ流れる。これを化学式で表せば
次のようになる。On the other hand, at the fuel electrode 25, the oxygen ions react with hydrogen or carbon monoxide 23 that has passed through the base tube 20 to emit electrons. The electrons flow from the (-) pole 25 'through the load 19 to the (+) pole air electrode 27'. This can be expressed as a chemical formula as follows.
空気極27において 燃料極25において H2＋O--→H2O＋2e- （２） 以上のように円筒状の固体電解質燃料電池について説
明したが、この他に燃料極、固体電解質、および空気極
等を板状に形成して、これらをサンドイッチ状に重ねる
方式のものがある。At air pole 27 In the fuel electrode 25 H 2 + O - → H 2 O + 2e - (2) or more as has been described cylindrical solid electrolyte fuel cell, the fuel electrode in addition, the solid electrolyte, and an air electrode or the like in a plate shape There is a method of forming and stacking these in a sandwich form.
しかし、単電池の起電力は、燃料極と空気極との酸素
分圧差によって決められる。すなわち、ネルンストの式
によると次のようになる。However, the electromotive force of the unit cell is determined by the oxygen partial pressure difference between the fuel electrode and the air electrode. That is, according to Nernst's formula, it becomes as follows.
ただし、 Ｒ＝8.31［j/mlk］ 気体定数 Ｆ＝9.65×104［c/rol］ファラデー定数 Ｔ ［Ｋ］ 温度 PX ［atm］ 分圧 Ａ 空気側 Ｆ 燃料側 Ｏ O2 Ｈ H2O KP［atm］1/2Ｈ＋1/2・O2→H2O 反応の平衡定数 以上（３）および（４）式から分かるように、単電池
の起電力を少しでも高く取るためには、空気極側の酸素
分圧差を高くする必要がある。しかし、空気極側だけ酸
素分圧差を高くしたり、あるいは多孔性を有する長い燃
料流路を同じ酸素分圧差にすることは、困難であった。 However, R = 8.31 [j / mlk] Gas constant F = 9.65 × 10 4 [c / rol] Faraday constant T [K] Temperature P X [atm] Partial pressure A Air side F Fuel side O O 2 H H 2 OK P [atm] 1/2 H + 1/2・ O 2 → H 2 O Equilibrium constant of reaction As can be seen from the above equations (3) and (4), in order to keep the electromotive force of a cell as high as possible, It is necessary to increase the oxygen partial pressure difference on the pole side. However, it has been difficult to increase the oxygen partial pressure difference only on the air electrode side or to make the long fuel passage having porosity the same oxygen partial pressure difference.
特に、電解質26を形成する場合には、プラズマ・アー
クの原料が粉末であると、粉末の粒子は完全に溶融しな
いうちに、不活性ガスとともに基体管側に飛ぶ。この場
合には、粉末の粒界に不活性ガスあるいは空気の巻き込
みができる。このため、電解質26内には、ボイドや粒界
にやる気孔が多く生じるので、この気孔を通して燃料
（水素または一酸化炭素）が空気極側にリークする。し
たがって、燃料極側に対する空気極即の酸素分圧差が低
くなるため、起電力は低下する。In particular, when forming the electrolyte 26, if the raw material of the plasma arc is a powder, the particles of the powder fly to the substrate tube side together with the inert gas before they are completely melted. In this case, inert gas or air can be entrained in the grain boundaries of the powder. Therefore, many voids and pores are formed in the electrolyte 26 at the grain boundaries, and the fuel (hydrogen or carbon monoxide) leaks to the air electrode side through these pores. Therefore, the oxygen partial pressure difference immediately with the air electrode with respect to the fuel electrode side is reduced, so that the electromotive force is reduced.
本発明は、以上のような問題を解決するために、電解
質膜の緻密度を向上できる固体電解質燃料電池における
電解質の薄膜形成方法および固体電解質燃料電池を提供
することを目的とする。In order to solve the above problems, it is an object of the present invention to provide a method for forming a thin film of an electrolyte in a solid electrolyte fuel cell and a solid electrolyte fuel cell capable of improving the density of the electrolyte membrane.
以上のような問題を解決するために、本発明の固体電
解質燃料電池における電解質の薄膜形成方法は、基体管
上に順次、燃料極、固体電解質およびインターコネクタ
・リード、空気極を溶射して集合電池を形成するもの
で、電解質の構成材料である酸化ジルコニウムをロッド
状に形成し、当該ロッド状酸化ジルコニウムをプラズマ
・アーク溶射機に、当該ロッド状酸化ジルコニウムがプ
ラズマ・アークの熱によって完全に溶融される速度で供
給すると共に、当該完全に溶融された酸化ジルコニウム
のみを不活性ガスと共に、回転している前記基体管に吹
き付けることを特徴とする。In order to solve the above problems, a method for forming a thin film of an electrolyte in a solid electrolyte fuel cell of the present invention is a method in which a fuel electrode, a solid electrolyte, an interconnector lead and an air electrode are sequentially sprayed and assembled on a base tube. A battery is formed by forming zirconium oxide, which is the constituent material of the electrolyte, into a rod shape, and the rod-shaped zirconium oxide is completely melted by the plasma arc spraying machine by the heat of the plasma arc. At the same rate, and only the completely melted zirconium oxide is sprayed together with an inert gas onto the rotating substrate tube.
本発明の固体電解質燃料電池は、前記薄膜形成方法に
よって形成されたセルからなることを特徴とする。The solid electrolyte fuel cell of the present invention is characterized by comprising cells formed by the thin film forming method.
本出願人は、プラズマ・アーク溶射方法において、粉
末原料の代わりに、電解質の構成材料である酸化ジルコ
ニウムをロッド状に形成し、当該ロッド状酸化ジルコニ
ウムをプラズマ・アーク溶射機の原料とすることに着目
した。In the plasma arc spraying method, the present applicant forms zirconium oxide, which is a constituent material of the electrolyte, in a rod shape instead of the powder raw material, and uses the rod-shaped zirconium oxide as a raw material of the plasma arc spraying machine. I paid attention.
また、本出願人は、酸化ジルコニウムがロッド状に形
成されているため、当該酸化ジルコニウムが完全に溶融
される速度に制御することが容易であることに気付い
た。Further, the applicant has found that since the zirconium oxide is formed in a rod shape, it is easy to control the rate at which the zirconium oxide is completely melted.
本発明は、ロッド状に成形された酸化ジルコニウムを
プラズマ・アークの熱によって完全に溶融した後に、こ
の完全に溶融した酸化ジルコニウムのみが不活性ガスと
共に基体管の表面に溶射される。そして、完全に溶融し
た酸化ジルコニウムは、不活性ガスと共に基体管の表面
に溶射された時に、展着し易くボイドあるいは粒界によ
る気孔が形成されない。したがって、このようなプラズ
マ溶射方法によって形成された薄膜は、気孔が少なく、
緻密度を向上させる。According to the present invention, after the zirconium oxide formed into a rod shape is completely melted by the heat of the plasma arc, only the completely melted zirconium oxide is sprayed on the surface of the base tube together with the inert gas. When the completely melted zirconium oxide is sprayed on the surface of the substrate tube together with the inert gas, it easily spreads and voids or voids due to grain boundaries are not formed. Therefore, the thin film formed by such a plasma spraying method has few pores,
Improves compactness.
また、上記プラズマ溶射方法により形成された電解質
は、気孔が少ないため、燃料がリークしないから、燃料
を効率良く燃焼する。Further, since the electrolyte formed by the plasma spraying method has few pores, the fuel does not leak, so that the fuel is efficiently burned.
さらに、上記方法により得られた電解質で構成した固
体電解質燃料電池の出力は向上した。Further, the output of the solid electrolyte fuel cell composed of the electrolyte obtained by the above method was improved.
第１図を参照しつつ本発明の一実施例を説明する。第
１図は本発明における固体電解質燃料電池薄膜形成方法
概念図である。An embodiment of the present invention will be described with reference to FIG. FIG. 1 is a conceptual diagram of a solid oxide fuel cell thin film forming method in the present invention.
第１図において、１は基体管で、たとえば、直径21m
m、長さ700mmの多孔質酸化ジルコニウム（ZrO2）から構
成されている。基体管１の上には、従来例と同様に、燃
料極、電解質、およびインターコネクタ・リード、空気
極を順次形成する。２は電解質等の被膜である。３は基
体管１を支える１方の軸受で、基体管１の他方は、基体
管回転装置４によって固定されている。そして、基体管
１の皮膜形成時には、基体管１は、前記基体管回転装置
４によって回転し得るように構成されている。In FIG. 1, reference numeral 1 is a base pipe, for example, a diameter of 21 m.
It is composed of porous zirconium oxide (ZrO 2 ) having a length of m and a length of 700 mm. A fuel electrode, an electrolyte, an interconnector lead, and an air electrode are sequentially formed on the base tube 1 as in the conventional example. Reference numeral 2 is a film such as an electrolyte. Reference numeral 3 denotes one bearing that supports the base tube 1, and the other of the base tubes 1 is fixed by a base tube rotating device 4. Then, when forming a film on the base tube 1, the base tube 1 is configured to be rotated by the base tube rotating device 4.
５はプラズマ・アーク溶射機の概略構成が示されてい
る。６はプラズマ・アーク溶射機の原料となるロッド
で、たとえば、電解質の薄膜を形成する場合、酸化ジル
コニウムである。７はロッド６を送るロッド送り装置
で、ロッドを矢印７′方向に送りつつ原料の供給を行
う。８はプラズマ・アーク発生装置で、電極９の間に高
熱のプラズマ・アーク10が発生する。11は不活性ガス供
給装置で、プラズマ・アーク10によって完全に溶融した
ロッド６の酸化ジルコニウムが、不活性ガスと共にノズ
ル12から基体管１に向かって溶射される。Reference numeral 5 shows a schematic structure of a plasma arc spraying machine. Reference numeral 6 is a rod which is a raw material of the plasma arc spraying machine, and is zirconium oxide when forming a thin film of the electrolyte. Reference numeral 7 denotes a rod feeding device for feeding the rod 6, which feeds the raw material while feeding the rod in the direction of arrow 7 '. A plasma arc generator 8 generates a high-heat plasma arc 10 between the electrodes 9. Reference numeral 11 is an inert gas supply device, and the zirconium oxide of the rod 6 completely melted by the plasma arc 10 is sprayed together with the inert gas from the nozzle 12 toward the substrate tube 1.
この時、基体管１に均等に被膜２が形成されるよう
に、基体管回転装置４により基体管１を回転させると共
に、プラズマ・アーク溶射機５も溶射機駆動装置13によ
って、レール14上を矢印15のごとく移動させる。したが
って、基体管１上には、端部から順次酸化ジルコニウム
の被膜２が形成される。At this time, the base tube 1 is rotated by the base tube rotating device 4 so that the coating film 2 is uniformly formed on the base tube 1, and the plasma arc sprayer 5 is also moved on the rail 14 by the sprayer drive device 13. Move it as shown by arrow 15. Therefore, the zirconium oxide coating film 2 is sequentially formed on the substrate tube 1 from the end.
ここで、第２図および第３図を参照しつつ本発明と従
来例とを比較する。第２図（イ）、（ロ）は本発明およ
び従来例において形成した被膜比較図、第３図（イ）、
（ロ）は本発明および従来例において形成した電解質酸
素分圧差説明図である。Here, the present invention and the conventional example will be compared with reference to FIG. 2 and FIG. FIGS. 2 (a) and 2 (b) are comparative views of coating films formed in the present invention and the conventional example, FIG. 3 (a),
(B) is an explanatory view of the electrolyte oxygen partial pressure difference formed in the present invention and the conventional example.
たとえば、本発明の電解質被膜は、完全に溶融したロ
ッド状酸化ジルコニウムを溶射して形成されるので、従
来の方法のように粉末の粒界に空気を巻き込むことがな
い。したがって、本発明の方法により形成された被膜２
は、第２図（イ）のごとく気孔16が少ない。これに対し
て、従来の方法の場合には、プラズマ・アーク溶射機の
原料が粉末のため、粉末が完全に溶融しないうちに溶射
される。このために粉末の粒界にボイドが生じたり、あ
るいは空気が巻き込まれ易く第２図（ロ）のごとく、気
孔16が本発明のものより存在する。For example, since the electrolyte coating of the present invention is formed by spraying completely molten rod-shaped zirconium oxide, air is not entrained in the grain boundaries of the powder unlike the conventional method. Therefore, the coating 2 formed by the method of the present invention
Has a small number of pores 16 as shown in FIG. On the other hand, in the case of the conventional method, since the raw material of the plasma arc sprayer is powder, the powder is sprayed before the powder is completely melted. Therefore, voids are generated in the grain boundaries of the powder, or air is apt to be entrained, and as shown in FIG. 2B, the pores 16 are present more than those of the present invention.
ここで、燃料が電解質を通過する場合を検討する。前
記（３）および（４）式で分かるように、燃料極に対す
る空気極の酸素分圧差の高い場合には、高い起電力が得
られる。すなわち、本発明の方法によって得られた被膜
２には、気孔16が少ないため、第３図（イ）に図示され
ているように、電解質内での燃料のリークは少ない。し
たがって、本発明の方法により形成された電解質の酸素
分圧差は、高く燃料の燃焼効率が良い。Now consider the case where the fuel passes through the electrolyte. As can be seen from the expressions (3) and (4), a high electromotive force can be obtained when the oxygen partial pressure difference between the air electrode and the fuel electrode is high. That is, since the coating film 2 obtained by the method of the present invention has few pores 16, there is little fuel leakage in the electrolyte, as shown in FIG. Therefore, the oxygen partial pressure difference of the electrolyte formed by the method of the present invention is high and the fuel combustion efficiency is good.
これに対して、従来の方法により形成された電解質で
は、気孔16が多いため、第３図（ロ）に図示されている
ように、電解質内での燃料のリークが多い。したがっ
て、従来例の方法により形成された電解質の酸素分圧差
は、低く燃料の燃焼効率が悪い。On the other hand, since the electrolyte formed by the conventional method has many pores 16, as shown in FIG. 3B, there is a large amount of fuel leakage in the electrolyte. Therefore, the oxygen partial pressure difference of the electrolyte formed by the conventional method is low and the fuel combustion efficiency is poor.
以上、本発明の実施例を詳述したが、本発明は、前記
実施例に限定されるものではない。そして、特許請求の
範囲に記載された本発明を逸脱することがなければ、種
々の設計変更を行うことが可能である。Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above embodiments. Various design changes can be made without departing from the present invention described in the claims.
たとえば、不活性ガスの種類および供給圧力、基体管
の回転速度、溶射機駆動装置の送り速度、あるいは被膜
の厚さ等は、適宜設計変更できる。For example, the type and supply pressure of the inert gas, the rotation speed of the substrate tube, the feed speed of the thermal sprayer drive device, the thickness of the coating, and the like can be appropriately designed and changed.
本発明によれば、電解質の構成材料である酸化ジルコ
ニウムをロッド状に形成し、当該ロッド状酸化ジルコニ
ウムを完全に溶融する速度で供給できるため、酸化ジル
コニウムがプラズマ・アークの熱によって完全に溶融し
た後に、酸化ジルコニウムのみを不活性ガスと共に基体
管の表面に溶射するので、ボイドや空気の巻き込みによ
る気孔が形成されない。According to the present invention, since zirconium oxide, which is a constituent material of the electrolyte, can be formed into a rod shape and the rod-shaped zirconium oxide can be supplied at a rate of completely melting the zirconium oxide, the zirconium oxide is completely melted by the heat of the plasma arc. After that, since only zirconium oxide is sprayed on the surface of the substrate tube together with the inert gas, voids or voids due to air entrapment are not formed.
したがって、本発明の方法によって形成された電解質
の薄膜は、気孔が少なく高い緻密度のため、燃料のリー
クがないから、燃料を効率良く燃焼する。Therefore, since the electrolyte thin film formed by the method of the present invention has few pores and high density, there is no fuel leak, and the fuel is efficiently burned.
また、本発明によれば、酸化ジルコニウムをロッド状
に形成しているため、完全に溶融される速度に制御する
ことが容易にできる。Further, according to the present invention, since the zirconium oxide is formed in a rod shape, it is possible to easily control the rate of complete melting.
また、本発明によれば、上記方法により得られた電解
質で構成した固体電解質燃料電池の出力は向上した。Further, according to the present invention, the output of the solid electrolyte fuel cell composed of the electrolyte obtained by the above method is improved.
第１図は本発明における固体電解質燃料電池薄膜形成方
法概念図、第２図（イ）、（ロ）は本発明および従来例
において形成した被膜比較図、第３図（イ）、（ロ）は
本発明および従来例において形成した電解質酸素分圧差
説明図、第４図は単電池の原理説明図、第５図は従来例
における固体電解質燃料電池説明図、第６図は固体電解
質燃料電池構造説明図である。 １……基体管 ２……被膜 ３……軸受 ４……基体管回転装置 ５……プラズマ・アーク溶射機 ６……ロッド ７……ロッド送り装置 ８……プラズマ・アーク発生装置 ９……電極 10……プラズマ・アーク 11……不活性ガス供給装置 12……ノズル 13……溶射機駆動装置 14……レールFIG. 1 is a conceptual diagram of a method for forming a solid electrolyte fuel cell thin film in the present invention, FIGS. 2 (a) and 2 (b) are comparative diagrams of coating films formed in the present invention and a conventional example, and FIGS. 3 (a) and 3 (b). Is an explanatory view of the partial pressure difference of the electrolyte oxygen formed in the present invention and the conventional example, FIG. 4 is an explanatory view of the principle of the unit cell, FIG. 5 is an explanatory view of the solid electrolyte fuel cell in the conventional example, and FIG. FIG. 1 ... Substrate tube 2 ... Coating 3 ... Bearing 4 ... Substrate tube rotating device 5 ... Plasma arc spraying machine 6 ... Rod 7 ... Rod feeding device 8 ... Plasma arc generating device 9 ... Electrode 10 …… plasma arc 11 …… inert gas supply device 12 …… nozzle 13 …… sprayer drive device 14 …… rail
Claims (2)
びインターコネクタ・リード、空気極を溶射して集合電
池を形成する固体電解質燃料電池における電解質の薄膜
形成方法において、 電解質の構成材料である酸化ジルコニウムをロッド状に
形成し、当該ロッド状酸化ジルコニウムをプラズマ・ア
ーク溶射機に、当該ロッド状酸化ジルコニウムがプラズ
マ・アークの熱によって完全に溶融される速度で供給す
ると共に、 当該完全に溶融された酸化ジルコニウムのみを不活性ガ
スと共に、回転している前記基体管に吹き付ける ことを特徴とする固体電解質燃料電池における電解質の
薄膜形成方法。1. A method for forming an electrolyte thin film in a solid electrolyte fuel cell, wherein a fuel electrode, a solid electrolyte, an interconnector lead, and an air electrode are sequentially sprayed on a base tube to form an assembled battery. A certain zirconium oxide is formed into a rod shape, and the rod-shaped zirconium oxide is supplied to a plasma arc sprayer at a rate at which the rod-shaped zirconium oxide is completely melted by the heat of the plasma arc, and is also completely melted. A method for forming a thin film of an electrolyte in a solid electrolyte fuel cell, characterized in that only the produced zirconium oxide is sprayed together with an inert gas onto the rotating substrate tube.
からなることを特徴とする請求項１記載の固体電解質燃
料電池。2. The solid electrolyte fuel cell according to claim 1, comprising a cell formed by the thin film forming method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1095426A JPH084011B2 (en) | 1989-04-17 | 1989-04-17 | Method for forming thin film of electrolyte in solid electrolyte fuel cell and solid electrolyte fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1095426A JPH084011B2 (en) | 1989-04-17 | 1989-04-17 | Method for forming thin film of electrolyte in solid electrolyte fuel cell and solid electrolyte fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0374059A JPH0374059A (en) | 1991-03-28 |
| JPH084011B2 true JPH084011B2 (en) | 1996-01-17 |
Family
ID=14137371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1095426A Expired - Lifetime JPH084011B2 (en) | 1989-04-17 | 1989-04-17 | Method for forming thin film of electrolyte in solid electrolyte fuel cell and solid electrolyte fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH084011B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61198570A (en) * | 1985-02-28 | 1986-09-02 | Mitsubishi Heavy Ind Ltd | Manufacture of solid electrolyte fuel cell |
| JPS63450A (en) * | 1986-06-20 | 1988-01-05 | Mitsubishi Heavy Ind Ltd | Formation of solid electrolyte |
| JPS6381768A (en) * | 1986-09-26 | 1988-04-12 | Mitsubishi Heavy Ind Ltd | Solid electrolyte fuel cell and manufacture thereof |
-
1989
- 1989-04-17 JP JP1095426A patent/JPH084011B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0374059A (en) | 1991-03-28 |
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