JP2004127804A - Film forming device and method of cell tube for cylindrical fuel cell - Google Patents

Film forming device and method of cell tube for cylindrical fuel cell Download PDF

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Publication number
JP2004127804A
JP2004127804A JP2002292224A JP2002292224A JP2004127804A JP 2004127804 A JP2004127804 A JP 2004127804A JP 2002292224 A JP2002292224 A JP 2002292224A JP 2002292224 A JP2002292224 A JP 2002292224A JP 2004127804 A JP2004127804 A JP 2004127804A
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tube
forming
slurry
mold
film
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JP4064777B2 (en
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Kazuo Tomita
冨田　和男
Osao Kudome
久留　長生
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Mitsubishi Heavy Industries Ltd
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Mitsubishi Heavy Industries Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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

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Abstract

<P>PROBLEM TO BE SOLVED: To reduce manufacturing manhours while maintaining the performance, compared with a conventional device. <P>SOLUTION: The film forming device of a cell tube for a cylindrical fuel cell forms a fuel electrode, an electrolyte, an interconnector, and an air electrode on the surface of a substrate pipe. The film forming device comprises an annular hollow metallic mold 21 arranged on the periphery of a base tube 22, a mold frame 23 provided at the base tube side of the hollow metallic mold 21, a slurry introduction tube 26 connected to the hollow metallic mold 21 for injecting film forming slurry 25 into the periphery of the base tube 22, and a gas introduction tube 28 for pressing the mold frame 23 by supplying gas to a hollow part 27 formed by the hollow metallic mold 21 and the mold frame 23. <P>COPYRIGHT: (C)2004,JPO

Description

【０００１】
【発明の属する技術分野】
本発明は、円筒型燃料電池セルチューブの製膜装置及び製膜方法に関する。
【０００２】
【従来の技術】
周知の如く、円筒型燃料電池としては、例えば図５に示すものが知られている。同燃料電池は、多孔質円筒管１の外周部に燃料極２、電解質３及び空気極４からなる単セルを形成し、これら単セル間をインタコネクタ５を用いて電気的に接続するものである。
【０００３】
ところで、こうした燃料電池において、各構成部材である燃料極２、電解質３、空気極４、インタコネクタ５は、従来スクリーン印刷法により各構成部材の材料であるスラリーを基体管に印刷、乾燥を繰り返すことにより製膜していた。しかし、各構成部材の膜厚は２０〜１０００μｍに分かれており、印刷法では１回に印刷できる膜厚は５〜１５０μｍであるため、厚い膜（例えば空気極の膜）では１０回程度の印刷が必要となる。従って、工数の低減には限界があった。
【０００４】
このため、本発明者等は、先に貼付法による製膜法を提案した（特開２００１−１７６５２３号公報）。この製膜法は、図４に示すように、基体管１１の表面に燃料極（図示せず）、電解質１２、インタコネクタ１３を予めスクリーン印刷用により順次製膜してセルチューブ１４を形成したものであり、このセルチューブ１４に空気極用のリボン状成膜材１５を貼着、巻装し、その後焼成により空気極を形成するものである。
【０００５】
【特許文献１】
特開２００１−１７６５２３号公報（第３−４頁、図４）
【０００６】
【発明が解決しようとする課題】
しかし、こうしたスクリーン印刷を用いた貼付法によれば、厚い膜の製膜が可能であるので工数を低減できるという長所を有するものの、焼成後の電解質と空気極界面の抵抗が高くなり、性能が低下するという問題があった。
【０００７】
本発明はこうした事情を考慮してなされたもので、基体管の外周部に配置される環状の中空金型と、この中空金型の基体管側に設けられた型枠と、前記中空金型に連結され，基体管の外周部に製膜用スラリーを注入するためのスラリー導入管と、前記中空金型と型枠とで形成される中空部に気体を供給して前記型枠を押圧する気体導入管とを具備した構成とすることにより、従来と比べ、少ない工数でかつ性能低下を回避しえる円筒型燃料電池セルチューブの製膜装置を提供することを目的とする。
【０００８】
また、本発明は、前記製膜装置を用いて、基体管の表面に燃料極、電解質、インタコネクタ及び空気極を製膜して円筒型燃料電池のセルチューブを製膜する方法であり、基体管の外周部に製膜用スラリーを貼着した後、気体導入管から気体を送って型枠を押圧することにより基体管に貼着した製膜用スラリーを押圧し、更に乾燥、焼成することにより、従来と比べ、少ない工数でかつ性能低下を回避しえる円筒型燃料電池セルチューブの製膜方法を提供することを目的とする。
【０００９】
更には、本発明は、前記基体管の表面に燃料極、電解質、インタコネクタを予めスクリーン印刷用により順次製膜してセルチューブを形成した後、このセルチューブに空気極用のリボン状製膜材を貼着、巻装し、焼成により空気極を形成する工程を具備し、前記リボン状製膜材は発泡材に製膜用スラリーを含浸させることにより、従来と比べ、少ない工数でかつ性能低下を回避しえる円筒型燃料電池セルチューブの製膜方法を提供することを目的とする。
【００１０】
【課題を解決するための手段】
本願第１の発明は、基体管の表面に燃料極、電解質、インタコネクタ及び空気極を製膜して円筒型燃料電池のセルチューブを製膜する装置において、前記基体管の外周部に配置される環状の中空金型と、この中空金型の基体管側に設けられた型枠と、前記中空金型に連結され，基体管の外周部に製膜用スラリーを注入するためのスラリー導入管と、前記中空金型と型枠とで形成される中空部に気体を供給して前記型枠を押圧する気体導入管とを具備することを特徴とする円筒型燃料電池セルチューブの製膜装置である。
【００１１】
本願第２の発明は、請求項１記載の製膜装置を用いて、基体管の表面に燃料極、電解質、インタコネクタ及び空気極を製膜して円筒型燃料電池のセルチューブを製膜する方法であり、基体管の外周部に製膜用スラリーを貼着した後、気体導入管から気体を送って型枠を押圧することにより基体管に貼着した製膜用スラリーを押圧し、更に乾燥、焼成することを特徴とする円筒型燃料電池セルチューブの製膜方法である。
【００１２】
本願第３の発明は、基体管の表面に燃料極、電解質、インタコネクタ及び空気極を製膜して円筒型燃料電池のセルチューブを製膜する方法において、前記基体管の表面に燃料極、電解質、インタコネクタを予めスクリーン印刷法により順次製膜してセルチューブを形成した後、このセルチューブに空気極用のリボン状製膜材を貼着、巻装し、焼成により空気極を形成する工程を具備し、前記リボン状製膜材は発泡材に製膜用スラリーを含浸させたものであることを特徴とする円筒型燃料電池のセルチューブの製膜方法である。
【００１３】
【発明の実施の形態】
以下、本発明の実施例に係る円筒型燃料電池セルチューブの製膜装置及びその製膜方法について更に詳しく説明する。
【００１４】
第１、２の発明において、型枠としては、例えばゴム枠のようにクッション性を有してかつ通気性が殆ど無い材料が好ましい。ここで、型枠の形状は特に限定されること無く、基体管上に堆積した製膜用スラリーを気体導入管から導入した気体により型枠を介して押圧できる形状であればよい。その例として、後述するが、図１〜図３のように中空金型と一体のもの、あるいは図６に示すように中空金型の内側で内側及び外側に移動可能なものが挙げられる。なお、気体導入管から導入する気体としては、例えば空気が挙げられるが、これに限定されず、窒素、アルゴン等の不活性ガスでもよい。
【００１５】
また、前記中空金型の数も特に制限されず、セルチューブの長さに応じて適宜設定することができる。更に、中空金型に連結するスラリー導入管の数も適宜設定すればよいが、その配置は、製膜用スラリーを基体管上にできるだけ均等に堆積するために基体管の周方向に沿って等間隔に配置することが好ましい。
【００１６】
第３の発明において使用される前記製膜用スラリーとしては、粉体濃度２０〜８０％のランタン系ペロブスカイトと溶剤からなるスラリーが挙げられる。ランタン系ペロブスカイトとしては、例えばＬａＭｎＯ３、ＬａＣｏＯ３等が挙げられる。前記発泡材としては、例えばウレタンフォームのようにサブミクロンから数百ミクロンの穴が得られるものが好ましい。ここで、穴径がサブミクロン未満ではガスが通りにくくセルの性能が低下し、逆に穴径が数百ミクロンを越えると電流が流れにくくなる。なお、粉体濃度を上記の範囲に設定するのは、濃度が２０％未満ではスラリーの粘度、降伏値が低すぎるからであり、濃度が８０％を越えるとスラリーの粘度、降伏値が高すぎ、発泡材に含浸しにくいからである。前記溶剤としては、例えば水、石油製製品が挙げられる。
【００１７】
【実施例】
以下、本発明の実施例について図面を参照して説明する。
（実施例１）
図１、図２及び図３を参照する。ここで、図１は本実施例１に係る円筒型燃料電池セルチューブの製膜装置の全体図、図２は図１の要部の拡大図、図３は図１のＸ−Ｘ線に沿う断面図を示す。
【００１８】
図中の符番２１は、基体管２２の外周部に複数個取り付けられた環状の中空金型を示す。前記中空金型２１の前記基体管２２側には、ゴム枠（型枠）２３が配置されている。前記中空金型２１には、基体管２２とゴム枠２３で形成される空間部２４に位置する基体管２２の外周部に製膜用スラリー２５を注入するためのスラリー導入管２６が中空金型２１の周方向に等間隔で設けられている（図２，３参照）。また、前記中空金型２１には、該中空金型２１とゴム枠２３で形成される中空部２７に連通する空気導入管（ガス導入管）２８が設けられている。
【００１９】
このように、実施例１に係る製膜装置は、基体管２２の外周部に配置される環状の中空金型２１と、該中空金型２１の基体管側に配置されたゴム枠２３と、前記中空金型２１が連結され，基体管２２の外周部に製膜用スラリー２５を注入するためのスラリー導入管２６と、前記中空金型２１と型枠２３とで形成される中空部２７に空気を供給して前記型枠２３を押圧する空気導入管２８とを具備した構成となっている。
【００２０】
こうした構成の製膜装置を用いて製膜を行う場合は次のようにして行う。
まず、基体管２２の外周部に複数個の中空金型２１を図１に示すように配置した。次に、スラリー導入管２６より中空金型２１の空間部２４に製膜用スラリー２５を注入して、空間部２４に位置する基体管２２上に堆積した。ここで、製膜用スラリー２５としては、空気極スラリーを用いた。つづいて、空気導入管２６から中空金型２１の中空部２７に空気を送り、これにより中空部２７を高圧にして前記ゴム枠２３を基体管２２側に押圧し、空間部２４の製膜用スラリー２５を基体管２２側に押し付ける。更に、中空金型２１を基体管２２から外した後、製膜用スラリー２５を乾燥、焼成することにより、空気極を形成した。また、空気極と同様な方法により、燃料極、電解質、インタコネクタを形成して円筒型燃料電池のセルチューブを製造した。
【００２１】
このような、製膜方法によれば、１回製膜用スラリーを注入した後、乾燥、焼成することにより膜厚が厚い燃料電池の構成部材も形成できるため、各構成部材ごとに印刷、乾燥工程を何度も繰り返す必要がないので、従来と比べ、少ない工数で各構成部材を形成することができる。また、従来の貼着法と比べて電池の性能低下を回避することができる。
【００２２】
（実施例２）
図６を参照する。図６は、本実施例２に係る円筒型燃料電池セルチューブの製膜装置の金型部分のみを示している。但し、図１〜図３と同部材は同符番を付し、要部のみ説明する。
図中の符番３１は、前記基体管２２の外周部に配置される環状の中空金型を示す。この金型３１は、前記基体管２２側で内側に折り曲げられ、前記ゴム枠２３を支持するための段差部３２を有している。ここで、ゴム枠２３は通常は点線Ｘのように位置している。スラリー導入管２６は、金型３１とゴム枠２３と基体管２２で形成される空間部２４の基体管上に製膜用スラリー２５を注入するように金型３１と連結している。また、空気導入管２８は、金型３１の外壁に取り付けられて、空気を導入することによりゴム枠２３を基体管側に押圧するように金型３１と連結している。
【００２３】
こうした製膜装置を用いて製膜を行う場合は次のようにして行う。
まず、基体管２２の外周部に複数個の金型３１を図１に示すように配置した。次に、スラリー導入管２５より空間部２４に製膜用スラリー２５を注入し、空間部２４に位置する基体管２２上に製膜用スラリー２８を堆積した。つづいて、空気導入管２８から中空金型２１の空洞部２７内に空気を送り、これにより空洞部２７内を高圧にしてゴム枠２３を基体管２２側に押圧し、製膜用スラリー２８を基体管２１側に押し付ける。更に、中空金型２１を基体管２２から外した後、製膜用スラリー２８を乾燥、焼成することにより、空気極を形成した。また、空気極と同様な方法により、燃料極、電解質、インタコネクタを形成して円筒型燃料電池のセルチューブを製造した。
【００２４】
（実施例３）
図７（Ａ），（Ｂ）を参照する。ここで、図７（Ａ）は本実施例３の製膜方法の説明図、図７（Ｂ）は焼成時のセルチューブの断面図を示す。但し、図５と同部材は同符番を付して説明する。
【００２５】
まず、基体管１の表面に燃料極２、電解質３、インタコネクタ５を予めスクリーン印刷用により順次製膜してセルチューブ４１を形成した。次に、このセルチューブ４１に空気極用のリボン状製膜材４２を貼着、巻装した。ここで、リボン状製膜材４２としては、ウレタンフォーム等の発泡材に製膜用スラリー２５を含浸させたものを用いた。また、製膜用スラリー２５としては、粉体濃度が例えば６０％のランタン系ペロブスカイトに溶剤を加えたスラリーを用いた。つづいて、図７（Ｂ）のようにセルチューブ４１に巻装したリボン状製膜材４２の境界部を例えばテープ４３で固定した後、焼成して空気極４を形成し、セルチューブを製造した。なお、焼成時、発泡材は飛散するので、比較的厚い空気極が得られる。
【００２６】
実施例３によれば、実施例１と同様な効果を得ることができる。
なお、焼成後の膜の気孔率は、発泡材の密度（気孔度）及び製膜用スラリー中の粉体濃度によって制御する。粉体濃度は、全体を１００％としたとき、２０〜８０％程度が好ましい。
【００２７】
【発明の効果】
以上詳述したように本発明によれば、基体管の外周部に配置される環状の中空金型と、この中空金型の基体管側に設けられた型枠と、前記中空金型に連結され，基体管の外周部に製膜用スラリーを注入するためのスラリー導入管と、前記中空金型と型枠とで形成される中空部に気体を供給して前記型枠を押圧する気体導入管とを具備した構成とすることにより、従来と比べ、少ない工数でかつ性能低下を回避しえる円筒型燃料電池セルチューブの製膜装置を提供できる。
【００２８】
また、本発明によれば、前記製膜装置を用いて、基体管の表面に燃料極、電解質、インタコネクタ及び空気極を製膜して円筒型燃料電池のセルチューブを製膜する方法であり、基体管の外周部に製膜用スラリーを貼着した後、気体導入管から気体を送って型枠を押圧することにより基体管に貼着した製膜用スラリーを押圧し、更に乾燥、焼成することにより、従来と比べ、少ない工数でかつ性能低下を回避しえる円筒型燃料電池セルチューブの製膜方法を提供できる。
【００２９】
更には、本発明によれば、基体管の表面に燃料極、電解質、インタコネクタを予めスクリーン印刷用により順次製膜してセルチューブを形成した後、このセルチューブに空気極用のリボン状製膜材を貼着、巻装し、焼成により空気極を形成する工程を具備し、前記リボン状製膜材は発泡材に製膜用スラリーを含浸させることにより、従来と比べ、少ない工数でかつ性能低下を回避しえる円筒型燃料電池セルチューブの製膜方法を提供できる。
【図面の簡単な説明】
【図１】本発明の実施例１に係る円筒型燃料電池セルチューブの製膜装置の全体図。
【図２】図１の要部の拡大図
【図３】図１のＸ−Ｘ線に沿う断面図
【図４】従来の円筒型燃料電池セルチューブの製膜方法の説明図。
【図５】円筒型燃料電池の説明図。
【図６】本発明の実施例２に係る円筒型燃料電池セルチューブの製膜装置の全体図。
【図７】本発明の実施例３に係る円筒型燃料電池セルチューブの製膜方法の説明図。
【符号の説明】
１，２２…基体管、
２…燃料極、
３…電解質、
５…インタコネクタ、
２１，３１…中空金型、
２３…ゴム枠（型枠）、
２４…空間部、
２５…製膜用スラリー、
２６…スラリー導入管、
２７…中空部、
２８…空気導入管（気体導入管）、
３２…段差部、
４１…セルチューブ、
４２…リボン状製膜材、
４３…テープ。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a film forming apparatus and a film forming method for a cylindrical fuel cell tube.
[0002]
[Prior art]
As is well known, for example, a cylindrical fuel cell shown in FIG. 5 is known. In the fuel cell, a single cell including a fuel electrode 2, an electrolyte 3 and an air electrode 4 is formed on an outer peripheral portion of a porous cylindrical tube 1, and these single cells are electrically connected using an interconnector 5. is there.
[0003]
Meanwhile, in such a fuel cell, the fuel electrode 2, the electrolyte 3, the air electrode 4, and the interconnector 5, which are the respective constituent members, repeatedly print and dry the slurry, which is the material of the respective constituent members, on the base tube by the conventional screen printing method. In this way, a film was formed. However, the film thickness of each component is divided into 20 to 1000 μm, and the film thickness that can be printed at one time in the printing method is 5 to 150 μm, so that a thick film (for example, a film of an air electrode) is printed about 10 times. Is required. Therefore, there is a limit in reducing the number of steps.
[0004]
For this reason, the present inventors have previously proposed a film forming method by the sticking method (Japanese Patent Application Laid-Open No. 2001-176523). In this film forming method, as shown in FIG. 4, a fuel electrode (not shown), an electrolyte 12, and an interconnector 13 were previously formed on the surface of the base tube 11 in advance by screen printing to form a cell tube 14. A ribbon-shaped film-forming material 15 for an air electrode is attached and wound on the cell tube 14, and then the air electrode is formed by firing.
[0005]
[Patent Document 1]
JP 2001-176523 A (page 3-4, FIG. 4)
[0006]
[Problems to be solved by the invention]
However, such an attachment method using screen printing has the advantage that the number of steps can be reduced because a thick film can be formed, but the resistance between the electrolyte and the air electrode interface after firing is increased, and the performance is increased. There was a problem of lowering.
[0007]
The present invention has been made in view of such circumstances, and has an annular hollow mold disposed on an outer peripheral portion of a base tube, a mold provided on the base tube side of the hollow mold, and the hollow mold. And pressurize the mold by supplying gas to a slurry introduction tube for injecting a slurry for film formation into the outer peripheral portion of the base tube, and a hollow portion formed by the hollow mold and the mold. An object of the present invention is to provide a film forming apparatus for a cylindrical fuel cell tube, which has a configuration including a gas introduction pipe and requires less man-hours and can avoid a decrease in performance as compared with the related art.
[0008]
Further, the present invention is a method of forming a fuel electrode, an electrolyte, an interconnector and an air electrode on the surface of a base tube using the film forming apparatus to form a cell tube of a cylindrical fuel cell. After adhering the film-forming slurry to the outer peripheral portion of the tube, the gas is sent from the gas introduction tube to press the mold, thereby pressing the film-forming slurry adhered to the base tube, and further drying and firing. Accordingly, an object of the present invention is to provide a method for forming a cylindrical fuel cell tube that requires less man-hours and avoids performance degradation as compared with the related art.
[0009]
Further, according to the present invention, a fuel electrode, an electrolyte, and an interconnector are sequentially formed on the surface of the base tube in advance by screen printing to form a cell tube, and then a ribbon-shaped film formation for an air electrode is formed on the cell tube. A process of attaching, winding, and baking a material to form an air electrode. The ribbon-like film forming material impregnates a foaming material with a film forming slurry, thereby reducing the number of processes and performance compared to the conventional method. It is an object of the present invention to provide a method of forming a cylindrical fuel cell tube that can avoid a decrease.
[0010]
[Means for Solving the Problems]
The first invention of the present application is an apparatus for forming a cell tube of a cylindrical fuel cell by forming a fuel electrode, an electrolyte, an interconnector, and an air electrode on the surface of a base tube. An annular hollow mold, a mold frame provided on the base tube side of the hollow mold, and a slurry introduction tube connected to the hollow mold for injecting a slurry for film formation into the outer peripheral portion of the base tube. And a gas introduction pipe for supplying gas to a hollow portion formed by the hollow mold and the mold to press the mold, and forming a film of the cylindrical fuel cell tube. It is.
[0011]
According to a second aspect of the present invention, a fuel electrode, an electrolyte, an interconnector, and an air electrode are formed on the surface of a base tube by using the film forming apparatus according to claim 1 to form a cell tube of a cylindrical fuel cell. The method is to apply the film-forming slurry to the outer peripheral portion of the substrate tube, and then press the mold-forming slurry by sending gas from the gas introduction tube to press the mold, and further press the film-forming slurry. A method for forming a cylindrical fuel cell tube, comprising drying and firing.
[0012]
The third invention of the present application is directed to a method of forming a fuel electrode, an electrolyte, an interconnector and an air electrode on the surface of a base tube to form a cell tube of a cylindrical fuel cell. After the electrolyte and the interconnector are sequentially formed into a film by a screen printing method to form a cell tube, a ribbon-like film forming material for an air electrode is attached to the cell tube, wound, and fired to form an air electrode. A method for forming a cell tube of a cylindrical fuel cell, comprising the steps of: forming the ribbon-shaped film-forming material by impregnating a foaming material with a film-forming slurry.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, a film forming apparatus and a film forming method for a cylindrical fuel cell tube according to an embodiment of the present invention will be described in more detail.
[0014]
In the first and second aspects of the present invention, the mold is preferably made of a material having cushioning properties and almost no air permeability, such as a rubber frame. Here, the shape of the mold is not particularly limited, and any shape may be used as long as the slurry for film formation deposited on the base tube can be pressed through the mold by gas introduced from the gas introduction tube. Examples thereof include, as will be described later, one integrated with the hollow mold as shown in FIGS. 1 to 3 or one movable inside and outside the hollow mold as shown in FIG. The gas introduced from the gas introduction pipe includes, for example, air, but is not limited thereto, and may be an inert gas such as nitrogen or argon.
[0015]
Further, the number of the hollow molds is not particularly limited, and can be appropriately set according to the length of the cell tube. Further, the number of slurry introduction pipes connected to the hollow mold may be set as appropriate, but the arrangement may be along the circumferential direction of the base tube in order to deposit the film-forming slurry on the base tube as evenly as possible. It is preferable to arrange them at intervals.
[0016]
Examples of the film-forming slurry used in the third invention include a slurry containing a lanthanum-based perovskite having a powder concentration of 20 to 80% and a solvent. Examples of the lanthanum-based perovskite include LaMnO 3 and LaCoO 3 . As the foaming material, a material having holes of submicron to several hundreds of micron, such as urethane foam, is preferable. Here, if the hole diameter is less than submicron, gas does not easily pass through, and the performance of the cell deteriorates. Conversely, if the hole diameter exceeds several hundred microns, it becomes difficult for current to flow. The reason why the powder concentration is set in the above range is that when the concentration is less than 20%, the viscosity and the yield value of the slurry are too low, and when the concentration exceeds 80%, the viscosity and the yield value of the slurry are too high. This is because it is difficult to impregnate the foam material. Examples of the solvent include water and petroleum products.
[0017]
【Example】
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
(Example 1)
Please refer to FIG. 1, FIG. 2 and FIG. Here, FIG. 1 is an overall view of a film forming apparatus for a cylindrical fuel cell tube according to the first embodiment, FIG. 2 is an enlarged view of a main part in FIG. 1, and FIG. 3 is along the line XX in FIG. FIG.
[0018]
Reference numeral 21 in the drawing denotes an annular hollow mold attached to the outer periphery of the base tube 22. On the base tube 22 side of the hollow mold 21, a rubber frame (mold) 23 is disposed. In the hollow mold 21, a slurry introduction pipe 26 for injecting a slurry 25 for film formation into an outer peripheral portion of the base tube 22 located in a space 24 formed by the base tube 22 and the rubber frame 23 is provided. 21 are provided at equal intervals in the circumferential direction (see FIGS. 2 and 3). Further, the hollow mold 21 is provided with an air introduction pipe (gas introduction pipe) 28 that communicates with a hollow portion 27 formed by the hollow mold 21 and the rubber frame 23.
[0019]
As described above, the film forming apparatus according to the first embodiment includes the annular hollow mold 21 disposed on the outer peripheral portion of the base tube 22, and the rubber frame 23 disposed on the base tube side of the hollow mold 21. The hollow mold 21 is connected to a slurry introduction pipe 26 for injecting the film forming slurry 25 into the outer peripheral portion of the base tube 22, and a hollow portion 27 formed by the hollow mold 21 and the mold frame 23. An air introduction pipe 28 for supplying air and pressing the mold 23 is provided.
[0020]
When a film is formed using a film forming apparatus having such a configuration, the film formation is performed as follows.
First, a plurality of hollow molds 21 were arranged on the outer peripheral portion of the base tube 22 as shown in FIG. Next, the slurry 25 for film formation was injected into the space 24 of the hollow mold 21 from the slurry introduction tube 26, and was deposited on the base tube 22 located in the space 24. Here, an air electrode slurry was used as the film forming slurry 25. Subsequently, air is sent from the air introduction pipe 26 to the hollow portion 27 of the hollow mold 21, whereby the pressure of the hollow portion 27 is increased to press the rubber frame 23 toward the base tube 22, thereby forming a film for the space portion 24. The slurry 25 is pressed against the base tube 22. Furthermore, after removing the hollow mold 21 from the base tube 22, the slurry 25 for film formation was dried and fired to form an air electrode. Further, a fuel electrode, an electrolyte, and an interconnector were formed in the same manner as the air electrode to manufacture a cell tube of a cylindrical fuel cell.
[0021]
According to such a film forming method, since the components of the fuel cell having a large film thickness can be formed by injecting the slurry for film forming once, and then drying and firing, the printing and drying are performed for each component. Since it is not necessary to repeat the process many times, each constituent member can be formed with fewer man-hours as compared with the related art. In addition, the performance of the battery can be prevented from deteriorating as compared with the conventional attachment method.
[0022]
(Example 2)
Please refer to FIG. FIG. 6 shows only the mold portion of the film forming apparatus for the cylindrical fuel cell tube according to the second embodiment. However, the same members as those in FIGS. 1 to 3 are denoted by the same reference numerals, and only the main parts will be described.
Reference numeral 31 in the figure denotes an annular hollow mold disposed on the outer peripheral portion of the base tube 22. The mold 31 is bent inward on the side of the base tube 22 and has a step 32 for supporting the rubber frame 23. Here, the rubber frame 23 is usually located as shown by a dotted line X. The slurry introduction pipe 26 is connected to the mold 31 so as to inject the film-forming slurry 25 onto the base tube in the space 24 formed by the mold 31, the rubber frame 23, and the base tube 22. The air introduction pipe 28 is attached to the outer wall of the mold 31 and is connected to the mold 31 so as to press the rubber frame 23 toward the base tube by introducing air.
[0023]
When a film is formed using such a film forming apparatus, the film formation is performed as follows.
First, a plurality of molds 31 were arranged on the outer peripheral portion of the base tube 22 as shown in FIG. Next, the slurry 25 for film formation was injected into the space 24 from the slurry introduction pipe 25, and the slurry 28 for film formation was deposited on the base tube 22 located in the space 24. Subsequently, air is sent from the air introduction pipe 28 into the hollow portion 27 of the hollow mold 21, whereby the pressure inside the hollow portion 27 is increased to press the rubber frame 23 toward the base tube 22, and the film forming slurry 28 is discharged. It is pressed against the base tube 21 side. Further, after removing the hollow mold 21 from the base tube 22, the film forming slurry 28 was dried and fired to form an air electrode. Further, a fuel electrode, an electrolyte, and an interconnector were formed in the same manner as the air electrode to manufacture a cell tube of a cylindrical fuel cell.
[0024]
(Example 3)
Reference is made to FIGS. 7A and 7B. Here, FIG. 7A is an explanatory view of the film forming method of the third embodiment, and FIG. 7B is a sectional view of the cell tube at the time of firing. However, the same members as those in FIG. 5 are described with the same reference numerals.
[0025]
First, the fuel electrode 2, the electrolyte 3, and the interconnector 5 were sequentially formed on the surface of the base tube 1 in advance by screen printing to form a cell tube 41. Next, a ribbon-shaped film forming material 42 for an air electrode was attached and wound on the cell tube 41. Here, as the ribbon-like film-forming material 42, a material obtained by impregnating a film-forming slurry 25 into a foaming material such as urethane foam was used. As the film forming slurry 25, a slurry in which a solvent was added to a lanthanum-based perovskite having a powder concentration of, for example, 60% was used. Subsequently, as shown in FIG. 7B, the boundary of the ribbon-shaped film forming material 42 wound around the cell tube 41 is fixed with, for example, a tape 43, and then fired to form the air electrode 4, thereby manufacturing the cell tube. did. During firing, the foam material is scattered, so that a relatively thick air electrode is obtained.
[0026]
According to the third embodiment, the same effect as that of the first embodiment can be obtained.
The porosity of the fired film is controlled by the density (porosity) of the foamed material and the powder concentration in the slurry for film formation. The powder concentration is preferably about 20 to 80% when the whole is 100%.
[0027]
【The invention's effect】
As described above in detail, according to the present invention, an annular hollow mold disposed on the outer peripheral portion of a base tube, a mold provided on the base tube side of the hollow mold, and a connection to the hollow mold A slurry introduction pipe for injecting a slurry for film formation into an outer peripheral portion of the base tube, and a gas introduction for supplying gas to a hollow portion formed by the hollow mold and the mold to press the mold. With the configuration including the tube, it is possible to provide a membrane forming apparatus for a cylindrical fuel cell tube that requires less man-hours and can avoid performance degradation as compared with the related art.
[0028]
Further, according to the present invention, there is provided a method for forming a fuel electrode, an electrolyte, an interconnector and an air electrode on the surface of a base tube by using the film forming apparatus to form a cell tube of a cylindrical fuel cell. After adhering the film forming slurry to the outer peripheral portion of the base tube, the gas is sent from the gas introduction tube to press the mold, thereby pressing the film forming slurry adhered to the base tube, and further drying and firing. By doing so, it is possible to provide a method for forming a cylindrical fuel cell tube that can reduce the number of steps and avoid performance degradation as compared with the related art.
[0029]
Furthermore, according to the present invention, after the fuel electrode, the electrolyte, and the interconnector are sequentially formed on the surface of the base tube by screen printing in advance to form a cell tube, the cell tube is formed into a ribbon shape for an air electrode. A process of attaching and winding a film material, forming an air electrode by firing, and by impregnating a foam material with a film-forming slurry, the ribbon-shaped film-forming material requires less man-hour and It is possible to provide a method for forming a cylindrical fuel cell tube capable of avoiding performance degradation.
[Brief description of the drawings]
FIG. 1 is an overall view of a cylindrical fuel cell tube forming apparatus according to a first embodiment of the present invention.
FIG. 2 is an enlarged view of a main part of FIG. 1; FIG. 3 is a cross-sectional view taken along the line XX of FIG. 1; FIG.
FIG. 5 is an explanatory diagram of a cylindrical fuel cell.
FIG. 6 is an overall view of a cylindrical fuel cell tube forming apparatus according to a second embodiment of the present invention.
FIG. 7 is an explanatory diagram of a method for forming a cylindrical fuel cell tube according to a third embodiment of the present invention.
[Explanation of symbols]
1,22 ... Base tube,
2. Fuel electrode,
3 ... electrolyte,
5. Interconnector,
21, 31 ... hollow mold,
23 ... rubber frame (mold),
24 ... space,
25 ... Membrane slurry,
26 ... Slurry introduction pipe,
27 ... hollow part,
28 ... air introduction pipe (gas introduction pipe),
32 ... step,
41 ... cell tube,
42 ... ribbon-shaped film-forming material,
43 ... Tape.

Claims (4)

基体管の表面に燃料極、電解質、インタコネクタ及び空気極を製膜して円筒型燃料電池のセルチューブを製膜する装置において、
前記基体管の外周部に配置される環状の中空金型と、この中空金型の基体管側に設けられた型枠と、前記中空金型に連結され，基体管の外周部に製膜用スラリーを注入するためのスラリー導入管と、前記中空金型と型枠とで形成される中空部に気体を供給して前記型枠を押圧する気体導入管とを具備することを特徴とする円筒型燃料電池セルチューブの製膜装置。In a device for forming a cell tube of a cylindrical fuel cell by forming a fuel electrode, an electrolyte, an interconnector and an air electrode on the surface of a base tube,
An annular hollow mold disposed on the outer periphery of the base tube, a mold provided on the base tube side of the hollow mold, and a film forming member connected to the hollow mold for forming a film on the outer periphery of the base tube; A cylinder comprising: a slurry introduction pipe for injecting slurry; and a gas introduction pipe for supplying gas to a hollow portion formed by the hollow mold and the mold to press the mold. -Type fuel cell tube forming equipment. 請求項１記載の製膜装置を用いて、基体管の表面に燃料極、電解質、インタコネクタ及び空気極を製膜して円筒型燃料電池のセルチューブを製膜する方法であり、
基体管の外周部に製膜用スラリーを貼着した後、気体導入管から気体を送って型枠を押圧することにより基体管に貼着した製膜用スラリーを押圧し、更に乾燥、焼成することを特徴とする円筒型燃料電池セルチューブの製膜方法。A method for forming a cell tube of a cylindrical fuel cell by forming a fuel electrode, an electrolyte, an interconnector and an air electrode on a surface of a base tube using the film forming apparatus according to claim 1,
After the slurry for film formation is adhered to the outer peripheral portion of the base tube, the gas is sent from the gas introduction tube to press the mold so that the slurry for film formation adhered to the base tube is pressed, and further dried and fired. A method for forming a cylindrical fuel cell tube according to claim 1. 基体管の表面に燃料極、電解質、インタコネクタ及び空気極を製膜して円筒型燃料電池のセルチューブを製膜する方法において、
前記基体管の表面に燃料極、電解質、インタコネクタを予めスクリーン印刷法により順次製膜してセルチューブを形成した後、このセルチューブに空気極用のリボン状製膜材を貼着、巻装し、焼成により空気極を形成する工程を具備し、
前記リボン状製膜材は発泡材に製膜用スラリーを含浸させたものであることを特徴とする円筒型燃料電池セルチューブの製膜方法。In a method of forming a fuel electrode, an electrolyte, an interconnector and an air electrode on a surface of a base tube to form a cell tube of a cylindrical fuel cell,
After a fuel electrode, an electrolyte, and an interconnector are sequentially formed on the surface of the base tube in advance by a screen printing method to form a cell tube, a ribbon-shaped film forming material for an air electrode is attached and wound on the cell tube. And comprising a step of forming an air electrode by firing,
The method for forming a cylindrical fuel cell tube according to claim 1, wherein the ribbon-shaped film-forming material is obtained by impregnating a foaming material with a film-forming slurry. 前記製膜用スラリーは、粉体濃度２０〜８０％のランタン系ペロブスカイトと溶剤からなるスラリーであることを特徴とする請求項３記載の円筒型燃料電池セルチューブの製膜方法。The method for forming a cylindrical fuel cell tube according to claim 3, wherein the slurry for film formation is a slurry comprising a lanthanum-based perovskite having a powder concentration of 20 to 80% and a solvent.
JP2002292224A 2002-10-04 2002-10-04 Cylindrical fuel cell tube forming apparatus and method Expired - Fee Related JP4064777B2 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008023952A1 (en) * 2006-08-25 2008-02-28 Lg Chem, Ltd. Structure for electrochemical device to improve safety and electrochemical device comprising the same
JP2009289754A (en) * 2009-08-07 2009-12-10 Toto Ltd Solid-oxide fuel cell

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008023952A1 (en) * 2006-08-25 2008-02-28 Lg Chem, Ltd. Structure for electrochemical device to improve safety and electrochemical device comprising the same
US9070955B2 (en) 2006-08-25 2015-06-30 Lg Chem, Ltd. Structure for electrochemical device to improve safety and electrochemical device comprising the same
US9178252B2 (en) 2006-08-25 2015-11-03 Lg Chem, Ltd. Structure for electrochemical device to improve safety and electrochemical device comprising the same
JP2009289754A (en) * 2009-08-07 2009-12-10 Toto Ltd Solid-oxide fuel cell

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