JP4288560B2 - Tubular solid oxide fuel cell - Google Patents

Tubular solid oxide fuel cell Download PDF

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JP4288560B2
JP4288560B2 JP2002319499A JP2002319499A JP4288560B2 JP 4288560 B2 JP4288560 B2 JP 4288560B2 JP 2002319499 A JP2002319499 A JP 2002319499A JP 2002319499 A JP2002319499 A JP 2002319499A JP 4288560 B2 JP4288560 B2 JP 4288560B2
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gas
introduction pipe
gas introduction
gas supply
fuel cell
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JP2004152723A (en
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幸作 藤永
進 相川
正宏 黒石
健 斎藤
俊哉 阿部
賢太郎 鈴木
弘明 竹内
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Toto 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

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Description

【０００１】
【産業上の利用分野】
本発明は、筒状固体酸化物形燃料電池に関し、さらに詳しくは片側先端が密封された筒状固体酸化物形燃料電池のガス分配構造に関する。
【０００２】
【従来の技術】
従来、筒状固体酸化物形燃料電池において、酸化剤ガスを細長い酸化剤導入管で分配して燃料電池の内部まで供給するものは、酸化剤ガスを供給する酸化剤の供給本管の一方端から他方端に流し、供給本管の軸線が分岐管の軸線に９０度より小さい角度で交差するように接続される酸化剤分配構造となっている。（特許文献１参照。）
【０００３】
【特許文献１】
特開平５−１５１９８５号広報（２〜4頁、図１）
【０００４】
しかしながら、従来の構成では、複数の固体酸化物形燃料電池セルの集合体よりなる燃料電池モジュールを形成した場合、固体酸化物形燃料電池セルはセラミック材料よりなるため、取付配置に対する寸法誤差を生じやすく、設置時に酸化剤導入管を最適な位置に配置することが困難であった。また、固体酸化物形燃料電池の発電反応で約７００〜１，０００℃において、供給本管と分岐管の接続部や分岐管を保持するフランジ部と固体酸化物形燃料電池セルとの熱膨張率の差や起動停止の熱サイクルによる応力により、固体酸化物形燃料電池セルが亀裂や破損するという問題があった。
【０００５】
【発明が解決しようとする課題】
本発明は以上のような従来技術の問題点を解決するためになされたものであり、その目的とするところは熱膨張率の差や起動停止の熱サイクルによる応力を許容できるガス分配器を有する信頼性の高い安全な筒状固体酸化物形燃料電池を提供することにある。
【０００６】
【課題を解決するための手段】
以上のような課題を解決する請求項１の発明は、空気極と燃料極との間に電解質を積層し、片側先端で密封された筒状固体酸化物形燃料電池セルと、ガスを供給するガス供給ダクトに接続されたバッファーとしてのガス供給容器と、このガス供給容器と連通し前記筒状固体酸化物形燃料電池セルの密封された先端内部へガスを供給する細長いガス導入管と、からなるガス分配器と、を備えた筒状固体酸化物形燃料電池において、前記ガス導入管の一端に設けられたガス導入管フランジと、このガス導入管フランジを固定支持する基準となる壁である接続壁に設けられ、前記ガス導入管の外径よりも大径であってこのガス導入管が挿入された接続孔と、前記ガス導入管フランジの上方より均等な面圧力を与える圧力保持手段と、前記ガス導入管フランジを支点として回転可能に支持する接触応力緩和手段と、によって、前記ガス導入管と前記ガス供給容器との接続部が形成されていることを特徴とする。
このように、ガス導入管の外径よりも大きな接続孔を設けてガス導入管と接続孔との隙間を形成し、ガス導入管を接続孔へ挿入することにより、セラミック材料よりなる燃料電池セルの集合体の燃料電池モジュールを形成した際に生ずる取付配置に対する寸法誤差と、燃料電池セルと接続壁との熱膨張率の差による運転時の位置ずれを考慮し、ガス導入管の組み立ての際、自在にガス導入管を取付けて寸法誤差を許容し、初期の燃料電池セルとガス導入管との接触を防ぐことができる。また、圧力保持手段が設けられることにより、面圧力を変化することでガス導入管の傾いたときのガス漏れ量を容易に制御することができる。さらに、接触応力緩和手段が設けられることにより、前述の熱膨張率の差や起動停止の熱サイクルによる固体酸化物形燃料電池セルとガス導入管との接触応力を緩和して固体酸化物形燃料電池セルの亀裂や破損を防ぐことができる。よって、信頼性の高い安全な発電をすることができる。
【０００７】
請求項２の発明は、前記ガス供給容器の内部には滞留したガスを前記ガス導入管へ供給するガス供給孔を複数有する平板状のガス供給壁が収納されていると共に、前記ガス供給容器の下面に前記接続孔が形成されており、このガス供給壁の自重により前記ガス導入管フランジを前記ガス供給容器の下面へ押し付けることによって前記圧力保持手段が構成されていること特徴とする。
これによって、平板の重量を変えてガス導入管を支持固定する面圧力を自在にでき、容易にガス漏れ量とガス導入管の傾きを制御することができる。
【０００８】
請求項３の発明は、前記ガス供給容器の下方に前記接続孔が形成された平板状の接続壁を設けると共に、前記ガス供給容器の下面にはガスを流出するガス供給孔を複数有しており、前記ガス導入管フランジを前記ガス供給容器の下面と前記接続壁で挟持することによって前記圧力保持手段が構成されていることを特徴とする。
これによって、ガス供給容器と接続壁の圧縮量によりガス導入管を支持固定する面圧力を自在にでき、容易にガス漏れ量とガス導入管の傾きを制御することができる。
【０００９】
請求項４の発明は、前記ガス導入管フランジを平面とし、その上下に弾性体のシール材を各孔基準で配置することをよって前記接触応力緩和手段が構成されていることを特徴とする。
これによって、筒状固体酸化物形燃料電池セル内部でガス導入管が自在に傾くことができ、熱膨張率の差や起動停止の熱サイクルによるガス導入管と筒状固体酸化物形燃料電池セルの接触応力を緩和して固体酸化物形燃料電池セルの亀裂や破損を防ぐことができる。
【００１２】
【発明の実施の形態】
以下、本発明の好適な実施形態について図面を参照して具体的かつ詳細に説明を行う。なお、以下の実施形態における筒状固体酸化物形燃料電池は、筒状セルの外側が燃料極であって内側が空気極であり、空気などの酸化剤ガスをガス分配器によって供給する構成について説明を行なう。
図１は、本発明の一実施例を示す筒状固体酸化物形燃料電池の概略図である。燃料電池容器１の中に、複数の片側先端が密封された筒状固体酸化物形燃料電池セル（以下、燃料電池セル）１２の集合体からなる燃料電池モジュール１３と、ガス導入管９とガス供給容器４とガス供給ダクト２とからなるガス分配器１０と、上部隔壁１１と、下部隔壁１５が収納され、ガス分配器１０はガス導入管９がガス供給容器４ に接続する接続部７を形成し、また、燃料電池セル１２は上部隔壁を貫通し、貫通部は非気密構造を形成している。このとき、燃料電池容器１は、耐熱ステンレス鋼やインコネル（登録商標）等で形成することができ、上部隔壁１１と下部隔壁１５は、通気性を有するセラミック系耐熱ボードや通気孔を有する耐熱ステンレス鋼、インコネル（登録商標）等で形成することができる。
【００１３】
図２は、図１に示すガス分配器１０の接合部７の拡大図である。ガス供給容器３の下面であり、ガス導入管９の外径より大きい接続孔２２を有する接続壁６を基準面とし、ガス導入管９が接続孔２２に挿入され、ガス接続壁６の上部より順に、下部シール材２１と、ガス導入管フランジ２０と、上部シール材１９と、ガス供給孔１８を有するガス供給壁５とを積層し、各孔を貫通して配置して形成されている。
【００１４】
図３は、図１に示す燃料電池セル１２の概略図である。燃料電池セル１２は、空気極２４の外周上に電解質２５と燃料極２６を密着積層した片側先端が密封された筒状セルである。空気極２４は、多孔質のＬａＣｏＯ３、ＬａＭｎＯ３、ＬａＦｅＯ３等のペロブスカイト型酸化物でＳｒやＣａ等をＬａサイトにドープしたもの、あるいはドープしないもの、またはそれらの複合材によりで形成されている。電解質２５は、ＹＳＺにより形成されている。燃料極２６は、多孔質のＮｉとＹＳＺのサーメットにより形成されている。
【００１５】
次に、このように構成された筒状固体酸化物形燃料電池の動作について説明を行う。空気は、ガス供給ダクト２よりガス分配器１０のガス供給容器４と接続部７とガス導入管９を介して燃料電池セル１２の先端内部に流れて空気極２４に供給され、また、燃料ガスは、燃料供給管１７と燃料分散室１６と下部隔壁１５の通気部とを介して燃料電池セル１２の外側に流れて燃料極２６に供給されると、電解質２５の両側で電気化学反応が起こり、電気と熱と水を発生する。この反応は水の電気化学反応の逆反応である。反応済みの排燃料ガスは上部隔壁１１の排出孔（図示しない）を介して燃焼室８に排出される。一方反応済みの排空気は、燃料電池セル１２の開放端２３から燃焼室８に排出される。燃焼室８では排燃料に含まれる残留酸素が混合して燃焼し、燃焼ガスは排気ガスダクト３を通じて排出される。固体酸化物形燃料電池の発電温度は約１０００℃であるため、発電室１４の温度も発電反応温度に近い温度になり、また、燃焼室８でも前述のような燃焼によってガス分配器１０の接続部７の周辺温度が約７００〜１０００℃となり、燃料電池セル１２とガス導入管９を支持する接続壁６との熱膨張差を生じる。しかしながら、セラミック材料よりなる燃料電池セル１２の集合体の燃料電池モジュール１３を形成した際に生ずる取付配置に対する寸法誤差と、燃料電池セル１２と接続壁６との熱膨張率の差による運転時の位置ずれを考慮し、ガス導入管９の外径よりも大きな接続孔２２を設けてガス導入管９と接続孔２２との隙間を形成し、ガス導入管９の組み立てで自在に取付けて寸法誤差を許容し、ガス導入管９を接続孔６へ挿入されるため、初期の燃料電池セル１２とガス導入管９との接触を防ぐことができる。また、ガス導入管９の一端に設けられたガス導入管フランジ２０の上方より均等な面圧力を与える圧力保持手段を有しているため、ガス導入管９の傾きを制御してガス漏れを抑えることができ、さらに、ガス導入管フランジ２０を支点として回転可能に支持する接触応力緩和手段を有しているため、熱膨張率の差や起動停止の熱サイクルによる燃料電池セル１２とガス導入管９の接触したときの応力を緩和して燃料電池セル１２の亀裂や破損を防ぐことができるため、信頼性の高い安全な発電を維持することができる。
【００１６】
この場合、圧力保持手段が、ガス供給孔１８を有するガス供給壁９を平板の重りで形成し、平板重量により約０．１〜１．５ｋｇ／ｃｍ２の面圧力を与えることが好ましい。これによって、ガス導入管９の位置ずれを防止し、ガス導入管フランジ２０の傾きを数度の範囲で制御でき、平板の重量を変えてガス導入管９を支持固定する面圧力を自在にでき、容易に接続部７からガス漏れ量とガス導入管９の傾きを制御することができる。よって、信頼性の高い安全な発電をすることができる。
【００１７】
接触応力緩和手段が、ガス導入管フランジ２０の上下に、ガス導入管９の外径と略同一の孔径を有する弾性体の上部シール材１９、下部シール材２１を各孔基準で配置され、また、下部シール材２１はガス導入管フランジ２０より大きい径で、ガス導入管９と一体で動けること形状であることが好ましい。例えば、ガス導入管フランジ２０を有するをガス導入管９の外径６ｍｍと、同じ約６ｍｍの孔径で上部シール材１９および下部シール材２１が設けられることによって、ガス導入管９と上部シール材１９と下部シール材２１を取付する時、孔径基準で容易に配置でき、また、ガス導入管９と下部シール材２１が密着して動くことができ、さらに、燃料電池セル１２の内部でガス導入管９が自在に傾きくことができるため、発電反応温度により周辺温度約７００〜１０００℃の高温域となる接続部７での熱膨張差や起動停止の熱サイクルによるガス導入管９と燃料電池セル１２との接触応力を緩和して燃料電池セル１２の亀裂や破損が防止できる。
【００１８】
上部シール材料１９と下部シール材料２１は、セラミック繊維や金属繊維等で形成することができるが、セラミック繊維により金属線で補強をしているもの、あるいは、目地材を塗布して補強をしているものを有する構成であることが好ましい。これによって、高温酸化後のシール材強度維持でき、シール材の弾性によりガス導入管９と上部シール材１９と下部シール材２１がなじむことができるため、シール材料の劣化を軽減してシール性能を維持できる。
【００１９】
ガス供給壁５と接続壁６の熱膨張係数と、燃料電池セル１２との熱膨張係数が略同一であることが好ましい。例えば、燃料電池セル１２の熱膨張係数が約１０．５×１０−６（ｃｍ／ｃｍ・℃）に対し、ガス供給壁５および接続壁６の熱膨張係数が約７．５〜１３．５×１０−６（ｃｍ／ｃｍ・℃）の気密性を有する耐熱ステンレス鋼やセラミック等で形成されることにより、ガス導入管９の熱膨張差による位置ずれや傾きを軽減でき、ガス供給壁５と接続壁６と、燃料電池セル１２との熱膨張率の差で生ずるガス導入管９と燃料電池セル１２の接触応力を緩和軽減することができる。
【００２０】
接続部７の周辺温度は、８００℃以下で制御されることをが好ましい。これによって、ガス供給壁５と上部シール材１９とガス導入管フランジ２０と下部シール材２１と接続壁６との熱膨張率の差を抑え、上部シール材と下部シール材の劣化を軽減できるため、接続部７のシール性能の低下を防止することができる。
【００２１】
図４は、本発明の他の実施例を示すガス分配器１０の圧力保持手段として、ガス供給容器４と接続壁６で圧縮し、ガス供給孔１８を有するガス供給容器４の下面のガス供給壁５により、ガス導入管９を支持固定する構造例を採用した例である。しかしながら、これは一例であり限定されるものではない。ガス供給容器４と接続壁６を挟み込んでねじで締め付け可能な圧縮部材２７で接続部７を圧縮する構造を形成している。このとき、圧縮部材２７でガス供給容器４の下面であるガス供給孔１８を有するガス供給壁５より、約０．１〜１．５ｋｇ／ｃｍ２の面圧力を与えることが好ましい。これによって、ガス供給容器４と接続壁６の圧縮量によりガス導入管９を支持固定する面圧力を自在にでき、ガス導入管９の位置ずれを防止し、容易に接続部７からガス漏れ量とガス導入管９の傾きを制御することができる。よって、信頼性の高い安全な発電をすることができる。
【００２２】
図５は、本発明の他の実施例を示す酸化材分配器１０の接触応力緩和手段として、ガス導入管９の外径より大きな孔径の接続孔２２を有する接続壁６の上に、下部シール材２１と略同一の外径を有するシール材支持板２８と、下部シール材２１と、球面で形成されるガス導入管フランジ２０と、ガス導入管フランジ２０の圧縮部を除いた部分にガス供給孔１８を有するガス供給壁５を配置形成し、ガス導入管フランジ２０を支点として回転可能に支持する構造例を採用した例である。しかしながら、これは一例であり限定されるものではない。このとき、ガス導入管フランジ２０の側面よりガスが供給され、接続孔２２をシール材支持板２８と下部シール材２１と球面で形成されるガス導入管フランジ２０でシールすると共に、ガス供給壁５で均等に圧縮支持され、また、シール材支持板２８は耐熱ステンレス鋼やインコネル（登録商標）等で形成されることが好ましい。例えば、下部シール材２１の内径が８ｍｍであるとすると、同じ約８ｍｍの孔径でシール材支持板２８を形成されることにより、ガス導入管９の外径とシール材２８との隙間の範囲で自在に傾くことができ、燃料電池セル１２の内部でガス導入管９が自在に傾きくことができ、また、シール材支持板２８が強度を有する材料で球面であるガス導入管フランジ２０が支持されるため、容易にガス供給壁５によりガス導入管９を支持すると共に、発電反応温度により周辺温度約７００〜１０００℃ の高温域となる接続部７での熱膨張差や起動停止の熱サイクルによるガス導入管９と燃料電池セル１２との接触応力を緩和して燃料電池セル１２の亀裂や破損が防止できる。
【００２４】
なお、前述の実施例にかかわらず、燃料ガスが燃料電池セル１２の内側を流れ、酸化剤ガスが燃料電池セルの外側に流れるように構成し、燃料ガスと酸化剤ガスを入れ替えて燃料ガス分配器として同様に形成することもできる。
【００２５】
【発明の効果】
以上の説明から明らかなように、本発明の筒状固体酸化物形燃料電池によれば、セラミック材料よりなる燃料電池セルの集合体の燃料電池モジュールを形成した際に生ずる取付配置に対する寸法誤差と、燃料電池セルと接続壁との熱膨張率の差による運転時の位置ずれを考慮し、ガス導入管の組み立ての際、自在にガス導入管を取付けて寸法誤差を許容し、初期の燃料電池セルとガス導入管との接触を防ぐことができ、また、ガス導入管の傾いたときのガス漏れ量を容易に制御することができ、さらに、熱膨張率の差や起動停止の熱サイクルに耐えうる信頼性の高い安全な筒状固体酸化物形燃料電池を実現できるため、安定した高効率な発電を行うことができる。
【図面の簡単な説明】
【図１】本発明の一実施例を示す筒状固体酸化物形燃料電池の概略図である。
【図２】本発明の一実施例に係わる接続部の拡大図である。
【図３】筒状固体酸化物形燃料電池セルの一例を示す概略図である。
【図４】本発明の他の実施例を示すガス分配器の圧力保持手段の概略図である。
【図５】本発明の他の実施例を示すガス分配器の接触応力緩和手段の概略図である。
【図６】本発明の一実施例に係わるガス導入管フランジの形状例を示す概略図である。
【符号の説明】
１ 燃料電池容器
２ ガス供給ダクト
３ 排気ガスダクト
４ ガス供給容器
５ ガス供給壁
６ 接続壁
７ 接続部
８ 燃焼室
９ ガス導入管
１０ ガス分配器
１１ 上部隔壁
１２ 筒状固体酸化物形燃料電池セル
１３ 燃料電池モジュール
１４ 発電室
１５ 下部隔壁
１６燃料分散室
１７ 燃料供給配管
１８ ガス供給孔
１９ 上部シール材
２０ ガス導入管フランジ
２１ 下部シール材
２２ 接続孔
２３ 開放端
２４ 空気極
２５ 電解質
２６ 燃料極
２７ 圧縮部材
２８ シール材支持板[0001]
[Industrial application fields]
The present invention relates to a tubular solid oxide fuel cell, and more particularly to a gas distribution structure of a tubular solid oxide fuel cell with one end sealed.
[0002]
[Prior art]
Conventionally, in a cylindrical solid oxide fuel cell, an oxidant gas is distributed by an elongated oxidant introduction pipe and supplied to the inside of the fuel cell. To the other end, and the oxidant distribution structure is connected so that the axis of the supply main pipe intersects the axis of the branch pipe at an angle smaller than 90 degrees. (See Patent Document 1.)
[0003]
[Patent Document 1]
Japanese Laid-Open Patent Publication No. 5-151985 (2-4 pages, Fig. 1)
[0004]
However, in the conventional configuration, when a fuel cell module composed of an assembly of a plurality of solid oxide fuel cells is formed, the solid oxide fuel cells are made of a ceramic material. It was easy and it was difficult to arrange the oxidant introduction pipe at the optimum position during installation. Further, at about 700 to 1,000 ° C. in the power generation reaction of the solid oxide fuel cell, the thermal expansion of the connection portion of the supply main pipe and the branch pipe, the flange portion holding the branch pipe, and the solid oxide fuel cell. There was a problem that the solid oxide fuel cell was cracked or damaged due to the difference in rate or the stress due to the thermal cycle of starting and stopping.
[0005]
[Problems to be solved by the invention]
The present invention has been made to solve the above-described problems of the prior art, and the object thereof is to have a gas distributor that can tolerate the difference in thermal expansion coefficient and the stress due to the thermal cycle of starting and stopping. An object of the present invention is to provide a highly reliable and safe cylindrical solid oxide fuel cell.
[0006]
[Means for Solving the Problems]
The invention according to claim 1, which solves the above-described problem, supplies a gas to a cylindrical solid oxide fuel cell in which an electrolyte is laminated between an air electrode and a fuel electrode and sealed at one end. A gas supply container as a buffer connected to the gas supply duct, and an elongated gas introduction pipe that communicates with the gas supply container and supplies gas into the sealed tip of the cylindrical solid oxide fuel cell. And a gas introducing pipe flange provided at one end of the gas introducing pipe, and a reference wall for fixing and supporting the gas introducing pipe flange. A connection hole provided in a connection wall and having a diameter larger than the outer diameter of the gas introduction pipe and into which the gas introduction pipe is inserted, and a pressure holding means for applying a uniform surface pressure from above the gas introduction pipe flange; The gas introduction pipe And contact stress relieving means for rotatably supporting the fulcrum flange, by characterized in that the connecting portion between the gas supply container and the gas inlet pipe is formed.
Thus, by providing a connection hole larger than the outer diameter of the gas introduction pipe to form a gap between the gas introduction pipe and the connection hole, and inserting the gas introduction pipe into the connection hole, a fuel cell made of a ceramic material When assembling the gas introduction pipe, taking into account the dimensional error in the mounting arrangement that occurs when the fuel cell module of the assembly of the above is formed and the positional deviation during operation due to the difference in the thermal expansion coefficient between the fuel cell and the connection wall The gas introduction pipe can be freely attached to allow a dimensional error, and contact between the initial fuel cell and the gas introduction pipe can be prevented. Further, by providing the pressure holding means, it is possible to easily control the amount of gas leakage when the gas introduction pipe is inclined by changing the surface pressure. Further, by providing contact stress relaxation means, the solid oxide fuel can be reduced by reducing the contact stress between the solid oxide fuel cell and the gas introduction pipe due to the difference in thermal expansion coefficient and the thermal cycle of starting and stopping. Battery cells can be prevented from cracking or breaking. Therefore, reliable and safe power generation can be performed.
[0007]
According to the invention of claim 2, a flat gas supply wall having a plurality of gas supply holes for supplying the retained gas to the gas introduction pipe is housed in the gas supply container. The connection hole is formed in the lower surface, and the pressure holding means is configured by pressing the gas introduction pipe flange against the lower surface of the gas supply container by its own weight of the gas supply wall.
Thus, the surface pressure for supporting and fixing the gas introduction pipe can be freely changed by changing the weight of the flat plate, and the amount of gas leakage and the inclination of the gas introduction pipe can be easily controlled.
[0008]
According to a third aspect of the present invention, a flat connection wall having the connection hole formed therein is provided below the gas supply container, and a plurality of gas supply holes through which gas flows out are provided on the lower surface of the gas supply container. The pressure holding means is configured by sandwiching the gas introduction pipe flange between the lower surface of the gas supply container and the connection wall.
Accordingly, the surface pressure for supporting and fixing the gas introduction pipe can be freely controlled by the compression amount of the gas supply container and the connection wall, and the gas leakage amount and the inclination of the gas introduction pipe can be easily controlled.
[0009]
The invention according to claim 4 is characterized in that the contact stress relaxation means is configured by arranging the gas introduction pipe flange as a flat surface and placing elastic sealing materials above and below the flange on the basis of each hole.
As a result, the gas introduction pipe can be freely tilted inside the cylindrical solid oxide fuel cell, and the gas introduction pipe and the cylindrical solid oxide fuel battery cell due to the difference in thermal expansion coefficient or the thermal cycle of start and stop It is possible to relax the contact stress of the solid oxide fuel cell and prevent cracking or breakage of the solid oxide fuel cell.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described specifically and in detail with reference to the drawings. In addition, the cylindrical solid oxide fuel cell in the following embodiments has a configuration in which the outside of the cylindrical cell is a fuel electrode and the inside is an air electrode, and an oxidant gas such as air is supplied by a gas distributor. Give an explanation.
FIG. 1 is a schematic view of a cylindrical solid oxide fuel cell showing one embodiment of the present invention. In the fuel cell container 1, a fuel cell module 13 composed of an assembly of a plurality of cylindrical solid oxide fuel cells (hereinafter referred to as fuel cells) 12 whose one end is sealed, a gas introduction pipe 9 and a gas A gas distributor 10 including a supply container 4 and a gas supply duct 2, an upper partition wall 11, and a lower partition wall 15 are accommodated. The gas distributor 10 has a connection portion 7 for connecting a gas introduction pipe 9 to the gas supply container 4. In addition, the fuel cell 12 penetrates through the upper partition, and the penetration part forms a non-airtight structure. At this time, the fuel cell container 1 can be formed of heat resistant stainless steel, Inconel (registered trademark), or the like, and the upper partition wall 11 and the lower partition wall 15 are made of a ceramic heat resistant board having air permeability or a heat resistant stainless steel having a vent hole. It can be formed of steel, Inconel (registered trademark) or the like.
[0013]
FIG. 2 is an enlarged view of the joint 7 of the gas distributor 10 shown in FIG. The connection wall 6 that is the lower surface of the gas supply container 3 and has a connection hole 22 larger than the outer diameter of the gas introduction pipe 9 is used as a reference plane, and the gas introduction pipe 9 is inserted into the connection hole 22 from above the gas connection wall 6. In order, the lower sealing material 21, the gas introduction pipe flange 20, the upper sealing material 19, and the gas supply wall 5 having the gas supply holes 18 are laminated and arranged through each hole.
[0014]
FIG. 3 is a schematic view of the fuel battery cell 12 shown in FIG. The fuel cell 12 is a cylindrical cell in which an electrolyte 25 and a fuel electrode 26 are closely stacked on the outer periphery of the air electrode 24 and sealed at one end. The air electrode 24 is formed of a porous perovskite oxide such as LaCoO 3 , LaMnO 3 , LaFeO 3 or the like, doped with Sr or Ca at the La site, or undoped, or a composite material thereof. Yes. The electrolyte 25 is made of YSZ. The fuel electrode 26 is formed of porous Ni and YSZ cermet.
[0015]
Next, the operation of the cylindrical solid oxide fuel cell configured as described above will be described. The air flows from the gas supply duct 2 through the gas supply container 4 of the gas distributor 10, the connection portion 7, and the gas introduction pipe 9 to the inside of the tip of the fuel cell 12 and is supplied to the air electrode 24. Flows to the outside of the fuel cell 12 through the fuel supply pipe 17, the fuel dispersion chamber 16, and the vent of the lower partition 15, and is supplied to the fuel electrode 26, an electrochemical reaction occurs on both sides of the electrolyte 25. Generate electricity, heat and water. This reaction is the reverse reaction of the electrochemical reaction of water. The reacted exhausted fuel gas is discharged to the combustion chamber 8 through a discharge hole (not shown) of the upper partition wall 11. On the other hand, the reacted exhaust air is discharged from the open end 23 of the fuel cell 12 to the combustion chamber 8. In the combustion chamber 8, residual oxygen contained in the exhaust fuel is mixed and burned, and the combustion gas is discharged through the exhaust gas duct 3. Since the power generation temperature of the solid oxide fuel cell is about 1000 ° C., the temperature of the power generation chamber 14 is also close to the power generation reaction temperature, and the combustion chamber 8 is also connected to the gas distributor 10 by combustion as described above. The ambient temperature of the part 7 is about 700 to 1000 ° C., and a difference in thermal expansion occurs between the fuel battery cell 12 and the connection wall 6 that supports the gas introduction pipe 9. However, a dimensional error with respect to the mounting arrangement that occurs when the fuel cell module 13 of the assembly of the fuel cells 12 made of a ceramic material is formed, and a difference in the thermal expansion coefficient between the fuel cell 12 and the connection wall 6 during operation. In consideration of misalignment, a connection hole 22 larger than the outer diameter of the gas introduction pipe 9 is provided to form a gap between the gas introduction pipe 9 and the connection hole 22 and can be freely attached by assembling the gas introduction pipe 9 to cause a dimensional error. Since the gas introduction pipe 9 is inserted into the connection hole 6, contact between the initial fuel cell 12 and the gas introduction pipe 9 can be prevented. In addition, since there is a pressure holding means for applying a uniform surface pressure from above the gas introduction pipe flange 20 provided at one end of the gas introduction pipe 9, the inclination of the gas introduction pipe 9 is controlled to suppress gas leakage. In addition, since it has contact stress relaxation means that rotatably supports the gas introduction pipe flange 20 as a fulcrum, the fuel cell 12 and the gas introduction pipe due to a difference in thermal expansion coefficient or a thermal cycle of start and stop Since the stress at the time of contact 9 can be relaxed to prevent the fuel cell 12 from being cracked or damaged, highly reliable and safe power generation can be maintained.
[0016]
In this case, it is preferable that the pressure holding means forms the gas supply wall 9 having the gas supply holes 18 with a weight of a flat plate and applies a surface pressure of about 0.1 to 1.5 kg / cm 2 by the flat plate weight. As a result, displacement of the gas introduction pipe 9 can be prevented, the inclination of the gas introduction pipe flange 20 can be controlled within a range of several degrees, and the surface pressure for supporting and fixing the gas introduction pipe 9 can be changed by changing the weight of the flat plate. The amount of gas leakage from the connecting portion 7 and the inclination of the gas introduction pipe 9 can be easily controlled. Therefore, reliable and safe power generation can be performed.
[0017]
The contact stress relaxation means is arranged above and below the gas introduction pipe flange 20 with an elastic upper seal material 19 and lower seal material 21 having a hole diameter substantially the same as the outer diameter of the gas introduction pipe 9 on the basis of each hole. The lower sealing material 21 preferably has a diameter larger than that of the gas introduction pipe flange 20 and a shape that can move integrally with the gas introduction pipe 9. For example, the gas introduction pipe 9 and the upper seal material 19 are provided by providing the upper seal material 19 and the lower seal material 21 with the gas introduction pipe flange 20 having the same diameter of about 6 mm as the outer diameter of the gas introduction pipe 9. And the lower sealing material 21 can be easily arranged on the basis of the hole diameter, the gas introduction pipe 9 and the lower sealing material 21 can move in close contact with each other, and the gas introduction pipe can be moved inside the fuel cell 12. 9 can be freely tilted, so that the gas introduction pipe 9 and the fuel battery cell due to the difference in thermal expansion at the connection portion 7 which becomes a high temperature range of about 700 to 1000 ° C. depending on the power generation reaction temperature and the thermal cycle of start and stop The contact stress with the fuel cell 12 can be relaxed, and the fuel cell 12 can be prevented from cracking or breaking.
[0018]
The upper sealing material 19 and the lower sealing material 21 can be formed of ceramic fibers, metal fibers, or the like, but are reinforced with ceramic fibers by metal wires, or by applying joint materials and reinforcing them. It is preferable that it is the structure which has what is. As a result, the strength of the sealing material after high-temperature oxidation can be maintained, and the gas introduction pipe 9, the upper sealing material 19, and the lower sealing material 21 can be adapted by the elasticity of the sealing material. Can be maintained.
[0019]
It is preferable that the thermal expansion coefficients of the gas supply wall 5 and the connection wall 6 and the thermal expansion coefficients of the fuel cells 12 are substantially the same. For example, the thermal expansion coefficient of the fuel cell 12 is about 10.5 × 10 −6 (cm / cm · ° C.), whereas the thermal expansion coefficients of the gas supply wall 5 and the connection wall 6 are about 7.5 to 13.5. By being formed of heat-resistant stainless steel or ceramic having a hermeticity of × 10 −6 (cm / cm · ° C.), it is possible to reduce misalignment and inclination due to a difference in thermal expansion of the gas introduction tube 9, and to supply the gas supply wall 5 In addition, the contact stress between the gas introduction pipe 9 and the fuel battery cell 12 caused by the difference in thermal expansion coefficient between the connection wall 6 and the fuel battery cell 12 can be reduced.
[0020]
It is preferable that the ambient temperature of the connection part 7 is controlled at 800 ° C. or lower. This suppresses the difference in thermal expansion coefficient among the gas supply wall 5, the upper seal material 19, the gas introduction pipe flange 20, the lower seal material 21, and the connection wall 6, thereby reducing deterioration of the upper seal material and the lower seal material. And the fall of the sealing performance of the connection part 7 can be prevented.
[0021]
FIG. 4 shows the gas supply of the lower surface of the gas supply container 4 compressed by the gas supply container 4 and the connection wall 6 and having the gas supply hole 18 as the pressure holding means of the gas distributor 10 showing another embodiment of the present invention. In this example, a structure example in which the gas introduction pipe 9 is supported and fixed by the wall 5 is adopted. However, this is an example and is not limited. A structure is formed in which the connecting portion 7 is compressed by a compression member 27 that is sandwiched between the gas supply container 4 and the connecting wall 6 and can be tightened with a screw. At this time, it is preferable to apply a surface pressure of about 0.1 to 1.5 kg / cm 2 from the gas supply wall 5 having the gas supply hole 18 which is the lower surface of the gas supply container 4 by the compression member 27. Accordingly, the surface pressure for supporting and fixing the gas introduction pipe 9 can be freely controlled by the compression amount of the gas supply container 4 and the connection wall 6, the displacement of the gas introduction pipe 9 can be prevented, and the amount of gas leakage from the connection portion 7 can be easily achieved. And the inclination of the gas introduction pipe 9 can be controlled. Therefore, reliable and safe power generation can be performed.
[0022]
FIG. 5 shows a lower seal on the connection wall 6 having a connection hole 22 having a larger diameter than the outer diameter of the gas introduction tube 9 as means for reducing the contact stress of the oxidant distributor 10 according to another embodiment of the present invention. Gas supply to a portion excluding the sealing member support plate 28 having substantially the same outer diameter as the member 21, the lower sealing member 21, the gas introduction pipe flange 20 formed of a spherical surface, and the compression part of the gas introduction pipe flange 20. This is an example in which a gas supply wall 5 having a hole 18 is arranged and formed, and a structure example in which the gas introduction pipe flange 20 is rotatably supported by a fulcrum is adopted. However, this is an example and is not limited. At this time, gas is supplied from the side surface of the gas introduction pipe flange 20, and the connection hole 22 is sealed by the gas introduction pipe flange 20 formed by the sealing material support plate 28, the lower sealing material 21, and the spherical surface, and the gas supply wall 5. The sealing material support plate 28 is preferably formed of heat resistant stainless steel, Inconel (registered trademark), or the like. For example, if the inner diameter of the lower seal material 21 is 8 mm, the seal material support plate 28 is formed with the same hole diameter of about 8 mm, so that the gap between the outer diameter of the gas introduction tube 9 and the seal material 28 is within the range. The gas introduction pipe 9 can be freely inclined inside the fuel battery cell 12, and the sealing material support plate 28 is supported by the gas introduction pipe flange 20 which is a spherical material made of a strong material. Therefore, the gas introduction wall 9 is easily supported by the gas supply wall 5, and the thermal expansion difference and the start / stop thermal cycle at the connection portion 7 that is in a high temperature range of about 700 to 1000 ° C. depending on the power generation reaction temperature. By reducing the contact stress between the gas introduction tube 9 and the fuel battery cell 12 due to the above, cracks and breakage of the fuel battery cell 12 can be prevented.
[0024]
Regardless of the embodiment described above, the fuel gas flows inside the fuel cell 12 and the oxidant gas flows outside the fuel cell, and the fuel gas and the oxidant gas are exchanged to distribute the fuel gas. It can be similarly formed as a vessel.
[0025]
【The invention's effect】
As is apparent from the above description, according to the cylindrical solid oxide fuel cell of the present invention, the dimensional error with respect to the mounting arrangement caused when the fuel cell module of the assembly of fuel cells made of ceramic material is formed. Considering the displacement during operation due to the difference in thermal expansion coefficient between the fuel cell and the connection wall, when assembling the gas introduction tube, the gas introduction tube can be freely attached to allow dimensional errors, and the initial fuel cell Contact between the cell and the gas inlet pipe can be prevented, and the amount of gas leakage when the gas inlet pipe is tilted can be easily controlled. Since a reliable and safe cylindrical solid oxide fuel cell that can withstand can be realized, stable and highly efficient power generation can be performed.
[Brief description of the drawings]
FIG. 1 is a schematic view of a cylindrical solid oxide fuel cell showing one embodiment of the present invention.
FIG. 2 is an enlarged view of a connection portion according to an embodiment of the present invention.
FIG. 3 is a schematic view showing an example of a cylindrical solid oxide fuel cell.
FIG. 4 is a schematic view of a pressure holding means of a gas distributor showing another embodiment of the present invention.
FIG. 5 is a schematic view of contact stress relaxation means of a gas distributor showing another embodiment of the present invention.
FIG. 6 is a schematic view showing an example of the shape of a gas introduction pipe flange according to an embodiment of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Fuel cell container 2 Gas supply duct 3 Exhaust gas duct 4 Gas supply container 5 Gas supply wall 6 Connection wall 7 Connection part 8 Combustion chamber 9 Gas introduction pipe 10 Gas distributor 11 Upper partition 12 Cylindrical solid oxide fuel cell 13 Fuel cell module 14 Power generation chamber 15 Lower partition wall 16 Fuel dispersion chamber 17 Fuel supply pipe 18 Gas supply hole 19 Upper seal material 20 Gas introduction pipe flange 21 Lower seal material 22 Connection hole 23 Open end 24 Air electrode 25 Electrolyte 26 Fuel electrode 27 Compression Member 28 Sealing material support plate

Claims (4)

空気極と燃料極との間に電解質を積層し、片側先端で密封された筒状固体酸化物形燃料電池セルと、
ガスを供給するガス供給ダクトに接続されたバッファーとしてのガス供給容器と、このガス供給容器と連通し前記筒状固体酸化物形燃料電池セルの密封された先端内部へガスを供給する細長いガス導入管と、からなるガス分配器と、
を備えた筒状固体酸化物形燃料電池において、
前記ガス導入管の一端に設けられたガス導入管フランジと、
このガス導入管フランジを固定支持する基準となる壁である接続壁に設けられ、前記ガス導入管の外径よりも大径であってこのガス導入管が挿入された接続孔と、
前記ガス導入管フランジの上方より均等な面圧力を与える圧力保持手段と、
前記ガス導入管フランジを支点として回転可能に支持する接触応力緩和手段と、
によって、前記ガス導入管と前記ガス供給容器との接続部が形成されていることを特徴とする筒状固体酸化物形燃料電池。A cylindrical solid oxide fuel battery cell in which an electrolyte is laminated between an air electrode and a fuel electrode and sealed at one end.
A gas supply container as a buffer connected to a gas supply duct for supplying gas, and an elongated gas introduction that communicates with the gas supply container and supplies gas into the sealed tip of the cylindrical solid oxide fuel cell. A gas distributor comprising: a tube;
In a cylindrical solid oxide fuel cell comprising:
A gas introduction pipe flange provided at one end of the gas introduction pipe;
A connection wall which is a reference wall for fixing and supporting the gas introduction pipe flange, a connection hole having a diameter larger than the outer diameter of the gas introduction pipe and into which the gas introduction pipe is inserted;
Pressure holding means for applying a uniform surface pressure from above the gas introduction pipe flange;
Contact stress relaxation means for rotatably supporting the gas introduction pipe flange as a fulcrum;
The cylindrical solid oxide fuel cell is characterized in that a connection portion between the gas introduction pipe and the gas supply container is formed by the above. 前記ガス供給容器の内部には滞留したガスを前記ガス導入管へ供給するガス供給孔を複数有する平板状のガス供給壁が収納されていると共に、前記ガス供給容器の下面に前記接続孔が形成されており、このガス供給壁の自重により前記ガス導入管フランジを前記ガス供給容器の下面へ押し付けることによって前記圧力保持手段が構成されていること特徴とする請求項１に記載の筒状固体酸化物形燃料電池。  A flat gas supply wall having a plurality of gas supply holes for supplying the retained gas to the gas introduction pipe is housed in the gas supply container, and the connection hole is formed in the lower surface of the gas supply container. 2. The cylindrical solid oxidation according to claim 1, wherein the pressure holding means is configured by pressing the gas introduction pipe flange against the lower surface of the gas supply container by its own weight of the gas supply wall. Physical fuel cell. 前記ガス供給容器の下方に前記接続孔が形成された平板状の接続壁を設けると共に、前記ガス供給容器の下面にはガスを流出するガス供給孔を複数有しており、前記ガス導入管フランジを前記ガス供給容器の下面と前記接続壁で挟持することによって前記圧力保持手段が構成されていることを特徴とする請求項１に記載の筒状固体酸化物形燃料電池。  A flat connection wall having the connection hole is provided below the gas supply container, and a plurality of gas supply holes through which gas flows out are provided on the lower surface of the gas supply container, and the gas introduction pipe flange 2. The cylindrical solid oxide fuel cell according to claim 1, wherein the pressure holding means is configured by sandwiching the gas between the lower surface of the gas supply container and the connection wall. 前記ガス導入管フランジを平面とし、その上下に弾性体のシール材を各孔基準で配置することをよって前記接触応力緩和手段が構成されていることを特徴とする請求項１〜３のいずれか１項に記載の筒状固体酸化物形燃料電池。  4. The contact stress relaxation means is configured by arranging the gas introduction pipe flange as a flat surface and disposing an elastic sealing material on the upper and lower sides thereof with respect to each hole. 2. A cylindrical solid oxide fuel cell according to item 1.
JP2002319499A 2002-11-01 2002-11-01 Tubular solid oxide fuel cell Expired - Fee Related JP4288560B2 (en)

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