JP3740459B2

JP3740459B2 - Fuel cell container and fuel cell

Info

Publication number: JP3740459B2
Application number: JP2002342862A
Authority: JP
Inventors: 広一朗菅井
Original assignee: Kyocera Corp
Current assignee: Kyocera Corp
Priority date: 2002-11-26
Filing date: 2002-11-26
Publication date: 2006-02-01
Anticipated expiration: 2022-11-26
Also published as: JP2004178933A

Description

【０００１】
【発明の属する技術分野】
本発明は、電解質部材を収容可能なセラミックスから成る小型で高信頼性の燃料電池用容器およびそれを用いた燃料電池に関するものである。
【０００２】
【従来の技術】
近年、これまでよりも低温で動作する小型燃料電池の開発が活発になされている。燃料電池には、これに用いる電解質の種類により、固体高分子電解質型燃料電池（Polymer Electrolyte Fuel Cell：以下、ＰＥＦＣと記す）やリン酸型燃料電池、あるいは固体電解質型燃料電池といったものが知られている。
【０００３】
中でもＰＥＦＣは、作動温度が80〜100℃程度という低温であり、
（１）出力密度が高く、小型化・軽量化が可能である、
（２）電解質が腐食性でなく、しかも作動温度が低いため、耐食性の面から電池構成材料の制約が少ないので、コスト低減が容易である、
（３）常温で起動できるため、起動時間が短い、
といった優れた特長を有している。このためＰＥＦＣは、以上のような特長を活かして、車両用の駆動電源や家庭用のコジェネレーションシステム等への適用ばかりでなく、携帯電話・ＰＤＡ（Personal Digital Assistants）・ノートパソコン・デジタルカメラやビデオ等の出力が数Ｗ〜数十Ｗの携帯電子機器用の電源としての用途が考えられてきている。
【０００４】
ＰＥＦＣは、大別して、例えば、白金や白金−ルテニウム等の触媒微粒子が付着した炭素電極から成る燃料極（アノード）と、白金等の触媒微粒子が付着した炭素電極から成る空気極（カソード）と、燃料極と空気極との間に介装されたフィルム状の電解質部材（以下、電解質部材と記す）とを有して構成されている。ここで、燃料極には、改質部を介して抽出された水素ガス（Ｈ₂）が供給され、一方、空気極には、大気中の酸素ガス（Ｏ₂）が供給されることにより、電気化学反応により所定の電気エネルギーが生成（発電）され、負荷に対する駆動電源（電圧／電流）となる電気エネルギーが生成される。
【０００５】
具体的には、燃料極に水素ガス（Ｈ₂）が供給されると、次の化学反応式（１）に示すように、上記触媒により電子（ｅ^-）が分離した水素イオン（プロトン；Ｈ⁺）が発生し、電解質部材を介して空気極側に通過するとともに、燃料極を構成する炭素電極により電子（ｅ^-）が取り出されて負荷に供給される。
３Ｈ₂ → ６Ｈ⁺＋６ｅ^- ・・・（１）
一方、空気極に空気が供給されると、次の化学反応式（２）に示すように、上記触媒により負荷を経由した電子（ｅ^-）と電解質部材を通過した水素イオン（Ｈ⁺）と空気中の酸素ガス（Ｏ₂）とが反応して水（Ｈ₂Ｏ）が生成される。
６Ｈ⁺＋３／２Ｏ₂＋６ｅ^- → ３Ｈ₂Ｏ・・・（２）
このような一連の電気化学反応（式（１）および式（２））は、概ね80〜100℃の比較的低温の温度条件で進行し、電力以外の副生成物は基本的に水（Ｈ₂Ｏ）のみとなる。
【０００６】
電解質部材を構成するイオン導電膜（交換膜）は、スルホン酸基を持つポリスチレン系の陽イオン交換膜、フルオロカーボンスルホン酸とポリビニリデンフルオライドとの混合膜、フルオロカーボンマトリックスにトリフルオロエチレンをグラフト化したもの等が知られており、最近ではパーフルオロカーボンスルホン酸膜（例えばナフィオン：商品名、デュポン社製）等が用いられている。
【０００７】
図３に、従来の燃料電池（ＰＥＦＣ）の構成を断面図で示す。同図において、21はＰＥＦＣ、23は電解質部材、24および25は電解質部材を挟持するように電解質部材23上に配置され、ガス拡散層および触媒層としての機能を有する一対の多孔質電極、すなわち燃料極および空気極であり、26はガスセパレータ、28は燃料流路、29は空気流路である。
【０００８】
ガスセパレータ26は、ガスセパレータ26の外形を形成する積層部およびガス流入出枠と、燃料流路28と空気流路29とを分離するセパレータ部と、このセパレータ部を貫通するように設けられた、電解質部材23の燃料極24および空気極25に対応するように配置された電極とから構成されている。電解質部材23の燃料極24、空気極25が電気的に直列および／または並列に接続されるようにガスセパレータ26を介して多数積層して電池の最小単位である燃料電池スタックとし、この燃料電池スタックを、箱体に収納したものが一般的なＰＥＦＣ本体である。
【０００９】
ガスセパレータ26に形成された燃料流路28を通して燃料極24には改質器から水蒸気を含む燃料ガス（水素に富むガス）が供給され、また、空気極25には空気流路29を通して大気中から酸化剤ガスとして空気が供給され、電解質部材23での化学反応により発電される。
【００１０】
【特許文献１】
特開2001−266910号公報
【特許文献２】
特表2001−507501号公報
【００１１】
【発明が解決しようとする課題】
しかしながら、このような高電圧・高容量の電池として従来より提案され開発されている燃料電池21は、スタック構造を有し構成要素が大面積化された大重量で大型の電池であり、小型電池としての燃料電池の利用は、従来はほとんど考えられていなかった。
【００１２】
すなわち、このような燃料電池21における従来のガスセパレータ26には、これを用いて電解質部材23を積層した積層体において、電解質部材23の側面が外部に露出していることによって、携帯時の落下等により損傷を受けやすく、燃料電池21全体の機械的信頼性を確保し難いという問題点があった。
【００１３】
また、携帯電子機器に燃料電池21を搭載するためには、従来の大型燃料とは異なった、コンパクト性・簡便性・安全性に優れる燃料電池用容器が必要になる。すなわち、汎用の化学電池のようなポータブル電源として適用するためには、作動温度までの温度上昇を短時間化するために、また熱容量を小さくするために、燃料電池用容器を小型化・低背化する必要があるが、従来の燃料電池21では熱容量の割合の大部分を占めるガスセパレータ26は、特にカーボン板の表面に切削加工で流路形成されるガスセパレータ26の場合など、薄肉化すると脆くなるため、数ｍｍの厚みが必要である。このため、小型化・低背化が困難であるという問題点もあった。
【００１４】
さらに、燃料電池21の出力電圧は、電解質部材23の表裏面の各電極24・25に供給されるガスの分圧によって決まる。すなわち、電解質部材23に供給された燃料ガスがガス流路28を進んで発電反応において消費されると、燃料極24の面上の燃料ガスの分圧が下がって出力電圧が下がる。これと同様に、空気も空気流路29を進んで消費されると、空気極25の面上の酸素の分圧が下がって出力電圧が下がる。従って、燃料ガスを均等に供給する必要があるが、従来の燃料電池21のガスセパレータ26は、特にカーボン板の表面に切削加工により流路を形成していることから、薄型化したときには流路の溝が狭くなるため、流路抵抗が大きくなり、均一なガス供給が困難であるという問題点もあった。
【００１５】
また、複数の電解質部材23とその対向する燃料極24・空気極25とガスセパレータ26との組み合わせが、任意に効率よく直列接続または並列接続されて、全体の出力電圧および出力電流が調整されるようにする必要があるが、従来の燃料電池21では電解質部材23を挟む燃料極および空気極から電気を取り出すためには、外部に引き出し接続する方法か、もしくはガスセパレータ26を導電性材料として重ね合わせ直列接続する方法しかなく、小型燃料電池においてはそれが困難であるという問題点もあった。
【００１６】
本発明は以上のような従来の技術の問題点に鑑み完成されたものであり、その目的は、電解質部材を収納可能な、小型で、堅牢な燃料電池用容器であり、また、ガスの均等供給・燃料電池容器内の温度勾配の均一化・高効率な電気接続を図ることができる信頼性のある燃料電池用容器およびそれを用いた燃料電池を提供することにある。
【００１７】
【課題を解決するための手段】
本発明の第１の燃料電池用容器は、下側および上側主面にそれぞれ第１および第２電極を有する電解質部材を収容する凹部を上面に複数個有するセラミックスから成る基体と、前記電解質部材の前記下側主面に対向する前記凹部の底面から前記基体の外面にかけて形成された第１流体流路と、導体ペーストを焼成して前記基体と一体的に形成されるとともに、前記電解質部材の前記第１電極に対向する前記凹部の底面に一端が配設され、他端が前記基体の外面に導出された第１配線導体と、前記基体の前記凹部の周囲の上面に前記凹部を覆って取着される、前記凹部を気密に封止する蓋体と、前記電解質部材の前記上側主面に対向する前記蓋体の下面から前記蓋体の外面にかけて形成された第２流体流路と、導体ペーストを焼成して前記蓋体と一体的に形成されるとともに、前記電解質部材の前記第２電極に対向する前記蓋体の前記蓋体の下面に一端が配設され、他端が前記蓋体の外面に導出された第２配線導体と、導体ペーストを焼成して前記基体と一体的に形成されるように前記基体に形成され、一端が前記複数の凹部のうち１つの凹部の底面で前記電解質部材の前記第１電極に対向するとともに、他端が他の凹部の底面で前記電解質部材の前記第１電極に対向する第３配線導体とを具備することを特徴とするものである。
また、本発明の第１の燃料電池用容器は、前記第１配線導体および前記第３配線導体の少なくとも一方が前記凹部の底面より１０μｍ以上突出するように形成されているか、または前記第２配線導体が前記蓋体の下面より１０μｍ以上突出するように形成されていることを特徴とするものである。
【００１８】
また、本発明の第２の燃料電池用容器は、下側および上側主面にそれぞれ第１および第２電極を有する電解質部材を収容する凹部を上面に複数個有するセラミックスから成る基体と、前記電解質部材の前記下側主面に対向する前記凹部の底面から前記基体の外面にかけて形成された第１流体流路と、導体ペーストを焼成して前記基体と一体的に形成されるとともに、前記電解質部材の前記第１電極に対向する前記凹部の底面に一端が配設され、他端が前記基体の外面にかけて形成された第１配線導体と、前記基体の前記凹部の周囲の上面に前記凹部を覆って取着される、前記凹部を気密に封止する蓋体と、前記電解質部材の前記上側主面に対向する前記蓋体の下面から前記蓋体の外面にかけて形成された第２流体流路と、導体ペーストを焼成して前記蓋体と一体的に形成されるとともに、前記電解質部材の前記第２電極に対向する前記蓋体の下面に一端が配設され、他端が前記蓋体の外面に導出された第２配線導体と、導体ペーストを焼成して前記基体と一体的に形成され、一端が前記複数の凹部のうち１つの凹部の底面で前記電解質部材の前記第１電極に対向するとともに、他端が前記基体の前記蓋体が取着される上面に導出された第４配線導体と、導体ペーストを焼成して前記蓋体と一体的に形成され、一端が前記蓋体の下面で他の凹部の前記電解質部材の前記第２電極に対向するとともに、他端が前記蓋体の前記基体の前記上面に取得される下面に前記第４配線導体の他端と対向するように導出された第５配線導体とを具備することを特徴とするものである。
また、本発明の第２の燃料電池用容器は、前記第１配線導体および前記第４配線導体の少なくとも一方が前記凹部の底面より１０μｍ以上突出するように形成されているか、または前記第２配線導体および前記第５配線導体の少なくとも一方が前記蓋体の下面より１０μｍ以上突出するように形成されていることを特徴とするものである。
【００１９】
また、本発明の第１の燃料電池は、上記構成の本発明の第１の燃料電池用容器の複数個の前記凹部に電解質部材を収容して、この電解質部材の前記下側および上側主面を前記第１および第２流体流路との間でそれぞれ流体の供給あるいは排出が可能なように配置するとともに、前記第１および第２配線導体を前記第１および第２電極に、ならびに前記第３配線導体を前記第１電極にそれぞれ電気的に接続し、前記基体の前記凹部の周囲の上面に前記凹部を覆って前記蓋体を取着して成ることを特徴とするものである。
【００２０】
また、本発明の第２の燃料電池は、上記構成の本発明の第２の燃料電池用容器の複数個の前記凹部に電解質部材を収容して、この電解質部材の前記下側および上側主面を前記第１および第２流体流路との間でそれぞれの流体の供給あるいは排出が可能なように配置するとともに、前記第１および第２配線導体を前記第１および第２電極に、ならびに前記第４および第５配線導体を前記第１および第２電極にそれぞれ電気的に接続し、前記基体の前記凹部の周囲の上面に前記凹部を覆うとともに前記第４および第５配線導体の前記他端同士を接続して前記蓋体を取着して成ることを特徴とするものである。
【００２１】
本発明の第１および第２の燃料電池用容器によれば、下側および上側主面にそれぞれ第１および第２電極を有する電解質部材を収容する凹部を上面に有するセラミックスから成る基体と、この基体の凹部の周囲の上面に凹部を覆って取着される、凹部を気密に封止する蓋体とを具備していることから、燃料電池用容器内を気密に封止することで、気体等の流体の漏れがなく、この容器の他にパッケージ等の容器を設ける必要がないので、効率良く動作させることができる燃料電池を得ることができるとともに、小型化にも有効なものとなる。また、凹部を上面に有するセラミックスから成る基体とこの凹部を封止する蓋体とで形成される箱体内に複数の電解質部材を収納して燃料電池とすることができるので、電解質部材が容器の外部に露出して損傷を受けたりすることがなく、燃料電池全体としての機械的信頼性が向上する。また、凹部および蓋体で構成される容器内部に一端が配設された第１〜第３配線導体、または第１，第２，第４および第５配線導体の他には電解質部材自体に無用な電気的接触をしないで済むので、信頼性および安全性の高い燃料電池を得ることができる。さらに、燃料電池用容器の構成材料としてセラミックスを用いたことにより、各種のガスを始めとする流体に対する耐食性に優れる燃料電池を得ることができる。
【００２２】
また、電解質部材の下側主面に対向する凹部の底面から基体の外面にかけて形成された第１流体流路と、電解質部材の上側主面に対向する蓋体の下面から蓋体の外面にかけて形成された第２流体流路とを具備していることから、複数のそれぞれの流体流路は、電解質部材を挟んで、それぞれ対向する内壁面に設けられているため、電解質部材へ供給される流体の均一供給性を向上させることができる。このような流体経路によれば、流体が電解質部材に対して垂直に流れるため、例えば、流体が水素ガスと空気（酸素）ガスとの場合に、電解質部材が下側および上側主面にそれぞれ有する第１および第２電極に供給される各ガス分圧が下がることはなく、所定の安定した出力電圧を得ることができるという効果がある。さらに、供給される流体の圧力、例えばガス分圧が安定するため、燃料電池用容器の内部温度の分布が均一化され、その結果、電解質部材に生じる熱応力を抑制することができ、燃料電池の信頼性を向上させることができる。さらにまた、それぞれの流体流路は基体と蓋体とに形成されるため、各流路の密閉性に優れ、本来は流路的に隔絶されるべき２種類の原料流体（例えば酸素ガスと水素ガスもしくはメタノール等）が混合してしまうことによって燃料電池としての機能が発現されなくなるようなことがなく、また、可燃性の流体が高温で混合された後に引火・爆発を起こす危険性もないので、安全な燃料電池を提供することができる。
【００２３】
さらに、本発明の第１の燃料電池用容器によれば、基体に形成された、一端が１つの凹部の底面で電解質部材の第１電極に対向するとともに、他端が他の凹部の底面で電解質部材の第１電極に対向する第３配線導体とを具備していることから、複数個の電解質部材を電気的に接続することでそれらを並列接続することが可能となる。その結果、燃料電池全体の出力電流の調整ができるため、電解質部材にて電気化学的に生成された電気を良好な状態で外部に取り出すことができる。
【００２４】
さらにまた、本発明の第２の燃料電池用容器によれば、電解質部材を収容する複数個の凹部を有する基体およびこれに取着される蓋体に形成された、一端が１つの凹部の底面で電解質部材の第１電極に対向するとともに、他端が基体の上面の蓋体が取着される部位に導出された第４配線導体と、一端が蓋体の下面で他の凹部の電解質部材の第２電極に対向するとともに、他端が蓋体の下面の基体の上面に取着される部位に第４配線導体の他端と対向するように導出された第５配線導体とを具備していることから、複数個の電解質部材を電気的に接続することでそれらを直列接続することが可能となる。その結果、一つ一つの電解質部材の発電では微小電圧であっても、直列接続により合計の電圧の調整ができるため、電解質部材にて電気化学的に生成された電気を良好な状態で外部に取り出すことが可能となる。
【００２５】
また、本発明の第１および第２の燃料電池によれば、本発明の第１および第２の燃料電池用容器の凹部に電解質部材を収容して、この電解質部材の下側および上側主面を第１および第２流体流路との間でそれぞれの流体がやりとり可能なように配置するとともに、第１および第２電極を第１〜第３配線導体、ならびに第１，第２，第４および第５配線導体にそれぞれ電気的に接続し、基体の凹部の周囲の上面に凹部を覆って蓋体を取着して成ることから、以上のような本発明の第１および第２の燃料電池用容器による特長を備えた、小型・堅牢で、ガスの均等供給・燃料電池容器内の温度勾配の均一化・高効率な電気接続を図ることができる信頼性のある燃料電池を得ることができるとともに、複数個の電解質部材を並列接続することにより燃料電池全体の出力電流の調整ができるため、あるいは複数個の電解質部材を直列接続することにより合計の電圧の調整ができるため、電解質部材にて電気化学的に生成された電気を良好な状態で外部に取り出すことができる。
【００２６】
従って、本発明の燃料電池用容器および燃料電池によれば、コンパクト性・簡便性・安全性に優れ、流体の均等供給・高効率な電気接続により、長期にわたり安定して作動させることができる燃料電池を提供することができる。
【００２７】
【発明の実施の形態】
次に、本発明を添付図面に基づき詳細に説明する。
【００２８】
図１は本発明の第１の燃料電池用容器およびそれを用いた第１の燃料電池について実施の形態の一例を示す断面図である。図１において、１は燃料電池、２は燃料電池用容器、３は電解質部材、４は第１電極、５は第２電極、６は基体、７は蓋体、８は第１流体流路、９は第２流体流路、10は第１配線導体、11は第２配線導体、12は第３配線導体である。
【００２９】
電解質部材３は、例えばイオン導電膜（交換膜）の両主面上に、下側主面に形成された第１電極４および上側主面に形成された第２電極５にそれぞれ対向するように、アノード側電極となる燃料極（図示せず）と、カソード側電極となる空気極（図示せず）とが一体的に形成されている。そして、電解質部材３で発電された電流を第１電極４，第２電極５へ流し、外部へ取り出すことができるものとなっている。
【００３０】
このような電解質部材３のイオン導電膜（交換膜）は、パーフルオロカーボンスルフォン酸樹脂、例えばナフィオン（商品名、デュポン社製）等のプロトン伝導性のイオン交換樹脂により構成されている。また、燃料極および空気極は、多孔質状態のガス拡散電極であり、多孔質触媒層とガス拡散層の両方の機能を兼ね備えるものである。これらの燃料極および空気極は、白金，パラジウムあるいはこれらの合金等の触媒を担持した導電性微粒子、例えばカーボン微粒子をポリテトラフルオロエチレンのような疎水性樹脂結合剤により保持した多孔質体によって構成されている。
【００３１】
電解質部材３の下側主面の第１電極４および上側主面の第２電極５は、白金や白金−ルテニウム等の触媒微粒子の付いた炭素電極を電解質部材３上にホットプレスする方法、または、白金や白金−ルテニウム等の触媒微粒子の付いた炭素電極材料と電解質材料を分散した溶液との混合物を電解質上に塗布または転写する方法等により形成される。
【００３２】
燃料電池用容器２は、凹部を有する基体６と蓋体７とから成り、電解質部材３を凹部の内部に搭載して気密に封止する役割を持ち、酸化アルミニウム（Ａｌ₂Ｏ₃）質焼結体，ムライト（３Ａｌ₂Ｏ₃・２ＳｉＯ₂）質焼結体，炭化珪素（ＳｉＣ）質焼結体，窒化アルミニウム（ＡｌＮ）質焼結体，窒化珪素（Ｓｉ₃Ｎ₄）質焼結体，ガラスセラミックス焼結体等のセラミックス材料で形成されている。
【００３３】
なお、ガラスセラミックス焼結体はガラス成分とフィラー成分とから成るが、ガラス成分としては、例えばＳｉＯ₂−Ｂ₂Ｏ₃系，ＳｉＯ₂−Ｂ₂Ｏ₃−Ａｌ₂Ｏ₃系，ＳｉＯ₂−Ｂ₂Ｏ₃−Ａｌ₂Ｏ₃−ＭＯ系（但し、ＭはＣａ，Ｓｒ，Ｍｇ，ＢａまたはＺｎを示す），ＳｉＯ₂−Ａｌ₂Ｏ₃−Ｍ¹Ｏ−Ｍ²Ｏ系（但し、Ｍ¹およびＭ²は同一または異なってＣａ，Ｓｒ，Ｍｇ，ＢａまたはＺｎを示す），ＳｉＯ₂−Ｂ₂Ｏ₃−Ａｌ₂Ｏ₃−Ｍ¹Ｏ−Ｍ²Ｏ系（但し、Ｍ¹およびＭ²は前記と同じである），ＳｉＯ₂−Ｂ₂Ｏ₃−Ｍ³ ₂Ｏ系（但し、Ｍ³はＬｉ，ＮａまたはＫを示す），ＳｉＯ₂−Ｂ₂Ｏ₃−Ａｌ₂Ｏ₃−Ｍ³ ₂Ｏ系（但し、Ｍ³は前記と同じである），Ｐｂ系ガラス，Ｂｉ系ガラス等が挙げられる。
【００３４】
また、フィラー成分としては、例えばＡｌ₂Ｏ₃，ＳｉＯ₂，ＺｒＯ₂とアルカリ土類金属酸化物との複合酸化物、ＴｉＯ₂とアルカリ土類金属酸化物との複合酸化物、Ａｌ₂Ｏ₃およびＳｉＯ₂から選ばれる少なくとも１種を含む複合酸化物（例えばスピネル，ムライト，コージェライト）等が挙げられる。
【００３５】
燃料電池用容器２は、凹部を有する基体６と蓋体７とから成り、基体６の凹部の周囲に凹部を覆って蓋体７を取着することによって凹部を気密に封止するため、半田や銀ろう等の金属接合材料での接合、エポキシ等の樹脂材料での接合、凹部の周囲の上面に鉄合金等で作られたシールリング等を接合してシームウェルドやエレクトロンビームやレーザ等で溶接する方法等によって、蓋体７が基体６に取着される。なお、蓋体７にも基体６と同様の凹部を形成しておいてもよい。
【００３６】
基体６および蓋体７は、それぞれ厚みを薄くし、燃料電池１の低背化を可能とするためには、機械的強度である曲げ強度が200ＭＰａ以上であることが好ましい。
【００３７】
基体６および蓋体７は、例えば相対密度が95％以上の緻密質からなる酸化アルミニウム質焼結体で形成されていることが好ましい。その場合であれば、例えば、まず酸化アルミニウム粉末に希土類酸化物粉末や焼結助剤を添加・混合して、酸化アルミニウム質焼結体の原料粉末を調整する。次いで、この酸化アルミニウム質焼結体の原料粉末に有機バインダおよび分散媒を添加・混合してペースト化し、このペーストからドクターブレード法によって、あるいは原料粉末に有機バインダを加え、プレス成形，圧延成形等によって、所定の厚みのグリーンシートを作製する。そして、このグリーンシートに対して、金型による打ち抜き，マイクロドリル，レーザ等により、第１流体流路８および第２流体流路９としての貫通穴、ならびに第1配線導体10，第２配線導体11および第３配線導体12を配設するための貫通孔を形成する。
【００３８】
第1配線導体10，第２配線導体11および第３配線導体12は、酸化を防ぐために、タングステンおよび／またはモリブデンで形成されているのが好ましい。その場合であれば、例えば、無機成分としてタングステンおよび／またはモリブデン粉末100質量部に対して、Ａｌ₂Ｏ₃を３〜20質量部，Ｎｂ₂Ｏ₅を0.5〜５質量部の割合で添加してなる導体ペーストを調製する。この導体ペーストをグリーンシートの貫通孔内に充填して、貫通導体としてのヴィア導体を形成する。
【００３９】
これらの導体ペースト中には、基体６や蓋体７のセラミックスとの密着性を高めるために、酸化アルミニウム粉末や、基体６や蓋体７を形成するセラミックス成分と同一の組成物粉末を、例えば0.05〜２体積％の割合で添加することも可能である。
【００４０】
なお、基体６や蓋体７の表層および内層への第1配線導体10，第２配線導体11および第３配線導体12の形成は、貫通孔へ導体ペーストを充填してヴィア導体を形成する前後あるいはそれと同時に、同様の導体ペーストをグリーンシートに対しスクリーン印刷，グラヴィア印刷等の方法で所定パターンに印刷塗布して形成する。
【００４１】
その後、導体ペーストを印刷し充填した所定枚数のシート状成形体を位置合わせして積層圧着した後、この積層体を、例えば非酸化性雰囲気中にて、焼成最高温度が1200〜1500℃の温度で焼成して、目的とするセラミックスの基体６や蓋体７および第1配線導体10，第２配線導体11，第３配線導体12を得る。
【００４２】
また、セラミックスから成る基体６や蓋体７は、その厚みを0.2ｍｍ以上とすることが好ましい。厚みが0.2ｍｍ未満では、強度が不足しがちなため、基体６に蓋体７を取着したときに発生する応力により、基体６および蓋体７に割れ等が発生しやすくなる傾向がある。他方、厚みが５ｍｍを超えると、薄型化・低背化が困難となるため、小型携帯機器に搭載する燃料電池としては不適切となり、また、熱容量が大きくなるため、電解質部材３の電気化学反応条件に相当する適切な温度にすばやく設定することが困難となる傾向がある。
【００４３】
第１配線導体10，第２配線導体11および第３配線導体12は、それぞれ電解質部材３の第１電極４および第２電極５に電気的に接続されて、電解質部材３で発電された電流を燃料電池用容器２の外部へ取り出すための導電路として機能する。
【００４４】
第１配線導体10は、基体６の凹部の底面の電解質部材３の第１電極４に対向する部位に一端が配設され、他端が基体６の外面に導出されて形成されている。このような第１配線導体10は、前述のように基体６と一体的に形成されている。また、第1配線導体10は、その両端を第１電極４に接触させやすいように基体６の凹部の底面より10μｍ以上高くするように形成するのが望ましい。この高さを得るためには、前述したように導体ペーストを印刷塗布して形成する際に、塗布厚みを厚くするように印刷条件を設定すればよい。また、第1配線導体10は第１電極４に対向させて複数配置し、第１配線導体10による電気損失を減少させることが望ましく、第1配線導体10の基体６の貫通部についてはφ50μｍ以上の径とすることが好ましい。
【００４５】
また、第２配線導体11は、蓋体７の下面の電解質部材３の第２電極５に対向する部位に一端が配設され、他端が蓋体７の外面に導出されて形成されている。このような第２配線導体11も、第１配線導体10と同様に、蓋体７と一体的に形成されている。また、第２配線導体11は、その両端を第２電極５に接触させやすいように蓋体７の下面より10μｍ以上高くするように形成するのが望ましい。この高さを得るためには、前述したように導体ペーストを印刷塗布して形成する際に、塗布厚みを厚くするように印刷条件を設定すればよい。また、第２配線導体11は第２電極５に対向させて複数配置し、第２配線導体11による電気損失を減少させることが望ましく、第２配線導体11の蓋体７の貫通部についてはφ50μｍ以上の径とすることが好ましい。
【００４６】
また、第３配線導体１２は、基体６の複数個の凹部のうち１つの凹部の底面の電解質部材３の第１電極４に対向する部位に一端が配設され、他端が他の凹部の底面で他の電解質部材３の第１電極４に対向する部位に配設されて基体６と一体的に形成されている。また、第３配線導体１２は、その両端を第１電極４に接触させやすいように基体６の凹部の底面より１０μｍ以上突出するように形成するのが望ましい。この高さを得るためには、前述したように導体ペーストを印刷塗布して形成する際に、塗布厚みを厚くするように印刷条件を設定すればよい。また、第３配線導体１２は第１電極４に対向させて複数配置し、第３配線導体１２による電気損失を減少させることが望ましく、第３配線導体１２の基体６の貫通部についてはφ５０μｍ以上の径とすることが好ましい。
【００４７】
これら第１配線導体10，第２配線導体11および第３配線導体12には、その露出する表面にニッケルから成る良導電性で、かつ耐蝕性およびロウ材との濡れ性が良好な金属をメッキ法により被着させておくと、第１配線導体10，第２配線導体11および第３配線導体12と、第１配線導体10，第２配線導体11および第３配線導体12ならびに外部電気回路との電気的接続を良好とすることができる。従って、第１配線導体10，第２配線導体11および第３配線導体12は、その露出する表面にニッケルから成る良導電性で、かつ耐蝕性およびロウ材との濡れ性が良好な金属をメッキ法により被着させておくことが好ましい。
【００４８】
そして、これら第１，第２および第３配線導体10・11・12と第１および第２電極４・５との電気的な接続は、基体６と蓋体７とで電解質部材３を挟み込むことによって、第1，第２および第３配線導体10・11・12と第1および第２電極４・５とを圧着接触させて電気的接続させる等の構成によって行なえばよい。
【００４９】
また、第１電極４および第２電極５に対向する基体６の凹部の底面および蓋体７の下面には、それぞれ第１流体流路８および第２流体流路９が配置されており、第１流体流路８は基体６の外面にかけて、また第２流体流路９は蓋体７の外面にかけて形成されている。これら第１および第２流体流路８・９は、それぞれ基体６や蓋体７に形成した貫通穴あるいは溝によって、燃料ガス例えば水素に富む改質ガス、あるいは酸化剤ガス例えば空気等の、電解質部材３へ供給される流体の通路として、あるいは反応で生成される水等の、反応後に電解質部材３から排出される流体の通路として設けられている。
【００５０】
第１流体流路８および第２流体流路９として基体６および蓋体７に形成される貫通穴あるいは溝は、電解質部材３に均等に燃料ガスや酸化剤ガス等の流体が供給されるように、燃料電池１の仕様に応じて、貫通穴の径や数、あるいは溝の幅，深さ，配置を決めればよい。
【００５１】
本発明の第１の燃料電池用容器２および第１の燃料電池１においては、第１流体流路８および第２流体流路９は、好適には、電解質部材３に均一な圧力で流体を流すため、φ0.1ｍｍ以上の穴径とし、間隔を一定にして配置するようにするとよい。
【００５２】
このように電解質部材３の第１電極４が形成された下側主面に対向させて第１流体流路８を、第２電極５が形成された上側主面に対向させて第２流体流路９を形成したことによって、電解質部材３の下側および上側主面と第１および第２流体流路８・９との間で流体がやりとり可能となり、その流体がそれぞれの流路を通して供給あるいは排出されることとなる。そして、例えば流体としてガスを供給する場合であれば、電解質部材３の第１電極４および第２電極５にそれぞれ供給されるガス分圧が下がることをなくすことができ、所定の安定した出力電圧を得ることができる。さらに、供給されるガス分圧が安定するため、燃料電池１の内部圧力が均一化され、その結果、電解質部材３に生じる熱応力を抑制することができるので、第１の燃料電池１の信頼性を向上させることができる。
【００５３】
以上の構成により、図１に示すような、電解質部材３を収納可能な、小型で堅牢な本発明の第１の燃料電池用容器２が得られ、高効率制御が可能な本発明の第１の燃料電池１が得られる。
【００５４】
次に図２は本発明の第２の燃料電池用容器およびそれを用いた第２の燃料電池について実施の形態の一例を示す断面図である。これらの図において、１’は燃料電池、２’は燃料電池用容器、３は電解質部材、４は第１電極、５は第２電極、６は基体、７は蓋体、８は第１流体流路、９は第２流体流路、10は第１配線導体、11は第２配線導体、13は第４配線導体、14は第５配線導体である。
【００５５】
図２の３から１１については図１と同様となる。第４配線導体１３は、基体６の複数個の凹部のうち１つの凹部の底面で電解質部材３の第１電極４に対向する部位に一端が配設され、他端が基体６の上面の蓋体７が取着される部位に導出されている。また、第５配線導体１４は、蓋体７の下面の、他の凹部の電解質部材３の第２電極５に対向する部位に一端が配設され、他端が蓋体７の下面の基体６の上面に取着される部位に第４配線導体１３の他端と対向するように導出されて形成されている。
【００５６】
このような第４配線導体１３は、第３配線導体１２と同様に、基体６と一体的に形成され、その一端を第１電極４に接触させやすいように基体６の凹部の底面より１０μｍ以上突出するように形成するのが望ましい。この高さを得るためには、前述したように導体ペーストを印刷塗布して形成する際に、塗布厚みを厚くするように印刷条件を設定すればよい。また、第４配線導体１３は第１電極４に対向させて複数配置し、第４配線導体１３による電気損失を減少させることが望ましく、第４配線導体１３の基体６の貫通部についてはφ５０μｍ以上の径とすることが好ましい。
【００５７】
また、第５配線導体１４も、第２配線導体１１と同様に、蓋体７と一体的に形成され、その一端を第２電極５に接触させやすいように蓋体７の下面より１０μｍ以上突出するように形成するのが望ましい。この高さを得るためには、前述したように導体ペーストを印刷塗布して形成する際に、塗布厚みを厚くするように印刷条件を設定すればよい。また、第５配線導体１４も第２電極５に対向させて複数配置し、第５配線導体１４による電気損失を減少させることが望ましく、第５配線導体１４の蓋体７の貫通部についてはφ５０μｍ以上の径とすることが好ましい。
【００５８】
図１および図２に示すように、本発明の第１および第２の燃料電池用容器２・２’ならびに第１および第２の燃料電池１・１’によれば、複数個の凹部を有する基体６の凹部のそれぞれに電解質部材３を収容するとともに、隣接する凹部の端部間にわたって第３配線導体12、または第４配線導体13および第５配線導体14を配設し、複数の電解質部材３の第１電極４の間、または第１電極４と第２電極５との間を電気的に接続し、両端となる位置に配置された電解質部材３に全体としての出力を取り出すように第１配線導体10および第２配線導体11をそれぞれに電気的に接続することで、第１〜第３配線導体10・11・12により、ならびに第１，第２，第４および第５配線導体10・11・13・14により３次元的に自由に配線ができるため、複数個の電解質部材３を任意に直列接続または並列接続することが可能となる。その結果、全体の出力電圧および出力電流を効率よく調整することが可能となるため、複数個の電解質部材３にて電気化学的に生成された電気を良好に外部に取り出すことができる燃料電池となる。
【００５９】
なお、本発明は以上の実施の形態の例に限定されるものではなく、本発明の要旨を逸脱しない範囲であれば、種々の変更を行なっても何ら差し支えない。例えば、第１流体流路や第２流体流路については、燃料電池全体を薄型化するため、基体または蓋体の側面からの流入口を設けるようにしてもよい。これによれば、特に携帯電子機器用として小型化を図る上で有効となる。さらに、第１および第２配線導体については、基体および蓋体の外面に導出される他端を、それぞれ同じ側の側面に引き出すように配設してもよい。これによれば、燃料電池の一方側面に配線や流路等をまとめることができ、小型化と外部への接合部の保護とが容易となり、信頼性の高い設計が可能となるとともに、長期間安定した作動が可能な燃料電池となる。
【００６０】
【発明の効果】
本発明の第１および第２の燃料電池用容器によれば、下側および上側主面にそれぞれ第１および第２電極を有する電解質部材を収容する凹部を上面に有するセラミックスから成る基体と、この基体の凹部の周囲の上面に凹部を覆って取着される、凹部を気密に封止する蓋体とを具備していることから、燃料電池用容器内を気密に封止することで、気体等の流体の漏れがなく、この容器の他にパッケージ等の容器を設ける必要がないので、効率良く動作させることができる燃料電池を得ることができるとともに、小型化にも有効なものとなる。また、凹部を上面に有するセラミックスから成る基体とこの凹部を封止する蓋体とで形成される箱体内に複数の電解質部材を収納して燃料電池とすることができるので、電解質部材が容器の外部に露出して損傷を受けたりすることがなく、燃料電池全体としての機械的信頼性が向上する。また、凹部および蓋体で構成される容器内部に一端が配設された第１〜第３配線導体、または第１，第２，第４および第５配線導体の他には電解質部材自体に無用な電気的接触をしないで済むので、信頼性および安全性の高い燃料電池を得ることができる。さらに、燃料電池用容器の構成材料としてセラミックスを用いたことにより、各種のガスを始めとする流体に対する耐食性に優れる燃料電池を得ることができる。
【００６１】
また、電解質部材の下側主面に対向する凹部の底面から基体の外面にかけて形成された第１流体流路と、電解質部材の上側主面に対向する蓋体の下面から蓋体の外面にかけて形成された第２流体流路とを具備していることから、複数のそれぞれの流体流路は、電解質部材を挟んで、それぞれ対向する内壁面に設けられているため、電解質部材へ供給される流体の均一供給性を向上させることができる。このような流体経路によれば、流体が電解質部材に対して垂直に流れるため、例えば、流体が水素ガスと空気（酸素）ガスとの場合に、電解質部材が下側および上側主面にそれぞれ有する第１および第２電極に供給される各ガス分圧が下がることはなく、所定の安定した出力電圧を得ることができるという効果がある。さらに、供給される流体の圧力、例えばガス分圧が安定するため、燃料電池用容器の内部温度の分布が均一化され、その結果、電解質部材に生じる熱応力を抑制することができ、燃料電池の信頼性を向上させることができる。さらにまた、それぞれの流体流路は基体と蓋体とに形成されるため、各流路の密閉性に優れ、本来は流路的に隔絶されるべき２種類の原料流体（例えば酸素ガスと水素ガスもしくはメタノール等）が混合してしまうことによって燃料電池としての機能が発現されなくなるようなことがなく、また、可燃性の流体が高温で混合された後に引火・爆発を起こす危険性もないので、安全な燃料電池を提供することができる。
【００６２】
また、本発明の第１および第２の燃料電池によれば、本発明の第１および第２の燃料電池用容器の凹部に電解質部材を収容して、この電解質部材の下側および上側主面を第１および第２流体流路との間でそれぞれの流体がやりとり可能なように配置するとともに、第１および第２電極を第１〜第３配線導体、ならびに第１，第２，第４および第５配線導体にそれぞれ電気的に接続し、基体の凹部の周囲の上面に凹部を覆って蓋体を取着して成ることから、電解質部材が露出して損傷を受けることがなく、また、凹部および蓋体で構成される容器内部に一端が配設された第１〜第３配線導体、ならびに第１，第２，第４および第５配線導体の他には電解質部材に無用な電気的接触をしないで済むので、信頼性および安全性の高い燃料電池を得ることができる。また、第１および第２流体流路は、電解質部材を挟んで、それぞれ対向する内壁面である基体の凹部の底面および蓋体の下面に設けられているため、電解質部材へ供給されるガスの均一供給性を向上させることができ、電解質部材の第１および第２電極に供給されるガス分圧が下がることをなくすことができるので、所定の安定した出力電圧を得ることができる。そして、電解質部材に生じる応力も抑制することができ、信頼性を向上させることができる。
【００６３】
さらに、本発明の第１の燃料電池用容器によれば、基体に形成された、一端が１つの凹部の底面で電解質部材の第１電極に対向するとともに、他端が他の凹部の底面で電解質部材の第１電極に対向する第３配線導体とを具備していることから、複数個の電解質部材を電気的に接続することでそれらを並列接続することが可能となる。その結果、燃料電池全体の出力電流の調整ができるため、電解質部材にて電気化学的に生成された電気を良好な状態で外部に取り出すことができる。
【００６４】
さらにまた、本発明の第２の燃料電池用容器によれば、電解質部材を収容する複数個の凹部を有する基体およびこれに取着される蓋体に形成された、一端が１つの凹部の底面で電解質部材の第１電極に対向するとともに、他端が基体の上面の蓋体が取着される部位に導出された第４配線導体と、一端が蓋体の下面で他の凹部の電解質部材の第２電極に対向するとともに、他端が蓋体の下面の基体の上面に取得される部位に第４配線導体の他端と対向するように導出された第５配線導体とを具備していることから、複数個の電解質部材を電気的に接続することでそれらを直列接続することが可能となる。その結果、一つ一つの電解質部材の発電では微小電圧であっても、直列接続により合計の電圧の調整ができるため、電解質部材にて電気化学的に生成された電気を良好な状態で外部に取り出すことが可能となる。
【００６５】
また、本発明の第１および第２の燃料電池によれば、本発明の第１および第２の燃料電池用容器の凹部に電解質部材を収容して、この電解質部材の下側および上側主面を第１および第２流体流路との間でそれぞれの流体がやりとり可能なように配置するとともに、第１および第２電極を第１〜第３配線導体、ならびに第１，第２，第４および第５配線導体にそれぞれ電気的に接続し、基体の凹部の周囲の上面に凹部を覆って蓋体を取着して成ることから、以上のような本発明の第１および第２の燃料電池用容器による特長を備えた、小型・堅牢で、ガスの均等供給・燃料電池容器内の温度勾配の均一化・高効率な電気接続を図ることができる信頼性のある燃料電池を得ることができるとともに、複数個の電解質部材を並列接続することにより燃料電池全体の出力電流の調整ができるため、あるいは複数個の電解質部材を直列接続することにより合計の電圧の調整ができるため、電解質部材にて電気化学的に生成された電気を良好な状態で外部に取り出すことができる。
【００６６】
従って、本発明の燃料電池用容器および燃料電池によれば、コンパクト性、簡便性・安全性に優れ、ガスの均等供給・高効率な電気接続により、長期にわたり安定して作動させることができる燃料電池を提供することができた。
【図面の簡単な説明】
【図１】本発明の第１の燃料電池用容器およびそれを用いた本発明の第１の燃料電池の実施の形態の一例を示す断面図である。
【図２】本発明の第２の燃料電池用容器およびそれを用いた本発明の第２の燃料電池の実施の形態の一例を示す断面図である。
【図３】従来の燃料電池の例を示す断面図である。
【符号の説明】
１，１’：燃料電池
２，２’：燃料電池用容器
３：電解質部材
４：第１電極
５：第２電極
６：基体
７：蓋体
８：第１流体流路
９：第２流体流路
10：第１配線導体
11：第２配線導体
12：第３配線導体
13：第４配線導体
14：第５配線導体[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a small and highly reliable fuel cell container made of ceramics that can accommodate an electrolyte member, and a fuel cell using the same.
[0002]
[Prior art]
In recent years, development of small fuel cells that operate at a lower temperature than before has been actively conducted. Depending on the type of electrolyte used for the fuel cell, a polymer electrolyte fuel cell (hereinafter referred to as PEFC), a phosphoric acid fuel cell, or a solid electrolyte fuel cell is known. ing.
[0003]
Among them, PEFC has a low operating temperature of about 80-100 ° C.
(1) The output density is high, and it is possible to reduce the size and weight.
(2) Since the electrolyte is not corrosive and the operating temperature is low, since there are few restrictions on the battery constituent materials from the viewpoint of corrosion resistance, cost reduction is easy.
(3) Since it can be started at room temperature, the startup time is short.
It has excellent features such as For this reason, PEFC takes advantage of the above features, not only for driving power sources for vehicles and home cogeneration systems, but also for mobile phones, PDAs (Personal Digital Assistants), laptop computers, digital cameras, The use as a power source for portable electronic devices having an output of several watts to several tens of watts has been considered.
[0004]
The PEFC is roughly classified, for example, a fuel electrode (anode) composed of a carbon electrode to which catalyst fine particles such as platinum and platinum-ruthenium are adhered, and an air electrode (cathode) composed of a carbon electrode to which catalyst fine particles such as platinum are adhered, A film-like electrolyte member (hereinafter referred to as an electrolyte member) interposed between the fuel electrode and the air electrode is configured. Here, the fuel electrode is provided with hydrogen gas (H₂) Is supplied to the air electrode, while oxygen gas (O₂) Is generated (electric power generation) by the electrochemical reaction, and electric energy serving as a driving power source (voltage / current) for the load is generated.
[0005]
Specifically, hydrogen gas (H₂) Is supplied, as shown in the following chemical reaction formula (1), electrons (e^-) Separated hydrogen ions (protons; H⁺) Are generated and pass through the electrolyte member to the air electrode side, and electrons (e^-) Is taken out and supplied to the load.
3H₂ → 6H⁺+ 6e^- ... (1)
On the other hand, when air is supplied to the air electrode, as shown in the following chemical reaction formula (2), electrons (e^-) And hydrogen ions (H⁺) And oxygen gas (O₂) Reacts with water (H₂O) is generated.
6H⁺+ 3 / 2O₂+ 6e^- → 3H₂O (2)
Such a series of electrochemical reactions (formula (1) and formula (2)) proceeds at a relatively low temperature condition of approximately 80 to 100 ° C., and by-products other than electric power are basically water (H₂O) only.
[0006]
The ion conductive film (exchange membrane) constituting the electrolyte member is a polystyrene-based cation exchange membrane having a sulfonic acid group, a mixed membrane of fluorocarbon sulfonic acid and polyvinylidene fluoride, and trifluoroethylene grafted on a fluorocarbon matrix. Recently, a perfluorocarbon sulfonic acid membrane (for example, Nafion: trade name, manufactured by DuPont) or the like has been used.
[0007]
FIG. 3 is a cross-sectional view showing the configuration of a conventional fuel cell (PEFC). In the figure, 21 is a PEFC, 23 is an electrolyte member, 24 and 25 are arranged on the electrolyte member 23 so as to sandwich the electrolyte member, and a pair of porous electrodes functioning as a gas diffusion layer and a catalyst layer, that is, A fuel electrode and an air electrode, 26 is a gas separator, 28 is a fuel flow path, and 29 is an air flow path.
[0008]
The gas separator 26 is provided so as to penetrate the separator portion and the gas inflow / outflow frame that form the outer shape of the gas separator 26, the separator portion that separates the fuel passage 28 and the air passage 29, and the separator portion. The electrode member is configured to correspond to the fuel electrode 24 and the air electrode 25 of the electrolyte member 23. The fuel electrode 24 and the air electrode 25 of the electrolyte member 23 are stacked in large numbers via a gas separator 26 so that the fuel electrode 24 and the air electrode 25 are electrically connected in series and / or in parallel. A general PEFC body is a stack in which a stack is housed.
[0009]
A fuel gas containing water vapor (a gas rich in hydrogen) is supplied from the reformer to the fuel electrode 24 through the fuel flow path 28 formed in the gas separator 26, and the air electrode 25 is supplied to the atmosphere through the air flow path 29 in the atmosphere. Then, air is supplied as an oxidant gas, and power is generated by a chemical reaction in the electrolyte member 23.
[0010]
[Patent Document 1]
JP 2001-266910 A
[Patent Document 2]
Special table 2001-507501 gazette
[0011]
[Problems to be solved by the invention]
However, the fuel cell 21 that has been conventionally proposed and developed as such a high-voltage / high-capacity battery is a large-sized, large-sized battery having a stack structure and a large area, and a small battery. Conventionally, the use of the fuel cell has been hardly considered.
[0012]
That is, in the conventional gas separator 26 in such a fuel cell 21, in the laminated body in which the electrolyte member 23 is laminated using the gas separator 26, the side surface of the electrolyte member 23 is exposed to the outside, so that it falls when being carried. As a result, there is a problem that the mechanical reliability of the entire fuel cell 21 is difficult to be secured.
[0013]
In addition, in order to mount the fuel cell 21 in a portable electronic device, a fuel cell container that is different from conventional large-sized fuels and has excellent compactness, simplicity, and safety is required. That is, in order to be applied as a portable power source such as a general-purpose chemical battery, the fuel cell container is reduced in size and height to shorten the temperature rise to the operating temperature and to reduce the heat capacity. In the conventional fuel cell 21, the gas separator 26, which occupies most of the heat capacity, is thinned, particularly in the case of the gas separator 26 in which the flow path is formed by cutting on the surface of the carbon plate. Since it becomes brittle, a thickness of several mm is required. For this reason, there also existed a problem that size reduction and height reduction were difficult.
[0014]
Further, the output voltage of the fuel cell 21 is determined by the partial pressure of the gas supplied to the electrodes 24 and 25 on the front and back surfaces of the electrolyte member 23. That is, when the fuel gas supplied to the electrolyte member 23 travels through the gas flow path 28 and is consumed in the power generation reaction, the partial pressure of the fuel gas on the surface of the fuel electrode 24 decreases and the output voltage decreases. In the same manner, when the air also travels through the air flow path 29 and is consumed, the partial pressure of oxygen on the surface of the air electrode 25 decreases, and the output voltage decreases. Therefore, it is necessary to supply the fuel gas evenly. However, the gas separator 26 of the conventional fuel cell 21 has a flow path formed by cutting on the surface of the carbon plate in particular. Since the groove is narrow, there is a problem that the flow resistance is increased and it is difficult to supply a uniform gas.
[0015]
Further, a combination of the plurality of electrolyte members 23 and the opposed fuel electrode 24 / air electrode 25 and gas separator 26 is arbitrarily and efficiently connected in series or in parallel to adjust the overall output voltage and output current. However, in the conventional fuel cell 21, in order to take out electricity from the fuel electrode and the air electrode sandwiching the electrolyte member 23, it is possible to draw out and connect to the outside, or the gas separator 26 is stacked as a conductive material. There is only a method of connecting them in series, and there is a problem that it is difficult in a small fuel cell.
[0016]
The present invention has been completed in view of the problems of the conventional techniques as described above, and an object of the present invention is a small and robust fuel cell container capable of accommodating an electrolyte member, and an equal gas. It is an object of the present invention to provide a reliable fuel cell container capable of achieving uniform supply and temperature gradient in the fuel cell container and highly efficient electrical connection, and a fuel cell using the same.
[0017]
[Means for Solving the Problems]
  A first fuel cell container according to the present invention comprises a base made of ceramics having a plurality of recesses on the upper surface for accommodating electrolyte members having first and second electrodes on the lower and upper main surfaces, respectively, and the electrolyte member. The first fluid flow path formed from the bottom surface of the recess facing the lower main surface to the outer surface of the base body, the conductor paste is baked and integrally formed with the base body, and the electrolyte member One end is disposed on the bottom surface of the recess facing the first electrode and the other end is led to the outer surface of the base body, and the top surface of the base body around the recess covers the recess. A lid body hermetically sealing the recess, a second fluid flow path formed from the lower surface of the lid body facing the upper main surface of the electrolyte member to the outer surface of the lid body, and a conductor The lid is baked by baking the paste The second wiring formed integrally and having one end disposed on the lower surface of the lid body facing the second electrode of the electrolyte member and the other end led to the outer surface of the lid body A conductor and a conductor paste are formed on the base so as to be integrally formed with the base by firing a conductor paste, and one end faces the first electrode of the electrolyte member at the bottom of one of the plurality of recesses In addition, the other end includes a third wiring conductor facing the first electrode of the electrolyte member at the bottom surface of another recess.
  In the first fuel cell container of the present invention, at least one of the first wiring conductor and the third wiring conductor is formed so as to protrude 10 μm or more from the bottom surface of the recess, or the second wiring The conductor is formed so as to protrude 10 μm or more from the lower surface of the lid.
[0018]
  The second fuel cell container of the present invention comprises a base made of ceramics having a plurality of recesses on the upper surface for accommodating electrolyte members having first and second electrodes on the lower and upper main surfaces, respectively, and the electrolyte. A first fluid flow path formed from the bottom surface of the recess facing the lower main surface of the member to the outer surface of the substrate; and a conductor paste that is formed integrally with the substrate by firing the paste; and the electrolyte member One end is disposed on the bottom surface of the recess facing the first electrode and the other end is formed on the outer surface of the base, and the upper surface around the recess of the base covers the recess. A lid body hermetically sealing the recess, and a second fluid flow path formed from the lower surface of the lid body facing the upper main surface of the electrolyte member to the outer surface of the lid body Firing conductor paste And a second end formed on the lower surface of the lid opposite to the second electrode of the electrolyte member and the other end led to the outer surface of the lid. A wiring conductor and a conductor paste are baked and integrally formed with the base, and one end faces the first electrode of the electrolyte member at the bottom of one of the plurality of recesses, and the other end A fourth wiring conductor led out to the upper surface of the base body to which the lid body is attached, and a conductor paste is baked and formed integrally with the lid body; A fifth wiring conductor that is opposed to the second electrode of the electrolyte member and is led so that the other end faces the other end of the fourth wiring conductor on the lower surface obtained on the upper surface of the base body of the lid It is characterized by comprising.
  In the second fuel cell container of the present invention, at least one of the first wiring conductor and the fourth wiring conductor is formed so as to protrude 10 μm or more from the bottom surface of the recess, or the second wiring At least one of the conductor and the fifth wiring conductor is formed so as to protrude from the lower surface of the lid by 10 μm or more.
[0019]
  Further, the first fuel cell of the present invention includes an electrolyte member accommodated in the plurality of recesses of the first fuel cell container of the present invention having the above-described configuration, and the lower and upper main surfaces of the electrolyte member. Are arranged so that fluid can be supplied to or discharged from the first and second fluid flow paths, respectively, and the first and second wiring conductors are arranged on the first and second electrodes, and the first Three wiring conductors are electrically connected to the first electrode, respectively, and the lid is attached to the upper surface around the recess of the base so as to cover the recess.
[0020]
  Further, the second fuel cell of the present invention includes an electrolyte member accommodated in the plurality of recesses of the second fuel cell container of the present invention having the above-described configuration, and the lower and upper main surfaces of the electrolyte member. Are arranged so that each fluid can be supplied to or discharged from the first and second fluid flow paths, and the first and second wiring conductors are disposed on the first and second electrodes, and The fourth and fifth wiring conductors are electrically connected to the first and second electrodes, respectively, and the other end of the fourth and fifth wiring conductors is covered with the upper surface around the recess of the base. It is characterized by being connected to each other and attaching the lid.
[0021]
According to the first and second fuel cell containers of the present invention, a base made of ceramics having a recess on the upper surface for accommodating an electrolyte member having first and second electrodes on the lower and upper main surfaces, respectively. Since the upper surface around the concave portion of the base body is attached to cover the concave portion and hermetically seals the concave portion, the fuel cell container is hermetically sealed, so that the gas is sealed. Since there is no leakage of fluid such as a container and there is no need to provide a container such as a package in addition to this container, it is possible to obtain a fuel cell that can be operated efficiently and to be effective for miniaturization. In addition, since a plurality of electrolyte members can be housed in a box formed by a ceramic body having a concave portion on the upper surface and a lid that seals the concave portion, a fuel cell can be obtained. The mechanical reliability of the entire fuel cell is improved without being exposed to the outside and being damaged. In addition to the first to third wiring conductors having one end disposed inside the container constituted by the recess and the lid, or the first, second, fourth and fifth wiring conductors, the electrolyte member itself is unnecessary. Therefore, it is possible to obtain a fuel cell with high reliability and safety. Furthermore, by using ceramics as the constituent material of the fuel cell container, it is possible to obtain a fuel cell having excellent corrosion resistance against fluids including various gases.
[0022]
Also, a first fluid channel formed from the bottom surface of the recess facing the lower main surface of the electrolyte member to the outer surface of the substrate, and formed from the lower surface of the lid body facing the upper main surface of the electrolyte member to the outer surface of the lid body. Since each of the plurality of fluid flow paths is provided on the inner wall surfaces facing each other across the electrolyte member, the fluid supplied to the electrolyte member The uniform supply performance can be improved. According to such a fluid path, since the fluid flows perpendicularly to the electrolyte member, for example, when the fluid is hydrogen gas and air (oxygen) gas, the electrolyte member has on the lower and upper main surfaces, respectively. Each gas partial pressure supplied to the first and second electrodes does not decrease, and there is an effect that a predetermined stable output voltage can be obtained. Further, since the pressure of the fluid to be supplied, for example, the gas partial pressure is stabilized, the distribution of the internal temperature of the fuel cell container is made uniform, and as a result, the thermal stress generated in the electrolyte member can be suppressed. Reliability can be improved. Furthermore, since each fluid flow path is formed in the base and the lid, each of the flow paths is excellent in hermeticity, and originally two types of raw material fluids (for example, oxygen gas and hydrogen) that should be isolated in the flow path are used. Gas or methanol, etc.) will not function as a fuel cell, and there is no risk of ignition or explosion after a flammable fluid is mixed at a high temperature. A safe fuel cell can be provided.
[0023]
  Further, according to the first fuel cell container of the present invention, one end formed on the base is opposed to the first electrode of the electrolyte member at the bottom surface of one recess, and the other end is the bottom surface of the other recess. Since the third wiring conductor facing the first electrode of the electrolyte member is provided, it is possible to connect a plurality of electrolyte members in parallel by electrically connecting them. As a result, since the output current of the entire fuel cell can be adjusted, the electricity generated electrochemically by the electrolyte member can be taken out in a good state.
[0024]
  Furthermore, according to the second container for a fuel cell of the present invention, the bottom surface of the recess having one end formed on the base body having a plurality of recesses for accommodating the electrolyte member and the lid attached to the base body. And a fourth wiring conductor that is opposed to the first electrode of the electrolyte member and whose other end is led out to a portion to which the lid on the upper surface of the base is attached, and an electrolyte member that has one end on the lower surface of the lid and the other recess And a fifth wiring conductor led out to face the other end of the fourth wiring conductor at a portion where the other end is attached to the upper surface of the base body on the lower surface of the lid. Therefore, it is possible to connect a plurality of electrolyte members in series by electrically connecting them. As a result, even when the voltage is generated by each electrolyte member, even if it is a minute voltage, the total voltage can be adjusted by series connection. Therefore, the electricity generated electrochemically by the electrolyte member can be externally maintained in good condition. It can be taken out.
[0025]
Further, according to the first and second fuel cells of the present invention, the electrolyte member is accommodated in the recesses of the first and second fuel cell containers of the present invention, and the lower and upper main surfaces of the electrolyte member. Are arranged so that each fluid can exchange between the first and second fluid flow paths, and the first and second electrodes are arranged in the first to third wiring conductors, and the first, second, and fourth electrodes. The first and second fuels of the present invention are electrically connected to the fifth and fifth wiring conductors, respectively, and the lid is attached to the upper surface around the concave portion of the base so as to cover the concave portion. To obtain a reliable fuel cell that is compact and robust with the features of a battery container, and that can provide a uniform gas supply, uniform temperature gradient in the fuel cell container, and highly efficient electrical connection. And by connecting multiple electrolyte members in parallel Since the output current of the entire battery can be adjusted, or the total voltage can be adjusted by connecting a plurality of electrolyte members in series, the electricity generated electrochemically by the electrolyte members can be kept in a good state. Can be taken out.
[0026]
Therefore, according to the fuel cell container and the fuel cell of the present invention, the fuel that is excellent in compactness, simplicity, and safety and that can be stably operated over a long period of time by uniform supply of fluid and highly efficient electrical connection. A battery can be provided.
[0027]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in detail with reference to the accompanying drawings.
[0028]
FIG. 1 is a sectional view showing an example of an embodiment of a first fuel cell container according to the present invention and a first fuel cell using the same. In FIG. 1, 1 is a fuel cell, 2 is a fuel cell container, 3 is an electrolyte member, 4 is a first electrode, 5 is a second electrode, 6 is a base, 7 is a lid, 8 is a first fluid flow path, 9 is a second fluid flow path, 10 is a first wiring conductor, 11 is a second wiring conductor, and 12 is a third wiring conductor.
[0029]
For example, the electrolyte member 3 faces the first electrode 4 formed on the lower main surface and the second electrode 5 formed on the upper main surface on both main surfaces of the ion conductive film (exchange membrane). A fuel electrode (not shown) serving as an anode side electrode and an air electrode (not shown) serving as a cathode side electrode are integrally formed. And the electric current generated with the electrolyte member 3 can be sent to the 1st electrode 4 and the 2nd electrode 5, and it can take out outside.
[0030]
The ion conductive film (exchange membrane) of the electrolyte member 3 is made of a proton conductive ion exchange resin such as perfluorocarbon sulfonic acid resin, for example, Nafion (trade name, manufactured by DuPont). Further, the fuel electrode and the air electrode are gas diffusion electrodes in a porous state, and have both functions of a porous catalyst layer and a gas diffusion layer. These fuel electrode and air electrode are constituted by a porous material in which conductive fine particles carrying a catalyst such as platinum, palladium, or an alloy thereof, for example, carbon fine particles are held by a hydrophobic resin binder such as polytetrafluoroethylene. Has been.
[0031]
The first electrode 4 on the lower main surface and the second electrode 5 on the upper main surface of the electrolyte member 3 are a method of hot pressing a carbon electrode with catalyst fine particles such as platinum or platinum-ruthenium on the electrolyte member 3, or Further, it is formed by a method of applying or transferring a mixture of a carbon electrode material with catalyst fine particles such as platinum or platinum-ruthenium and a solution in which an electrolyte material is dispersed onto the electrolyte.
[0032]
The fuel cell container 2 includes a base 6 having a recess and a lid 7, and has a function of mounting the electrolyte member 3 inside the recess and hermetically sealing the aluminum oxide (Al₂O_Three) Quality sintered body, mullite (3Al₂O_Three・ 2SiO₂) Sintered body, silicon carbide (SiC) sintered body, aluminum nitride (AlN) sintered body, silicon nitride (Si)_ThreeN_Four) It is made of ceramic materials such as quality sintered body and glass ceramic sintered body.
[0033]
The glass ceramic sintered body is composed of a glass component and a filler component.₂-B₂O_ThreeSystem, SiO₂-B₂O_Three-Al₂O_ThreeSystem, SiO₂-B₂O_Three-Al₂O_Three-MO system (where M represents Ca, Sr, Mg, Ba or Zn), SiO₂-Al₂O_Three-M¹OM²O system (however, M¹And M²Are the same or different and represent Ca, Sr, Mg, Ba or Zn), SiO₂-B₂O_Three-Al₂O_Three-M¹OM²O system (however, M¹And M²Is the same as above), SiO₂-B₂O_Three-M^Three ₂O system (however, M^ThreeRepresents Li, Na or K), SiO₂-B₂O_Three-Al₂O_Three-M^Three ₂O system (however, M^ThreeIs the same as described above), Pb-based glass, Bi-based glass and the like.
[0034]
Moreover, as a filler component, for example, Al₂O_Three, SiO₂, ZrO₂And TiO, a complex oxide of alkaline earth metal oxides₂Al oxide of alkaline earth metal oxide, Al₂O_ThreeAnd SiO₂And composite oxides containing at least one selected from (for example, spinel, mullite, cordierite).
[0035]
The fuel cell container 2 is composed of a base 6 having a recess and a lid 7, and covers the recess around the recess of the base 6 to attach the lid 7 so that the recess is hermetically sealed. Bonding with metal bonding materials such as silver brazing, bonding with resin materials such as epoxy, bonding with a seal ring made of iron alloy etc. on the upper surface around the recess with seam weld, electron beam, laser etc. The lid body 7 is attached to the base body 6 by a welding method or the like. The lid 7 may be formed with a recess similar to the base 6.
[0036]
In order to reduce the thickness of the base body 6 and the lid body 7 and to reduce the height of the fuel cell 1, the bending strength, which is mechanical strength, is preferably 200 MPa or more.
[0037]
The base body 6 and the lid body 7 are preferably formed of an aluminum oxide sintered body made of a dense material having a relative density of 95% or more, for example. In that case, for example, rare earth oxide powder and a sintering aid are first added to and mixed with the aluminum oxide powder to adjust the raw material powder of the aluminum oxide sintered body. Next, an organic binder and a dispersion medium are added to and mixed with the raw material powder of this aluminum oxide sintered body to form a paste. From this paste, an organic binder is added to the raw material powder by the press blade method, press forming, rolling forming, etc. Thus, a green sheet having a predetermined thickness is produced. Then, through the green sheet, through holes as the first fluid flow path 8 and the second fluid flow path 9 as well as the first wiring conductor 10 and the second wiring conductor are formed by punching with a mold, micro drill, laser, or the like. A through hole for arranging 11 and the third wiring conductor 12 is formed.
[0038]
The first wiring conductor 10, the second wiring conductor 11, and the third wiring conductor 12 are preferably formed of tungsten and / or molybdenum in order to prevent oxidation. In that case, for example, 100 parts by mass of tungsten and / or molybdenum powder as an inorganic component, Al₂O_Three3 to 20 parts by mass, Nb₂O_FiveIs prepared at a ratio of 0.5 to 5 parts by mass. The conductor paste is filled into the through hole of the green sheet to form a via conductor as a through conductor.
[0039]
In these conductor pastes, in order to improve the adhesion of the substrate 6 and the lid 7 to the ceramic, aluminum oxide powder or the same composition powder as the ceramic component forming the substrate 6 and the lid 7 is used. It is also possible to add 0.05 to 2% by volume.
[0040]
The first wiring conductor 10, the second wiring conductor 11, and the third wiring conductor 12 are formed on the surface layer and the inner layer of the base body 6 and the lid body 7 before and after the via conductor is formed by filling the through hole with a conductive paste. Or at the same time, a similar conductor paste is formed by printing and applying to a predetermined pattern on a green sheet by a method such as screen printing or gravure printing.
[0041]
Then, after aligning and laminating and pressing a predetermined number of sheet-like molded bodies filled with printed conductor paste, the laminated body is heated at a maximum firing temperature of 1200 to 1500 ° C., for example, in a non-oxidizing atmosphere. To obtain the target ceramic substrate 6, lid 7, first wiring conductor 10, second wiring conductor 11, and third wiring conductor 12.
[0042]
Moreover, it is preferable that the base | substrate 6 and the cover body 7 which consist of ceramics shall be 0.2 mm or more in thickness. If the thickness is less than 0.2 mm, the strength tends to be insufficient. Therefore, the base 6 and the lid 7 tend to be easily cracked due to the stress generated when the lid 7 is attached to the base 6. On the other hand, if the thickness exceeds 5 mm, it will be difficult to reduce the thickness and height, making it unsuitable as a fuel cell to be mounted on a small portable device, and increasing the heat capacity. It tends to be difficult to quickly set an appropriate temperature corresponding to the conditions.
[0043]
The first wiring conductor 10, the second wiring conductor 11, and the third wiring conductor 12 are electrically connected to the first electrode 4 and the second electrode 5 of the electrolyte member 3, respectively, and the current generated by the electrolyte member 3 is generated. It functions as a conductive path for taking it out of the fuel cell container 2.
[0044]
The first wiring conductor 10 is formed such that one end is disposed at a portion facing the first electrode 4 of the electrolyte member 3 on the bottom surface of the recess of the base 6 and the other end is led out to the outer surface of the base 6. Such a first wiring conductor 10 is formed integrally with the base 6 as described above. The first wiring conductor 10 is preferably formed so as to be 10 μm or more higher than the bottom surface of the concave portion of the base 6 so that both ends thereof can be easily brought into contact with the first electrode 4. In order to obtain this height, as described above, when the conductor paste is formed by printing and coating, the printing conditions may be set so as to increase the coating thickness. In addition, it is desirable that a plurality of first wiring conductors 10 be arranged opposite to the first electrode 4 to reduce electrical loss due to the first wiring conductors 10 and the through portion of the first wiring conductor 10 through the base 6 is φ50 μm or more. It is preferable to set it as the diameter.
[0045]
The second wiring conductor 11 is formed such that one end is disposed on the lower surface of the lid 7 facing the second electrode 5 of the electrolyte member 3 and the other end is led out to the outer surface of the lid 7. . Similar to the first wiring conductor 10, the second wiring conductor 11 is also formed integrally with the lid body 7. The second wiring conductor 11 is preferably formed so as to be 10 μm or more higher than the lower surface of the lid 7 so that both ends thereof are easily brought into contact with the second electrode 5. In order to obtain this height, as described above, when the conductor paste is formed by printing and coating, the printing conditions may be set so as to increase the coating thickness. Further, it is desirable to arrange a plurality of second wiring conductors 11 so as to face the second electrode 5, and to reduce electrical loss due to the second wiring conductors 11, and for the penetrating portion of the lid 7 of the second wiring conductor 11, φ50 μm It is preferable to set it as the above diameter.
[0046]
  The third wiring conductor 12 has one end disposed at a portion facing the first electrode 4 of the electrolyte member 3 on the bottom surface of one of the plurality of recesses of the base 6 and the other end of the other recess. The bottom surface of the other electrolyte member 3 is integrally formed with the substrate 6 so as to be disposed at a portion facing the first electrode 4. The third wiring conductor 12 is desirably formed so as to protrude at least 10 μm from the bottom surface of the concave portion of the base 6 so that both ends thereof can be easily brought into contact with the first electrode 4. In order to obtain this height, as described above, when the conductor paste is formed by printing and coating, the printing conditions may be set so as to increase the coating thickness. Further, it is desirable that a plurality of third wiring conductors 12 be arranged opposite to the first electrode 4 to reduce the electrical loss due to the third wiring conductors 12, and the through-hole portion of the base 6 of the third wiring conductor 12 is φ50 μm or more. It is preferable to set it as the diameter.
[0047]
The first wiring conductor 10, the second wiring conductor 11 and the third wiring conductor 12 are plated with a metal having good conductivity made of nickel and having good corrosion resistance and wettability with the brazing material. The first wiring conductor 10, the second wiring conductor 11, and the third wiring conductor 12, the first wiring conductor 10, the second wiring conductor 11, the third wiring conductor 12, and the external electric circuit The electrical connection can be made good. Accordingly, the first wiring conductor 10, the second wiring conductor 11, and the third wiring conductor 12 are plated with a metal having good conductivity made of nickel and having good corrosion resistance and wettability with the brazing material. It is preferably deposited by the method.
[0048]
The first, second and third wiring conductors 10, 11, 12 and the first and second electrodes 4, 5 are electrically connected by sandwiching the electrolyte member 3 between the base 6 and the lid 7. Thus, the first, second and third wiring conductors 10, 11 and 12 and the first and second electrodes 4 and 5 may be brought into pressure contact and electrically connected.
[0049]
In addition, a first fluid channel 8 and a second fluid channel 9 are disposed on the bottom surface of the recess of the base 6 facing the first electrode 4 and the second electrode 5 and the bottom surface of the lid body 7, respectively. The first fluid channel 8 is formed over the outer surface of the base 6, and the second fluid channel 9 is formed over the outer surface of the lid 7. These first and second fluid flow paths 8 and 9 are formed by electrolytes such as fuel gas, for example, reformed gas rich in hydrogen, or oxidant gas, such as air, through through holes or grooves formed in the base body 6 and the lid body 7, respectively. It is provided as a passage for fluid supplied to the member 3 or as a passage for fluid discharged from the electrolyte member 3 after the reaction, such as water produced by the reaction.
[0050]
Through holes or grooves formed in the base body 6 and the lid body 7 as the first fluid flow path 8 and the second fluid flow path 9 allow fluid such as fuel gas and oxidant gas to be supplied to the electrolyte member 3 evenly. In addition, the diameter and number of through holes, or the width, depth, and arrangement of the grooves may be determined according to the specifications of the fuel cell 1.
[0051]
In the first fuel cell container 2 and the first fuel cell 1 of the present invention, the first fluid channel 8 and the second fluid channel 9 are preferably configured so that the electrolyte member 3 is fluidized at a uniform pressure. In order to make it flow, it is preferable that the hole diameter is φ0.1 mm or more, and the interval is fixed.
[0052]
In this way, the first fluid flow path 8 is made to face the lower main surface on which the first electrode 4 of the electrolyte member 3 is formed, and the second fluid flow is made to face the upper main surface on which the second electrode 5 is formed. By forming the passage 9, fluid can be exchanged between the lower and upper main surfaces of the electrolyte member 3 and the first and second fluid flow paths 8, 9. Will be discharged. For example, in the case of supplying a gas as a fluid, it is possible to prevent the partial pressure of the gas supplied to the first electrode 4 and the second electrode 5 of the electrolyte member 3 from decreasing, and a predetermined stable output voltage. Can be obtained. Furthermore, since the supplied gas partial pressure is stabilized, the internal pressure of the fuel cell 1 is made uniform, and as a result, the thermal stress generated in the electrolyte member 3 can be suppressed, so that the reliability of the first fuel cell 1 can be reduced. Can be improved.
[0053]
With the above configuration, a small and robust first fuel cell container 2 of the present invention capable of accommodating the electrolyte member 3 as shown in FIG. 1 is obtained, and the first efficiency of the present invention capable of high efficiency control is obtained. The fuel cell 1 is obtained.
[0054]
Next, FIG. 2 is a cross-sectional view showing an example of an embodiment of a second fuel cell container of the present invention and a second fuel cell using the same. In these drawings, 1 'is a fuel cell, 2' is a fuel cell container, 3 is an electrolyte member, 4 is a first electrode, 5 is a second electrode, 6 is a base, 7 is a lid, and 8 is a first fluid. A flow path, 9 is a second fluid flow path, 10 is a first wiring conductor, 11 is a second wiring conductor, 13 is a fourth wiring conductor, and 14 is a fifth wiring conductor.
[0055]
  2 are the same as those in FIG. One end of the fourth wiring conductor 13 is disposed on the bottom surface of one of the plurality of recesses of the base 6 at the portion facing the first electrode 4 of the electrolyte member 3, and the other end is a lid on the top surface of the base 6. It is led out to the part where the body 7 is attached. The fifth wiring conductor 14 has one end disposed on the lower surface of the lid 7 facing the second electrode 5 of the electrolyte member 3 in the other recess, and the other end is the base 6 on the lower surface of the lid 7. Is formed so as to be opposed to the other end of the fourth wiring conductor 13 at a portion attached to the upper surface of the fourth wiring conductor 13.
[0056]
  Similar to the third wiring conductor 12, the fourth wiring conductor 13 is formed integrally with the base body 6, and 10 μm or more from the bottom surface of the concave portion of the base body 6 so that one end of the fourth wiring conductor 13 can easily come into contact with the first electrode 4. It is desirable to form so that it may protrude. In order to obtain this height, as described above, when the conductor paste is formed by printing and coating, the printing conditions may be set so as to increase the coating thickness. Further, it is desirable that a plurality of fourth wiring conductors 13 be arranged opposite to the first electrode 4 to reduce the electric loss caused by the fourth wiring conductors 13, and the through-hole portion of the base 6 of the fourth wiring conductor 13 is φ50 μm or more. It is preferable to set it as the diameter.
[0057]
  Similarly to the second wiring conductor 11, the fifth wiring conductor 14 is formed integrally with the lid body 7, and protrudes at least 10 μm from the lower surface of the lid body 7 so that one end of the fifth wiring conductor 14 can be easily brought into contact with the second electrode 5. It is desirable to form so as to. In order to obtain this height, as described above, when the conductor paste is formed by printing and coating, the printing conditions may be set so as to increase the coating thickness. Further, it is desirable that a plurality of fifth wiring conductors 14 be arranged opposite to the second electrode 5 to reduce the electric loss caused by the fifth wiring conductors 14, and the through-hole portion of the lid 7 of the fifth wiring conductor 14 is φ50 μm. It is preferable to set it as the above diameter.
[0058]
As shown in FIGS. 1 and 2, according to the first and second fuel cell containers 2, 2 ′ and the first and second fuel cells 1, 1 ′ of the present invention, a plurality of recesses are provided. The electrolyte member 3 is accommodated in each of the recesses of the base 6, and the third wiring conductor 12 or the fourth wiring conductor 13 and the fifth wiring conductor 14 are disposed between the end portions of the adjacent recesses, and a plurality of electrolyte members are provided. The first electrodes 4 of the three or the first electrode 4 and the second electrode 5 are electrically connected, and the output is taken out as a whole to the electrolyte member 3 arranged at both ends. By electrically connecting the first wiring conductor 10 and the second wiring conductor 11 to each other, the first to third wiring conductors 10, 11, and 12, and the first, second, fourth, and fifth wiring conductors 10・ Since it is possible to wire freely three-dimensionally by 11, 13, and 14, multiple electrolyte parts Optionally it is possible to be connected in series or parallel connection 3. As a result, the overall output voltage and output current can be adjusted efficiently, so that a fuel cell that can satisfactorily take out the electricity electrochemically generated by the plurality of electrolyte members 3 is provided. Become.
[0059]
It should be noted that the present invention is not limited to the embodiments described above, and various modifications can be made without departing from the scope of the present invention. For example, with respect to the first fluid channel and the second fluid channel, an inflow port from the side surface of the base body or the lid may be provided in order to reduce the thickness of the entire fuel cell. This is effective in reducing the size especially for portable electronic devices. Furthermore, about the 1st and 2nd wiring conductor, you may arrange | position so that the other end derived | led-out to the outer surface of a base | substrate and a cover body may each be pulled out to the side surface of the same side. According to this, wiring and flow paths can be integrated on one side of the fuel cell, facilitating miniaturization and protection of joints to the outside, enabling a highly reliable design, and The fuel cell can be operated stably.
[0060]
【The invention's effect】
According to the first and second fuel cell containers of the present invention, a base made of ceramics having a recess on the upper surface for accommodating an electrolyte member having first and second electrodes on the lower and upper main surfaces, respectively. Since the upper surface around the concave portion of the base body is attached to cover the concave portion and hermetically seals the concave portion, the fuel cell container is hermetically sealed, so that the gas is sealed. Since there is no leakage of fluid such as a container and there is no need to provide a container such as a package in addition to this container, it is possible to obtain a fuel cell that can be operated efficiently and to be effective for miniaturization. In addition, since a plurality of electrolyte members can be housed in a box formed by a ceramic body having a concave portion on the upper surface and a lid that seals the concave portion, a fuel cell can be obtained. The mechanical reliability of the entire fuel cell is improved without being exposed to the outside and being damaged. In addition to the first to third wiring conductors having one end disposed inside the container constituted by the recess and the lid, or the first, second, fourth and fifth wiring conductors, the electrolyte member itself is unnecessary. Therefore, it is possible to obtain a fuel cell with high reliability and safety. Furthermore, by using ceramics as the constituent material of the fuel cell container, it is possible to obtain a fuel cell having excellent corrosion resistance against fluids including various gases.
[0061]
Also, a first fluid channel formed from the bottom surface of the recess facing the lower main surface of the electrolyte member to the outer surface of the substrate, and formed from the lower surface of the lid body facing the upper main surface of the electrolyte member to the outer surface of the lid body. Since each of the plurality of fluid flow paths is provided on the inner wall surfaces facing each other across the electrolyte member, the fluid supplied to the electrolyte member The uniform supply performance can be improved. According to such a fluid path, since the fluid flows perpendicularly to the electrolyte member, for example, when the fluid is hydrogen gas and air (oxygen) gas, the electrolyte member has on the lower and upper main surfaces, respectively. Each gas partial pressure supplied to the first and second electrodes does not decrease, and there is an effect that a predetermined stable output voltage can be obtained. Further, since the pressure of the fluid to be supplied, for example, the gas partial pressure is stabilized, the distribution of the internal temperature of the fuel cell container is made uniform, and as a result, the thermal stress generated in the electrolyte member can be suppressed. Reliability can be improved. Furthermore, since each fluid flow path is formed in the base and the lid, each of the flow paths is excellent in hermeticity, and originally two types of raw material fluids (for example, oxygen gas and hydrogen) that should be isolated in the flow path are used. Gas or methanol, etc.) will not function as a fuel cell, and there is no risk of ignition or explosion after a flammable fluid is mixed at a high temperature. A safe fuel cell can be provided.
[0062]
Further, according to the first and second fuel cells of the present invention, the electrolyte member is accommodated in the recesses of the first and second fuel cell containers of the present invention, and the lower and upper main surfaces of the electrolyte member. Are arranged so that each fluid can exchange between the first and second fluid flow paths, and the first and second electrodes are arranged in the first to third wiring conductors, and the first, second, and fourth electrodes. And the fifth wiring conductor, respectively, and the lid is attached to the upper surface around the concave portion of the base body so that the electrolyte member is not exposed and damaged. In addition to the first to third wiring conductors having one end disposed inside the container constituted by the recess and the lid, and the first, second, fourth, and fifth wiring conductors, there is no use for the electrolyte member. A reliable and safe fuel cell is obtained because there is no need for mechanical contact Door can be. In addition, since the first and second fluid flow paths are provided on the bottom surface of the concave portion of the base body and the lower surface of the lid body, which are the inner wall surfaces facing each other with the electrolyte member interposed therebetween, the gas supplied to the electrolyte member The uniform supply can be improved, and the partial pressure of gas supplied to the first and second electrodes of the electrolyte member can be prevented from being lowered, so that a predetermined stable output voltage can be obtained. And the stress which arises in an electrolyte member can also be controlled and reliability can be improved.
[0063]
  Further, according to the first fuel cell container of the present invention, one end formed on the base is opposed to the first electrode of the electrolyte member at the bottom surface of one recess, and the other end is the bottom surface of the other recess. Since the third wiring conductor facing the first electrode of the electrolyte member is provided, it is possible to connect a plurality of electrolyte members in parallel by electrically connecting them. As a result, since the output current of the entire fuel cell can be adjusted, the electricity generated electrochemically by the electrolyte member can be taken out in a good state.
[0064]
  Furthermore, according to the second container for a fuel cell of the present invention, the bottom surface of the recess having one end formed on the base body having a plurality of recesses for accommodating the electrolyte member and the lid attached to the base body. And a fourth wiring conductor that is opposed to the first electrode of the electrolyte member and whose other end is led out to a portion to which the lid on the upper surface of the base is attached, and an electrolyte member that has one end on the lower surface of the lid and the other recess And a fifth wiring conductor led out so as to face the other end of the fourth wiring conductor at a portion where the other end is acquired on the upper surface of the base body of the lower surface of the lid body. Therefore, it is possible to connect a plurality of electrolyte members in series by electrically connecting them. As a result, even when the voltage is generated by each electrolyte member, even if it is a minute voltage, the total voltage can be adjusted by series connection. Therefore, the electricity generated electrochemically by the electrolyte member can be externally maintained in good condition. It can be taken out.
[0065]
Further, according to the first and second fuel cells of the present invention, the electrolyte member is accommodated in the recesses of the first and second fuel cell containers of the present invention, and the lower and upper main surfaces of the electrolyte member. Are arranged so that each fluid can exchange between the first and second fluid flow paths, and the first and second electrodes are arranged in the first to third wiring conductors, and the first, second, and fourth electrodes. The first and second fuels of the present invention are electrically connected to the fifth and fifth wiring conductors, respectively, and the lid is attached to the upper surface around the concave portion of the base so as to cover the concave portion. To obtain a reliable fuel cell that is compact and robust with the features of a battery container, and that can provide a uniform gas supply, uniform temperature gradient in the fuel cell container, and highly efficient electrical connection. And by connecting multiple electrolyte members in parallel Since the output current of the entire battery can be adjusted, or the total voltage can be adjusted by connecting a plurality of electrolyte members in series, the electricity generated electrochemically by the electrolyte members can be kept in a good state. Can be taken out.
[0066]
Therefore, according to the fuel cell container and the fuel cell of the present invention, the fuel that is excellent in compactness, simplicity, and safety, and that can be stably operated over a long period of time by uniform gas supply and high-efficiency electrical connection. Batteries could be provided.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of an embodiment of a first fuel cell container of the present invention and a first fuel cell of the present invention using the same.
FIG. 2 is a cross-sectional view showing an example of an embodiment of a second fuel cell container of the present invention and a second fuel cell of the present invention using the same.
FIG. 3 is a cross-sectional view showing an example of a conventional fuel cell.
[Explanation of symbols]
1,1 ': Fuel cell
2, 2 ': Fuel cell container
3: Electrolyte member
4: First electrode
5: Second electrode
6: Substrate
7: Lid
8: First fluid flow path
9: Second fluid flow path
10: First wiring conductor
11: Second wiring conductor
12: Third wiring conductor
13: Fourth wiring conductor
14: Fifth wiring conductor

Claims

A base body made of ceramics having a plurality of recesses on the upper surface for accommodating electrolyte members having first and second electrodes on the lower and upper main surfaces, respectively, and a bottom surface of the recesses facing the lower main surface of the electrolyte member A first fluid flow path formed from the outer surface of the substrate to the outer surface of the substrate, a conductor paste is baked to be integrally formed with the substrate, and one end is formed on the bottom surface of the recess facing the first electrode of the electrolyte member. Is disposed, and the other end is led to the outer surface of the base body, and the concave portion is attached to the upper surface around the concave portion of the base body so as to hermetically seal the concave portion. A lid, a second fluid channel formed from the lower surface of the lid facing the upper main surface of the electrolyte member to the outer surface of the lid, and a conductor paste that is fired to be integrated with the lid Before being formed A second wiring conductor having one end disposed on the lower surface of the lid of the lid facing the second electrode of the electrolyte member and the other end led to the outer surface of the lid; Formed on the base so as to be formed integrally with the base, one end of the plurality of recesses facing the first electrode of the electrolyte member at the bottom of one of the recesses , and the other end of the other recess And a third wiring conductor facing the first electrode of the electrolyte member on the bottom surface of the fuel cell container.

At least one of the first wiring conductor and the third wiring conductor is formed to protrude from the bottom surface of the recess by 10 μm or more, or the second wiring conductor protrudes from the bottom surface of the lid by 10 μm or more. The fuel cell container according to claim 1, wherein the container is formed.

A base body made of ceramics having a plurality of recesses on the upper surface for accommodating electrolyte members having first and second electrodes on the lower and upper main surfaces, respectively, and a bottom surface of the recesses facing the lower main surface of the electrolyte member A first fluid flow path formed from the outer surface of the substrate to the outer surface of the substrate, a conductor paste is baked to be integrally formed with the substrate, and one end is formed on the bottom surface of the recess facing the first electrode of the electrolyte member. Is disposed, and the other end is attached to the outer surface of the base body, and the concave portion is attached to the upper surface around the concave portion of the base body so as to hermetically seal the concave portion. A lid, a second fluid channel formed from the lower surface of the lid facing the upper main surface of the electrolyte member to the outer surface of the lid, and a conductor paste that is fired to be integrated with the lid With being formed A second wiring conductor having one end disposed on the lower surface of the lid member facing the second electrode of the electrolyte member and the other end led to the outer surface of the lid member; One end of the plurality of recesses facing the first electrode of the electrolyte member at the bottom of one of the plurality of recesses , and the other end on the top surface of the base body to which the lid is attached. The derived fourth wiring conductor and a conductor paste are baked and formed integrally with the lid, and one end faces the second electrode of the electrolyte member in the other recess on the lower surface of the lid, And a fifth wiring conductor led out so as to face the other end of the fourth wiring conductor on a lower surface obtained on the upper surface of the base body of the lid body. container.

At least one of the first wiring conductor and the fourth wiring conductor is formed so as to protrude 10 μm or more from the bottom surface of the recess, or at least one of the second wiring conductor and the fifth wiring conductor is the lid body The fuel cell container according to claim 3, wherein the fuel cell container is formed so as to protrude 10 μm or more from the lower surface of the fuel cell.

An electrolyte member is accommodated in the plurality of recesses of the fuel cell container according to claim 1 or 2, and the lower and upper main surfaces of the electrolyte member are connected to the first and second fluid flow paths. The first and second wiring conductors are electrically connected to the first and second electrodes, and the third wiring conductor is electrically connected to the first electrode, respectively. The fuel cell is formed by connecting the lid to the upper surface around the recess of the base and covering the recess.

An electrolyte member is accommodated in the plurality of recesses of the fuel cell container according to claim 3 or 4, and the lower and upper main surfaces of the electrolyte member are connected to the first and second fluid flow paths. The first and second wiring conductors are disposed on the first and second electrodes, and the fourth and fifth wiring conductors are disposed on the first and second wiring conductors. Each of the second electrodes is electrically connected, and the upper surface around the recess of the base is covered with the recess, and the other ends of the fourth and fifth wiring conductors are connected to each other to attach the lid. A fuel cell characterized by comprising: