JP4403363B2

JP4403363B2 - Conductive catalyst particle manufacturing apparatus and vibration apparatus

Info

Publication number: JP4403363B2
Application number: JP2003121550A
Authority: JP
Inventors: 健二香取; 俊明金光; 透穂苅
Original assignee: Sony Corp
Current assignee: Sony Corp
Priority date: 2003-04-25
Filing date: 2003-04-25
Publication date: 2010-01-27
Anticipated expiration: 2023-04-25
Also published as: JP2004321973A

Description

【０００１】
【発明が属する技術分野】
本発明は、導電性触媒粒子の製造装置及び振動装置に関するものである。
【０００２】
【従来の技術】
従来、ガス拡散性触媒電極は、導電性粉体としてのカーボンに触媒としての白金が担持されている触媒粒子を、撥水性樹脂としての例えばフッ素樹脂及びイオン伝導体と共にシート状に成形する（特開平５−３６４１８号）か、或いはカーボンシート上に塗布する工程を経て製造される。
【０００３】
この電極を、固体高分子型燃料電池等の燃料電池を構成する水素分解用電極として用いた場合、白金等の触媒によって燃料がイオン化され、生じた電子は導電性カーボンを伝って流れ、また水素をイオン化することで生じるプロトン（Ｈ⁺）はイオン伝導体を介してイオン伝導膜に流れる。ここで、ガスを通す間隙、電気を通すカーボン、イオンを通すイオン伝導体及び燃料や酸化剤をイオン化するための触媒物質が必要になる。
【０００４】
導電性粉体としてのカーボン粉体の表面に白金（触媒物質）を付着させる方法としては、例えば、スパッタ法等の物理的蒸着法が用いられる（例えば、後記の特許文献１参照）。
【０００５】
特許文献１の導電性触媒粒子の製造装置は、図１２に示すように、導電性粉体１の表面に、スパッタ法等の物理的蒸着法により触媒物質を付着させ、また前記の物理的蒸着時に、導電性粉体１が収容された容器３２を振動子３３上に配置し、振動子３３によって容器３２と共に容器３２内の導電性粉体１を振動させる。
【０００６】
特許文献１に係る発明によれば、スパッタ法等の物理的蒸着法を用いるので、これにより得られる導電性触媒粒子は、触媒物質が導電性粉体１の表面にのみ付着している。従って、少ない触媒量で良好な触媒作用を得ることができ、また触媒物質とガスとの接触面積が十分に確保されるので、反応に寄与する触媒物質の比表面積が大きくなり、触媒能も向上する。また、導電性粉体１を振動させながら、導電性粉体１の表面に物理的蒸着法により触媒物質を付着させるので、導電性粉体１は振動により十分に混合され、容器３２部の一箇所に留まることがなくなる。従って、導電性粉体１は、粉体層の表面のみならず、内部のものも表面へ出て、触媒物質を全ての導電性粉体１に対して均一に付着させることができる。
【０００７】
【特許文献１】
特開２００３−３３６６８号公報（１０欄８〜２３行目、図１）
【０００８】
【発明が解決しようとする課題】
上記した特許文献１において、スパッタ法等の物理的蒸着の際には熱が発生する。この熱によって導電性粉体を収容する容器自体が高温となり（例えば約３００℃）、導電性粉体に担持した触媒物質が焼結してサイズが大きくなってしまったり、容器が変形してしまうという問題が生じるため、導電性粉体の容器側を冷却する必要がある。しかしながら、図１２に示すように、振動子３３によって容器３２を振動させて物理的蒸着を行っているため、冷却が困難であった。このため、スパッタ法等の物理的蒸着時の発熱が低減するようにスパッタ投入電力を制限せざるを得ず、作製時間が長時間かかってしまう。
【０００９】
また、スパッタ終了後、触媒物質の温度が高い状態のまま得られた導電性触媒粒子を空気に晒した場合、触媒物質が燃焼し易いため、空気に晒す前に触媒物質を冷却しなければならず、このことが作製時間をより長くしている。
【００１０】
本発明は、上述したような問題点を解決するためになされたものであって、その目的は、全ての導電性粉体に均一に触媒物質を付着することができ、作業時間を短縮することができる、導電性触媒粒子の製造装置及び振動装置を提供することにある。
【００１１】
【課題を解決するための手段】
即ち、本発明は、導電性粉体を振動させる振動手段と、前記導電性粉体を冷却する冷却手段と、前記導電性粉体の表面に触媒物質を付着させる物理的蒸着手段とを有し、前記導電性粉体を収容する収容容器が、前記振動手段による振動を伝達する基体上に配され、前記基体に前記冷却手段が設けられ、少なくとも前記物理的蒸着手段と、前記導電性粉体を収容する前記収容容器とが密閉容器内に設置され、物理的蒸着時には前記密閉容器内を真空状態とし、物理的蒸着後には前記密閉容器内を不活性ガス雰囲気とする、導電性触媒粒子の製造装置であって、
前記収容容器の上部開口を閉塞可能な閉塞手段を有し、前記物理的蒸着後に前記密閉容器内の密閉状態を保持しながら、前記密閉容器内への前記不活性ガスの導入と前記閉塞手段による前記収容容器の前記閉塞とを行えるように構成した、
導電性触媒粒子の製造装置に係るものである。
【００１２】
また、導電性粉体を振動させる振動手段と、前記導電性粉体を冷却する冷却手段と、前記導電性粉体を収容する収容容器とを有し、前記収容容器が、前記振動手段による振動を伝達する基体上に配され、前記基体に前記冷却手段が設けられている、振動装置であって、前記振動手段と前記基体とを接続する接続手段の少なくとも一部分が絶縁物質により形成されている、振動装置に係るものである。
【００１３】
本発明によれば、前記導電性粉体を冷却する前記冷却手段として、前記収容容器を配する前記基体に設けられた冷却手段を有するので、前記物理的蒸着手段を用いて前記導電性粉体の表面に前記触媒物質を付着させる際に発熱しても、上述したような前記触媒物質の焼結や前記収容容器の熱変形等の問題が起きることはない。従って、前記物理的蒸着手段への投入電力を増加することができ、導電性触媒粒子の作製時間を短縮することができる。また、従来例のように、作製した導電性触媒粒子を空気に晒す前に、長時間かけて触媒物質を冷却する必要はなく、前記の冷却時間を短縮することができる。
しかも、少なくとも前記物理的蒸着手段と、前記導電性粉体を収容する前記収容容器とが密閉容器内に設置され、物理的蒸着時には前記密閉容器内を真空状態とし、物理的蒸着後には前記密閉容器内を不活性ガス雰囲気とし、前記収容容器の上部開口を閉塞可能な閉塞手段を有し、前記物理的蒸着後に前記密閉容器内の密閉状態を保持しながら、前記密閉容器内への前記不活性ガスの導入と前記閉塞手段による前記収容容器の前記閉塞とを行えるように構成しているので、活性が高い前記触媒物質は十分な冷却後でも空気中で燃焼する場合があっても、窒素ガス等の前記不活性ガス雰囲気で前記導電性触媒粒子を取り出すことができ、活性の高い前記導電性触媒粒子を作製することができる。
【００１４】
また、前記導電性粉体を振動させる前記振動手段を有し、前記導電性粉体を振動させながら、前記導電性粉体の表面に前記物理的蒸着手段により前記触媒物質を付着させるので、前記導電性粉体は十分に混合され、一箇所に留まることがなくなる。従って、前記導電性粉体は、粉体層の表面のみならず、内部のものも表面へ出て、前記触媒物質を全ての前記導電性粉体に対して均一に付着させることができる。
そして、前記振動手段と前記基体とを接続する接続手段の少なくとも一部分が絶縁物質により形成されているので、前記収容容器をプラス電位の状態で保持することができ、高周波スパッタによる物理的蒸着をより効率的に行うことができる。
【００１５】
さらに、前記導電性粉体の表面に、前記物理的蒸着手段によって、前記触媒物質を付着させるので、低温で、結晶性の良好な触媒物質を前記導電性粉体の表面にのみ（即ち、前記導電性粉体の表面に存在する細孔から内部に入り込まずに）付着することができ、得られる前記導電性触媒粒子は、より少ない量で良好な触媒作用を呈し、また前記触媒物質とガスとの接触面積が十分に確保されるので、反応に寄与する前記触媒物質の比表面積が大きくなり、触媒能も向上する。
【００１６】
【発明の実施の形態】
本発明に基づく装置は、基体上に前記導電性粉体を収容する収容容器が配され、前記基体に前記冷却手段が設けられているが、前記基体と前記収容容器とが着脱可能に構成されていることが好ましい。さらに、前記冷却手段が、基体に設けられた冷媒通路からなっていることが好ましい。これにより、物理的蒸着時の発熱による前記収容容器の熱変形等をより効果的に防ぐことができる。また、前記基体と前記収容容器とが着脱可能であり、容易に前記収容容器を取り外すことができるため、例えば冷媒が漏れ出す心配はなく、生産性の向上を図ることができる。
【００１７】
前記物理的蒸着手段として、前記触媒物質をターゲットとするスパッタ法を用いることが望ましい。前記スパッタ法は、容易に生産することが可能で、生産性が高く、また成膜性も良好である。
【００１８】
また、前記スパッタ法のほかに、前記物理的蒸着手段としてパルスレーザーデポジション法を用いてもよい。前記パルスレーザーデポジション法は、成膜における制御が容易であり、成膜性も良好である。
【００１９】
前記スパッタ法又はパルスレーザーデポジション法によって、前記触媒物質を付着させることにより、低温で、結晶性の良好な触媒物質を前記導電性粉体の表面にのみ（即ち、前記導電性粉体に存在する細孔内に入り込まずに）付着することができ、得られる前記導電性触媒粒子は、より少ない量で良好な触媒作用を得ることができ、また前記触媒物質とガスとの接触面積が十分に確保されるので、反応に寄与する前記触媒物質の比表面積が大きくなり、触媒能も向上することができる。
【００２０】
本発明に基づく製造装置は、少なくとも前記物理的蒸着手段と、前記導電性粉体を収容する前記収容容器とが密閉容器内に設置され、物理的蒸着時には前記密閉容器内を真空状態とし、物理的蒸着後には前記密閉容器内を不活性ガス雰囲気とする。
【００２１】
また、前記収容容器の上部開口を閉塞可能な閉塞手段を有し、前記物理的蒸着後に前記密閉容器内の密閉状態を保持しながら、前記密閉容器内への前記不活性ガスの導入と前記閉塞手段による前記収容容器の前記閉塞とを行えるように構成する。
【００２２】
具体的には、前記密閉容器の本体部と蓋体部との間の周囲に伸縮可能な伸縮部材が設けられ、前記物理的蒸着後に前記密閉容器内の密閉状態を保持しながら前記伸縮部材の伸長下で前記蓋体部が前記本体部から離脱され、かつこの離脱状態で前記密閉容器内への前記不活性ガスの導入と前記閉塞手段による前記収容容器の前記閉塞とを行えるように構成することが好ましい。
【００２３】
活性が高い前記触媒物質は十分な冷却後でも空気中で燃焼する場合があるが、本発明に基づく製造装置によれば、窒素ガス等の前記不活性ガス雰囲気で前記導電性触媒粒子を取り出すことができるので、活性の高い前記導電性触媒粒子も作製することができる。
【００２４】
また、本発明に基づく装置は、前記振動手段と前記基体とを接続する接続手段の少なくとも一部分が絶縁物質により形成されている。
【００２５】
以下、本発明の好ましい実施の形態を各種の例に基づいて図面参照下に説明する。
【００２６】
例１
図１は、導電性触媒粒子の製造装置の一例の概略図である。
【００２７】
図１（ａ）に示すように、この導電性触媒粒子の製造装置は、導電性粉体１を振動させる振動手段２と、基体３に設けられた冷媒通路４からなる冷却手段５（図１（ｂ））と、基体３上に配された導電性粉体１を収容する収容容器６と、前記触媒物質をターゲット７とする前記スパッタ法による前記物理的蒸着手段とを有する。振動手段２としては、電磁コイル式又は超音波ホーンからなる振動子を用いることができる。また、基体３と収容容器６とが着脱可能に構成されていることが好ましい。
【００２８】
この装置において、冷却手段５は、図１（ｂ）に示すように、基体３に設けられた冷媒通路４からなることが好ましい。そして、物理的蒸着時に冷媒通路４に冷媒１０、例えば１０〜４０℃の冷水を通すことにより、前記冷却を効果的に行うことができる。冷媒通路４としては、例えば真空中での使用に耐えるフレキシブルなステンレス等の金属のチューブを用いることができる。
【００２９】
この導電性触媒粒子の製造装置によれば、導電性粉体１を冷却する冷却手段５を有するので、スパッタ法によって導電性粉体１の表面に前記触媒物質を付着させる際に発熱しても、前記触媒物質の焼結や収容容器６の熱変形等の問題が起きることはない。従って、スパッタへの投入電力を増加することができ、前記導電性触媒粒子の作製時間を短縮することができる。また、作製した前記導電性触媒粒子を空気に晒す前に行う前記冷却の時間を短縮することができる。
【００３０】
また、導電性粉体１を振動させる振動手段２を有し、導電性粉体１を振動させながら、導電性粉体１の表面にスパッタ法により前記触媒物質を付着させるので、導電性粉体１は十分に混合され、収容容器６の一箇所に留まることがなくなる。従って、導電性粉体１は、粉体層の表面のみならず、内部のものも表面へ出て、前記触媒物質を全ての導電性粉体１に対して均一に付着させることができる。
【００３１】
さらに、導電性粉体１の表面に、スパッタ法によって前記触媒物質を付着させるので、低温で、結晶性の良好な前記触媒物質を導電性粉体１の表面にのみ（即ち、導電性粉体１の表面に存在する細孔から内部に入り込まずに）付着することができ、得られる前記導電性触媒粒子は、より少ない量で良好な触媒作用を呈し、また前記触媒物質とガスとの接触面積が十分に確保されるので、反応に寄与する前記触媒物質の比表面積が大きくなり、触媒能も向上する。
【００３２】
この装置を用いて作製される前記導電性触媒粒子は、図２（Ａ）に示すように、触媒物質８が、例えば導電性粉体１の表面に存在する細孔（図示省略）に入り込まずに、導電性粉体１の表面にのみ付着している。従って、より少ない触媒量で良好な触媒作用を得ることができ、また触媒物質８とガスとの接触面積が十分に確保されるので、反応に寄与する触媒物質８の比表面積が大きくなり、触媒能も向上する。
【００３３】
また、図２（Ｂ）に示すように、導電性粉体１の表面にイオン伝導体９を付着させ、更にこのイオン伝導体９の表面に、スパッタ法等の前記物理的蒸着手段により触媒物質８を付着させることも可能である。この場合、前記物理的蒸着手段によって触媒物質８を付着させるので、例えば触媒物質８の結晶性を良好にするための熱処理を行う必要がなく、イオン伝導体９の性能を損なうことなく、触媒物質８を付着させることができる。
【００３４】
図２に示す（Ａ）、（Ｂ）のいずれの前記導電性触媒粒子も、触媒能と導電性を共に発揮する上で、導電性粉体１に対して、触媒物質８を１０〜１０００重量％の割合で付着させることが好ましく、触媒物質８としては、Ｐｔ、Ｉｒ、Ｒｈ、Ｒｕ等の貴金属材料を用いることが好ましい。
【００３５】
導電性粉体１の電気抵抗は１０^-3Ω・ｍ以下であることが好ましく、カーボン、ＩＴＯ（Indium tin oxide：インジウム酸化物にスズをドープした導電性酸化物）及びＳｎＯ₂のうちの少なくとも１種を用いることが好ましい。
【００３６】
導電性粉体１としてカーボンを用いるとき、このカーボンの比表面積を３００ｍ²／ｇ以上とすることが好ましく、３００ｍ²／ｇ未満の場合、前記導電性触媒粒子としての特性が低下することがある。
【００３７】
また、前記導電性触媒粒子を用いてガス拡散性触媒電極を作製した場合、ガス透過性が重要な性能となるが、導電性粉体１としてカーボンを用いるとき、このカーボンの吸油量を２００ｍｌ／１００ｇ以上とすることで、良好なガス透過性を得ることができる。
【００３８】
例２
上記した製造装置を用いて前記導電性触媒粒子を製造し、装置内から前記導電性触媒粒子を取り出す際に前記導電性触媒粒子を空気に晒すと、前記導電性触媒粒子が燃焼してしまう場合がある。このため、本発明に基づく導電性触媒粒子の製造装置は、少なくとも前記物理的蒸着手段と、前記導電性粉体を収容する前記収容容器とが密閉容器内に設置され、物理的蒸着時には前記密閉容器内を真空状態とし、物理的蒸着後には前記密閉容器内を不活性ガス（例えば窒素ガス）雰囲気とすることが好ましい。
【００３９】
また、前記収容容器の上部開口を閉塞可能な閉塞手段を有し、前記物理的蒸着後に前記密閉容器内の密閉状態を保持しながら、前記密閉容器内への前記不活性ガスの導入と前記閉塞手段による前記収容容器の前記閉塞とを行えるように構成することが好ましい。
【００４０】
活性が高い前記触媒物質は、十分な冷却後でも空気中で燃焼する場合があるが、本発明に基づく製造装置によれば、窒素ガス等の前記不活性ガス雰囲気で前記導電性触媒粒子を取り出すことができるので、活性の高い前記導電性触媒粒子も作製することが可能となる。
【００４１】
図３は、前記導電性触媒粒子を前記不活性ガス雰囲気で取り出せるように構成された本発明に基づく導電性触媒粒子の製造装置の概略断面図である。
【００４２】
図３（ａ）に示すように、本発明に基づく製造装置は、前記触媒物質をターゲット７とする前記スパッタ法による前記物理的蒸着手段と、基体３に設けられた冷媒通路４からなる冷却手段５と、導電性粉体１を収容する収容容器６とが密閉容器１１内に設置され、かつ密閉容器１１の本体部１１ａと蓋体部１１ｂとの間の周囲に伸縮可能な例えば高分子フィルム製の伸縮部材１２が設けられている。また、収容容器６の上部開口１３を閉塞可能な前記閉塞手段としての蓋材１４が配されている。なお、振動手段２及び冷却手段５の構造等は、上記に図１を参照して説明したと同様とする。
【００４３】
まず、前記物理的蒸着時には密閉容器１１内を真空状態とする。前記物理的蒸着後、密閉状態を保持しながら不活性ガス導入口１５から不活性ガス（例えば窒素ガス）３４を導入し、密閉容器１１内を不活性ガス雰囲気とする。
【００４４】
次に、図３（ｂ）に示すように、密閉容器１１内を不活性ガス雰囲気とした後、密閉状態を保持しながら伸縮部材１２の伸長下で蓋体部１１ｂを本体部１１ａから離脱し（図中、矢印３５の方向）、かつこの離脱状態で前記閉塞手段としての蓋材１４を仮想線で示す収容容器６の上部開口１３の位置まで移動させ、収容容器６の前記閉塞を行う。ここで、図示するように、伸縮部材１２には例えばグローブ１６が設けられており、このグローブ１６を用いることによって、密閉容器１１内の密閉状態における不活性ガス雰囲気を保持しながら、蓋材１４を移動させることができる。
【００４５】
そして、伸縮部材１２を取り外して蓋体部１１ｂを本体部１１ａから離脱し、密閉容器１１内を開放し、導電性粉体１の表面に前記触媒物質が付着されてなる前記導電性触媒粒子が収容された収容容器６を取り出すことができる。このとき、収容容器６は、上部開口１３が蓋材１４により閉塞された状態なので、その内部は前記不活性ガス雰囲気が保持されている。
【００４６】
活性が高い前記触媒物質は十分な冷却後でも空気中で燃焼する場合があるが、本発明に基づく製造装置によれば、窒素ガス等の前記不活性ガス雰囲気で前記導電性触媒粒子を取り出すことができるので、活性の高い前記導電性触媒粒子も作製することができる。
【００４７】
例３
前記物理的蒸着手段として高周波スパッタを用いた場合、プラス電荷とマイナス電荷を交互に印加するので、Ａｒ⁺等の陽イオンが前記ターゲットだけでなく、多方向に向かって飛んでしまう。しかしながら、実質的に、前記導電性粉体を含む前記収容容器側は前記ターゲットからの粒子によりプラス電位の状態なので、前記陽イオンが前記導電性粉体に衝突して損傷を与えることを低減できる。
【００４８】
本発明に基づく装置において、前記振動手段がアースされている場合、前記収容容器及び前記冷却手段を上記したプラス電位の状態で保持するために、前記振動手段と前記収容容器及び前記冷却手段とが電気的に絶縁されていることが好ましい。
【００４９】
即ち、本発明に基づく装置は、図４に示すように、振動手段２と基体３とを接続する接続手段１７の少なくとも一部分が絶縁物質１８により形成されていることが好ましい。また、基体３に設けられた冷媒通路４の少なくとも一部分も絶縁物質１８により形成されていることが好ましい。これにより、収容容器６及び冷却手段５を上記したプラス電位の状態で保持することができ、前記高周波スパッタによる前記物理的蒸着をより効率的に行うことができる。
【００５０】
例４
本発明に基づく装置は、前記収容容器に振動増幅手段が設けられていることが好ましい。これにより、前記導電性粉体と、前記振動増幅手段とを前記振動手段によって同時に振動させながら、前記導電性粉体の表面に、前記物理的蒸着手段により前記触媒物質を付着させることができ、前記導電性粉体は、より振動されて十二分に混合され、前記収容容器の一箇所に留まることがなくなる。従って、前記導電性粉体は、粉体層の表面のみならず、内部のものも表面へ出て、前記触媒物質を全ての前記導電性粉体に対して一層容易にかつ均一に付着させることができる。
【００５１】
ここで、前記振動増幅手段としては、図５に示すように、表面が平滑なボール１９を用いることができる。また、振動手段２によって導電性粉体１及び前記振動増幅手段としてのボール１９に与える前記振動の周波数は、導電性粉体１を十二分に混合するには、５〜２００Ｈｚであることが好ましく、また、前記振動の振幅も同様の理由から±（０．５〜２０）ｍｍであることが好ましい（その他の例の場合も同様）。
【００５２】
この場合、ボール１９は、直径１〜１０ｍｍのセラミックス又は金属製のボールであることが好ましい。
【００５３】
上述したような、好ましいとする各条件範囲内の環境下、導電性粉体１の表面に、例えば前記スパッタ法によって前記触媒物質を付着させれば、導電性粉体１は、より一層の良好な振動をすることができるので、導電性粉体１の表面に、前記触媒物質をより一層均一に付着することが可能である。上記した各範囲から外れた場合、即ち、ボール１９の径が１ｍｍ未満の場合又は１０ｍｍを超える場合、前記振動数が５Ｈｚ未満の場合又は２００Ｈｚを超える場合、或いは、前記振幅が±０．５ｍｍ未満の場合等には、導電性粉体１は良好な振動をすることができず、流動せずに収容容器６の底部に滞留したままの導電性粉体１が生じ易く、均一な成膜ができなくなることがある。また、前記振幅が２０ｍｍを超えた場合、導電性粉体１の飛び出すおそれがあり、収量が減少することがある。
【００５４】
図６に、導電性粉体１及び前記振動増幅手段としてのボール１９を配置した収容容器６の概略図を示すように、導電性粉体１の分布領域の面積Ｓに対する、ボール１９の総面積Ａの比率を３０〜８０％とすることが好ましい。この比率が小さすぎると、導電性粉体１の混合が不十分となり易く、また大きすぎると、導電性粉体１の割合が小さくなってスパッタによる前記触媒物質の付着効率が悪くなり易く、前記触媒物質の付着した前記導電性触媒粒子の生産効率が不十分となる場合がある。
【００５５】
図７に、導電性粉体１及び前記振動増幅手段としてのボール１９を配置した収容容器６の一部拡大概略断面図を示すように、導電性粉体１がなす層厚ｔに対し、前記振動増幅手段としてのボール１９の径Ｒを１０〜７０％とすることが好ましい。この径がその範囲外であると、上記の面積比率の場合と同様の理由で不利となり易い。
【００５６】
本発明に基づく製造装置は、前記ボールに代えて、前記振動増幅手段として、ワイヤーが平面的にみて略渦巻状、略同心円状又は略折返し状のパターンをなすように一体に形成された部品を用い、この部品を前記収容容器の底面上に少なくとも一部が非固定状態で（この非固定状態とは、それ自体が三次元的に自由に振動するような状態である：以下、同様）設置し、この部品上に、前記導電性粉体を配置し、前記振動をかけてもよい。
【００５７】
図８は、前記振動増幅手段として、ワイヤーが平面的にみて渦巻状のパターンをなすように一体に形成された部品２０を用いた、本発明に基づく振動装置の概略図である。但し、上記した冷媒通路は図示省略している（以下、同様）。
【００５８】
図９は、前記振動増幅手段として、ワイヤーが平面的にみて同心円状のパターンをなすように一体に形成された（即ち、径方向に連結された）部品２１を用いた、本発明に基づく振動装置の概略断面図である。
【００５９】
図１０は、前記振動増幅手段として、ワイヤーが平面的にみて折返し状のパターンをなすように一体に形成された部品２２を用いた、本発明に基づく振動装置の概略断面図である。
【００６０】
図８〜図１０に示されるいずれの場合も、部品２０、２１又は２２を収容容器６の底面上に非固定状態で設置し、この部品２０、２１又は２２上に、導電性粉体１を配置し、前記振動をかけると、部品２０、２１又は２２の形状は保持されたまま振動するため、導電性粉体１は、より一層振動され、より良好に流動することができる。このとき、前記スパッタ法等の前記物理的蒸着手段により、導電性粉体１の表面に、前記触媒物質を付着すれば、収容容器６内の導電性粉体１は、その表面のみならず内部のものも含めて全体にわたって、均一に前記触媒物質を付着することができる。
【００６１】
こうした効果を得る上で、渦巻状、同心円状又は折返し状のパターンに形成された前記ワイヤーは直径１〜１０ｍｍの金属製ワイヤーであり、渦巻状、同心円状又は折返し状のパターンに形成された前記部品の外径が前記容器の内径より約５ｍｍ小さく、またパターンのピッチが５〜１５ｍｍであることが好ましい。これらの値を外れた条件の場合、導電性粉体１の混合が不十分となり易く、また触媒物質の付着効率が低下し易い。
【００６２】
また、上記したボールを用いた場合と同様の理由から、前記導電性粉体がなす層厚に対し、前記振動増幅手段としての、前記ワイヤーが平面的にみて渦巻状、同心円状又は折返し状のパターンをなすように一体に形成された前記部品の厚みが１０〜７０％であることが好ましい。
【００６３】
本発明に基づく製造装置を用いて得られる前記導電性触媒粒子は、それ自体でもプレス加工等により触媒層を形成できるが、樹脂によって結着して成膜すると、上記導電性触媒粒子を多孔性のガス透過性集電体上に十分な強度で保持できるので、例えばガス拡散性触媒電極を製造するに際してより好ましい。
【００６４】
本発明に基づく製造装置を用いて作製される前記導電性触媒粒子は、上記したように前記ガス拡散性触媒電極の構成材料として用いられ、このガス拡散性触媒電極は、例えば燃料電池として構成されている電気化学デバイスに適用することができる。
【００６５】
即ち、第１極と、第２極と、これらの両極間に挟持されたイオン伝導体とからなる基本的構造体において、前記第１極及び第２極のうち少なくとも前記第１極に本発明に基づく製造装置を用いて作製された前記導電性触媒粒子を含有する前記ガス拡散性触媒電極を適用することができる。
【００６６】
図１１は、前記ガス拡散性触媒電極を用いた具体例の燃料電池を示す。ここで、図１１中の触媒層２３は、本発明に基づく製造装置を用いて作製された前記導電性粉体（例えばカーボン粉体）の表面にのみ前記触媒物質（例えば白金）が付着している前記導電性触媒粒子の他、場合によっては、イオン伝導体、撥水性樹脂（例えばフッ素系）及び造孔剤（ＣａＣＯ₃）との混合物からなる混合層である。前記ガス拡散性触媒電極は、触媒層２３と、多孔性のガス透過性集電体としての例えばカーボンシート２４とからなる多孔性のガス拡散性触媒電極である。但し、狭義には、触媒層２３のみをガス拡散性触媒電極と称してもよい。また、前記ガス拡散性触媒電極を用いた第１極と、第２極との間には、イオン伝導部２５が挟着されている。
【００６７】
この燃料電池は、互いに対向する、端子２６付きの負極（燃料極又は水素極）２７、及び端子２８付きの正極（酸素極）２９を有し、これらの両極間にイオン伝導部２５が挟着されている。使用時には、負極２７側ではＨ₂流路３０中に水素が通される。燃料（Ｈ₂）が流路３０を通過する間に水素イオンを発生し、この水素イオンは負極２７で発生した水素イオン及びイオン伝導部２５で発生した水素イオンと共に正極２９側へ移動し、そこでＯ₂流路３１を通る酸素（空気）と反応し、これにより所望の起電力が取り出される。
【００６８】
かかる燃料電池は、本発明に基づく製造装置を用いて作製される前記導電性触媒粒子を含有する前記ガス拡散性触媒電極が前記第１極及び第２極を構成しているので、良好な触媒作用を有しており、また前記触媒物質とガス（Ｈ₂）との接触面積が十分に確保されるので、反応に寄与する前記触媒物質の比表面積が大きくなり、触媒能も向上して、良好な出力特性が得られる。
【００６９】
本発明に基づく製造装置を用いて作製される前記導電性触媒粒子を含有する前記ガス拡散性触媒電極中に、或いは前記電気化学デバイスを構成する前記第１極と、第２極との両極間に挟持された前記イオン伝導部に、使用可能な前記イオン伝導体としては、一般的なナフィオン（登録商標）（デュポン社製のパーフルオロスルホン酸樹脂）等が挙げられる。
【００７０】
【実施例】
以下、実施例に基づいて本発明を具体的に説明する。
【００７１】
実施例１
まず、基体に前記冷媒通路としてのフレキシブル配管を設けて前記冷却手段とし、この冷却手段と前記振動手段とを前記接続手段を用いて接続した。次に、前記基体上に、前記導電性粉体としてのカーボン粉体を収容させた前記収容容器を熱伝導が良好な状態でチャックによって着脱可能に設置した。
【００７２】
前記基体と前記振動手段とを接続する前記接続手段の一部分は絶縁物質により形成し、前記収容容器を含む前記冷却手段をアースから電気的に絶縁し、電気的にフローティングの状態で、前記振動手段を用いて、振幅±５ｍｍ、振動数３６Ｈｚの振動を発生させながら、スパッタを行った。
【００７３】
なお、スパッタ投入電力を２Ｗ／ｃｍ²としてカーボン粉体に白金を付着させ、白金担持カーボン粉体を作製した。スパッタ時の前記収容容器の温度を測定したところ、７０℃程度であった。
【００７４】
そして、スパッタ終了後、水冷を続けたところ、２０分後には前記収容容器の温度は３０℃以下に冷却され、ここで前記白金担持カーボン粉体が収容された前記収容容器を取り出した。
【００７５】
また、本実施例の装置は、図３に示すように、窒素ガス雰囲気で前記収容容器を前記密閉容器から取り出せるように構成し、作製した白金担持カーボン粉体を酸素（空気）に触れないようにした。得られた白金担持カーボン粉体を水と軽く混錬し、空気中で燃焼しない状態にした後、大気中で触媒インクを作製した。
【００７６】
上記のようにして得られた白金担持カーボン粉体を、バインダーとしてのパーフルオロスルホン酸及び有機溶媒としてのｎＰＡ（ノルマルプロピルアルコール）と共に混練し、この混合液を、カーボン粉体と撥水性樹脂が塗布されたカーボンシート上に塗布乾燥させ、ガス拡散性触媒電極を作製した。このガス拡散性触媒電極をイオン交換膜（パーフルオロスルホン酸）の両面側に配置し、図１１に示すような燃料電池を作製し、出力を測定した。なお、本実施例で得られた出力（単位ｍＷ／ｃｍ²）を相対値で１００％とし、これを基準値とした。
【００７７】
比較例１
前記冷却手段を設置しなかった以外は、上記の実施例と同様にしてスパッタ投入電力を２Ｗ／ｃｍ²としてスパッタを行い、白金担持カーボン粉体を作製したところ、スパッタ時の前記収容容器の温度は３００℃まで上昇しており、スパッタ終了後、３０℃まで冷却するには３時間必要であった。さらに、過熱状態になったため、触媒能力が低下し、得られた白金担持カーボン粉体を用いて上記と同様にして作製した燃料電池の出力は、上記の実施例に対して、９０％程度となった。
【００７８】
なお、前記基体と前記振動手段とを電気的に絶縁せず、カーボン粉体がアース電位となるようにした以外は、上記の実施例と同様にしてスパッタにより白金担持カーボン粉体を作製した。この場合、燃料電池の出力を測定したところ、上記の実施例に対して、９０％であった。これは、逆スパッタにより、触媒の粒子が乱されたものと考えられる。
【００７９】
また、作製した白金担持カーボン粉体をチャンバーから取り出す際に、窒素ガス雰囲気とせず、大気雰囲気でチャンバーを開いた以外は、上記の実施例と同様にして白金担持カーボン粉体を作製した。この場合、白金の割合が４０重量％程度までは、燃えずに触媒インクが作製できたが、４０重量％を超える領域では十分な冷却後でも、大気中の酸素によって燃焼し、触媒インクを作製することができなかった。
【００８０】
以上、本発明を実施の形態及び実施例について説明したが、上述の例は、本発明の技術的思想に基づき種々に変形が可能である。
【００８１】
例えば、本発明に基づく導電性触媒粒子の製造装置及び振動装置において、その形状、構成、材質等は本発明を逸脱しない限り、適宜選択可能である。
【００８２】
また、本発明に基づく製造装置を用いて前記導電性触媒粒子を作製し、得られた前記導電性触媒粒子を含有させてなる前記ガス拡散性触媒電極を用いた前記燃料電池について説明したが、ガス拡散性触媒電極は、前記燃料電池の逆反応である水素製造装置にも応用できる。
【００８３】
【発明の作用効果】
本発明によれば、前記導電性粉体を冷却する前記冷却手段として、前記収容容器を配する前記基体に設けられた冷却手段を有するので、前記物理的蒸着手段を用いて前記導電性粉体の表面に前記触媒物質を付着させる際に発熱しても、前記触媒物質の焼結や前記収容容器の熱変形等の問題が起きることはない。従って、前記物理的蒸着手段への投入電力を増加することができ、導電性触媒粒子の作製時間を短縮することができる。また、作製した導電性触媒粒子を空気に晒す前の冷却時間を短縮することができる。
しかも、少なくとも前記物理的蒸着手段と、前記導電性粉体を収容する前記収容容器とが密閉容器内に設置され、物理的蒸着時には前記密閉容器内を真空状態とし、物理的蒸着後には前記密閉容器内を不活性ガス雰囲気とし、前記収容容器の上部開口を閉塞可能な閉塞手段を有し、前記物理的蒸着後に前記密閉容器内の密閉状態を保持しながら、前記密閉容器内への前記不活性ガスの導入と前記閉塞手段による前記収容容器の前記閉塞とを行えるように構成しているので、活性が高い前記触媒物質は十分な冷却後でも空気中で燃焼する場合があっても、窒素ガス等の前記不活性ガス雰囲気で前記導電性触媒粒子を取り出すことができ、活性の高い前記導電性触媒粒子を作製することができる。
【００８４】
また、前記導電性粉体を振動させる前記振動手段を有し、前記導電性粉体を振動させながら、前記導電性粉体の表面に、前記物理的蒸着手段により前記触媒物質を付着させるので、前記導電性粉体は十分に混合され、一箇所に留まることがなくなる。従って、前記導電性粉体は、粉体層の表面のみならず、内部のものも表面へ出て、前記触媒物質を全ての前記導電性粉体に対して均一に付着させることができる。
そして、前記振動手段と前記基体とを接続する接続手段の少なくとも一部分が絶縁物質により形成されているので、前記収容容器をプラス電位の状態で保持することができ、高周波スパッタによる物理的蒸着をより効率的に行うことができる。
【００８５】
さらに、前記導電性粉体の表面に、前記物理的蒸着手段によって、前記触媒物質を付着させるので、低温で、結晶性の良好な触媒物質を前記導電性粉体の表面にのみ（即ち、前記導電性粉体の表面に存在する細孔から内部に入り込まずに）付着することができ、得られる前記導電性触媒粒子は、より少ない量で良好な触媒作用を呈し、また前記触媒物質とガスとの接触面積が十分に確保されるので、反応に寄与する前記触媒物質の比表面積が大きくなり、触媒能も向上する。
【図面の簡単な説明】
【図１】本発明の実施の形態を説明するための導電性触媒粒子の製造装置の一例の概略断面図である。
【図２】同、製造装置を用いて得られる導電性触媒粒子を示す概略断面図である。
【図３】同、本発明に基づく装置の例の概略断面図である。
【図４】同、本発明に基づく装置の他の例の概略断面図である。
【図５】同、製造装置に用いる振動装置の概略断面図である。
【図６】同、本発明に基づく装置における、容器の一部拡大概略図である。
【図７】同、本発明に基づく振動装置の一部拡大概略断面図である。
【図８】同、他の振動装置の概略断面図である。
【図９】同、更に他の振動装置の概略断面図である。
【図１０】同、本発明に基づく振動装置の概略断面図である。
【図１１】同、本発明に基づく製造装置を用いて得られる導電性触媒粒子を含有するガス拡散性触媒電極を用いた燃料電池の概略構成図である。
【図１２】従来例による導電性触媒粒子の製造装置の概略断面図である。
【符号の説明】
１…導電性粉体、２…振動手段、３…基体、４…冷媒通路、５…冷却手段、
６…収容容器、７…ターゲット、８…触媒物質、９…イオン伝導体、
１０…冷媒、１１…密閉容器、１１ａ…本体部、１１ｂ…蓋体部、
１２…伸縮部材、１３…上部開口、１４…蓋材、１５…不活性ガス導入口、
１６…グローブ、１７…接続手段、１８…絶縁物質、１９…ボール、
２０、２１、２２…振動増幅手段、２３…触媒層、２４…ガス透過性集電体、
２５…イオン伝導部、２６、２８…端子、２７…負極、２９…正極、
３０…Ｈ₂流路、３１…Ｏ₂流路、３４…不活性ガス[0001]
[Technical field to which the invention belongs]
The present invention relates to an apparatus for producing conductive catalyst particles and a vibration device.
[0002]
[Prior art]
Conventionally, a gas diffusive catalyst electrode is formed by molding catalyst particles in which platinum as a catalyst is supported on carbon as a conductive powder together with, for example, a fluororesin and an ion conductor as a water repellent resin (special feature). No. 5-36418) or a process of coating on a carbon sheet.
[0003]
When this electrode is used as an electrode for hydrogen decomposition constituting a fuel cell such as a polymer electrolyte fuel cell, the fuel is ionized by a catalyst such as platinum, and the generated electrons flow through conductive carbon, and hydrogen Proton (H⁺) Flows to the ion conducting membrane through the ion conductor. Here, a gap through which gas passes, carbon through which electricity passes, an ion conductor through which ions pass, and a catalyst material for ionizing fuel and oxidant are required.
[0004]
As a method for attaching platinum (catalyst substance) to the surface of the carbon powder as the conductive powder, for example, a physical vapor deposition method such as a sputtering method is used (see, for example, Patent Document 1 described later).
[0005]
As shown in FIG. 12, the apparatus for producing conductive catalyst particles of Patent Document 1 attaches a catalyst substance to the surface of the conductive powder 1 by a physical vapor deposition method such as a sputtering method, and the physical vapor deposition described above. Sometimes, the container 32 containing the conductive powder 1 is placed on the vibrator 33, and the conductive powder 1 in the container 32 is vibrated together with the container 32 by the vibrator 33.
[0006]
According to the invention according to Patent Document 1, since a physical vapor deposition method such as sputtering is used, the conductive catalyst particles obtained thereby have a catalytic substance attached only to the surface of the conductive powder 1. Therefore, good catalytic action can be obtained with a small amount of catalyst, and the contact area between the catalyst substance and the gas is sufficiently secured, so that the specific surface area of the catalyst substance contributing to the reaction is increased and the catalytic performance is also improved. To do. In addition, since the catalyst substance is adhered to the surface of the conductive powder 1 by physical vapor deposition while vibrating the conductive powder 1, the conductive powder 1 is sufficiently mixed by vibration to form one part of the container 32 parts. No longer stays in place. Accordingly, the conductive powder 1 can be exposed not only on the surface of the powder layer but also on the inside thereof, so that the catalyst substance can be uniformly attached to all the conductive powders 1.
[0007]
[Patent Document 1]
JP 2003-33668 A (column 10, lines 8 to 23, FIG. 1)
[0008]
[Problems to be solved by the invention]
In Patent Document 1 described above, heat is generated during physical vapor deposition such as sputtering. Due to this heat, the container containing the conductive powder itself becomes a high temperature (for example, about 300 ° C.), and the catalyst material carried on the conductive powder sinters and becomes large in size, or the container is deformed. Therefore, it is necessary to cool the container side of the conductive powder. However, as shown in FIG. 12, since the container 32 is vibrated by the vibrator 33 and physical vapor deposition is performed, cooling is difficult. For this reason, it is necessary to limit the power supplied to the sputtering so that heat generation during physical vapor deposition such as sputtering is reduced, and the manufacturing time is long.
[0009]
In addition, when the conductive catalyst particles obtained with the catalyst material at a high temperature are exposed to air after sputtering, the catalyst material is likely to burn, so the catalyst material must be cooled before being exposed to air. This makes the production time longer.
[0010]
The present invention has been made to solve the above-described problems, and its purpose is to uniformly attach a catalytic substance to all conductive powders, and to shorten the working time. An object of the present invention is to provide an apparatus for producing conductive catalyst particles and a vibration apparatus capable of achieving the above.
[0011]
[Means for Solving the Problems]
  That is, the present invention includes a vibrating means for vibrating the conductive powder, a cooling means for cooling the conductive powder, and a physical vapor deposition means for attaching a catalyst substance to the surface of the conductive powder. A storage container for storing the conductive powder is disposed on a base for transmitting vibrations by the vibration means, and the cooling means is provided on the base;At least the physical vapor deposition means and the container for containing the conductive powder are installed in a sealed container, and the inside of the sealed container is evacuated during physical vapor deposition, and the inside of the sealed container after physical vapor deposition. An inert gas atmosphere,Conductive catalyst particle manufacturing equipmentBecause
    The container has a closing means capable of closing the upper opening of the container, and the sealing is performed after the physical vapor deposition.  While maintaining the sealed state in the container, the introduction of the inert gas into the sealed container and the closing  Constructed to be able to perform the closure of the storage container by a closing means,
Conductive catalyst particle manufacturing equipmentIt is related to.
[0012]
  And a vibration means for vibrating the conductive powder, a cooling means for cooling the conductive powder, and a storage container for storing the conductive powder, wherein the storage container is vibrated by the vibration means. The vibration device is disposed on a base body that transmits heat and is provided with the cooling means.A vibration device in which at least a part of connection means for connecting the vibration means and the base is formed of an insulating material.It is related to.
[0013]
  According to the present invention, since the cooling means for cooling the conductive powder includes the cooling means provided on the base body on which the container is disposed, the conductive powder is used by using the physical vapor deposition means. Even if heat is generated when the catalyst material is adhered to the surface of the metal, problems such as sintering of the catalyst material and thermal deformation of the storage container as described above do not occur. Therefore, the input power to the physical vapor deposition means can be increased, and the production time of the conductive catalyst particles can be shortened. Further, unlike the conventional example, it is not necessary to cool the catalyst material over a long time before exposing the produced conductive catalyst particles to the air, and the cooling time can be shortened.
  In addition, at least the physical vapor deposition means and the container for housing the conductive powder are installed in a sealed container, and the inside of the sealed container is evacuated during physical vapor deposition, and the sealed after physical vapor deposition. The container has an inert gas atmosphere, and has a closing means capable of closing the upper opening of the container, and maintains the sealed state in the sealed container after the physical vapor deposition, Since the introduction of the active gas and the closing of the container by the closing means can be performed, the highly active catalytic substance may be burned in air even after sufficient cooling. The conductive catalyst particles can be taken out in the inert gas atmosphere such as gas, and the conductive catalyst particles having high activity can be produced.
[0014]
  In addition, the vibration means for vibrating the conductive powder, the catalyst material is attached to the surface of the conductive powder by the physical vapor deposition means while vibrating the conductive powder. The conductive powder is sufficiently mixed and does not stay in one place. Accordingly, not only the surface of the powder layer but also the inside of the conductive powder comes to the surface, and the catalyst substance can be uniformly attached to all the conductive powders.
  In addition, since at least a part of the connecting means for connecting the vibrating means and the base is formed of an insulating material, the container can be held in a positive potential state, and physical vapor deposition by high frequency sputtering can be further performed. Can be done efficiently.
[0015]
Further, since the catalyst substance is adhered to the surface of the conductive powder by the physical vapor deposition means, the catalyst substance having good crystallinity is applied only to the surface of the conductive powder at a low temperature (that is, the The conductive catalyst particles obtained can adhere to the surface of the conductive powder (without entering the inside through the pores) and exhibit good catalytic action in a smaller amount, and the catalyst substance and gas Is sufficiently secured, the specific surface area of the catalytic material contributing to the reaction is increased, and the catalytic performance is also improved.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
  In the apparatus according to the present invention, a storage container for storing the conductive powder is disposed on a base, and the cooling means is provided on the base. The base and the storage container are configured to be detachable. It is preferable. Furthermore, it is preferable that the cooling means comprises a refrigerant passage provided in the base. Thereby, the thermal deformation etc. of the said storage container by the heat_generation | fever at the time of physical vapor deposition can be prevented more effectively. Moreover, since the said base | substrate and the said storage container can be attached or detached and the said storage container can be removed easily, there is no fear that a refrigerant | coolant leaks out, for example, and productivity can be aimed at.
[0017]
As the physical vapor deposition means, it is desirable to use a sputtering method using the catalyst material as a target. The sputtering method can be easily produced, has high productivity, and has good film formability.
[0018]
In addition to the sputtering method, a pulse laser deposition method may be used as the physical vapor deposition means. The pulse laser deposition method is easy to control in film formation and has good film formability.
[0019]
By attaching the catalyst substance by the sputtering method or the pulse laser deposition method, the catalyst substance having good crystallinity is present only on the surface of the conductive powder at a low temperature (that is, present in the conductive powder). The conductive catalyst particles obtained can obtain good catalytic action in a smaller amount, and the contact area between the catalyst substance and the gas is sufficient. Therefore, the specific surface area of the catalyst substance contributing to the reaction is increased, and the catalytic ability can be improved.
[0020]
  In the manufacturing apparatus according to the present invention, at least the physical vapor deposition means and the container for housing the conductive powder are installed in a sealed container, and the inside of the sealed container is in a vacuum state at the time of physical vapor deposition. After the chemical vapor deposition, the inside of the sealed container is set to an inert gas atmosphere.
[0021]
  In addition, there is a closing means capable of closing the upper opening of the container, and the introduction of the inert gas into the sealed container and the blocking while maintaining the sealed state in the sealed container after the physical vapor deposition. The container is configured to be able to perform the closing of the container.
[0022]
Specifically, an expandable / contractible member is provided around the body portion and the lid portion of the sealed container, and the expandable member of the expandable member is maintained while maintaining the sealed state in the sealed container after the physical vapor deposition. The lid part is detached from the main body part under extension, and the inert gas can be introduced into the sealed container and the container can be closed by the closing means in this detached state. It is preferable.
[0023]
The catalytic material having high activity may burn in the air even after sufficient cooling. However, according to the manufacturing apparatus based on the present invention, the conductive catalyst particles are taken out in the inert gas atmosphere such as nitrogen gas. Therefore, the conductive catalyst particles having high activity can also be produced.
[0024]
  In the apparatus according to the present invention, at least a part of the connecting means for connecting the vibrating means and the base is formed of an insulating material.
[0025]
  Hereinafter, preferred embodiments of the present invention will be described.Based on various examplesSee drawingUnderexplain.
[0026]
Example 1
  FIG. 1 is a schematic view of an example of an apparatus for producing conductive catalyst particles.
[0027]
  As shown in FIG.thisThe conductive catalyst particle manufacturing apparatus includes a vibrating means 2 for vibrating the conductive powder 1, a cooling means 5 (FIG. 1 (b)) including a refrigerant passage 4 provided in the base 3, and a base 3. A storage container 6 for storing the conductive powder 1 and the physical vapor deposition means by the sputtering method using the catalyst material as a target 7. As the vibration means 2, a vibrator comprising an electromagnetic coil type or an ultrasonic horn can be used. Moreover, it is preferable that the base | substrate 3 and the storage container 6 are comprised so that attachment or detachment is possible.
[0028]
  thisIn the apparatus, the cooling means 5 is preferably composed of a refrigerant passage 4 provided in the base 3 as shown in FIG. And the said cooling can be performed effectively by letting the refrigerant | coolant 10, for example, 10-40 degreeC cold water, pass through the refrigerant path 4 at the time of physical vapor deposition. As the refrigerant passage 4, for example, a flexible metal tube such as stainless steel that can be used in a vacuum can be used.
[0029]
  thisAccording to the apparatus for producing conductive catalyst particles, since the cooling means 5 for cooling the conductive powder 1 is provided, even when heat is generated when the catalyst substance is attached to the surface of the conductive powder 1 by the sputtering method, Problems such as sintering of the catalyst material and thermal deformation of the container 6 do not occur. Therefore, it is possible to increase the power input to the sputtering and to shorten the time for producing the conductive catalyst particles. In addition, the cooling performed before the produced conductive catalyst particles are exposed to air.ofTime can be shortened.
[0030]
In addition, it has a vibrating means 2 for vibrating the conductive powder 1, and the catalyst substance is adhered to the surface of the conductive powder 1 by sputtering while vibrating the conductive powder 1. 1 is sufficiently mixed and does not stay in one place of the container 6. Therefore, not only the surface of the powder layer but also the inside of the conductive powder 1 comes out to the surface, and the catalyst substance can be uniformly attached to all the conductive powders 1.
[0031]
Further, since the catalyst substance is adhered to the surface of the conductive powder 1 by sputtering, the catalyst substance having good crystallinity is applied only to the surface of the conductive powder 1 at a low temperature (that is, the conductive powder). The conductive catalyst particles obtained can exhibit good catalytic action in a smaller amount and contact between the catalytic material and the gas. Since the area is sufficiently secured, the specific surface area of the catalyst substance contributing to the reaction is increased, and the catalytic ability is also improved.
[0032]
  thisAs shown in FIG. 2 (A), the conductive catalyst particles produced using the apparatus are such that the catalyst material 8 does not enter pores (not shown) present on the surface of the conductive powder 1, for example. It adheres only to the surface of the conductive powder 1. Therefore, a good catalytic action can be obtained with a smaller amount of catalyst, and a sufficient contact area between the catalyst substance 8 and the gas is ensured, so that the specific surface area of the catalyst substance 8 contributing to the reaction is increased, and the catalyst The performance is also improved.
[0033]
Further, as shown in FIG. 2B, an ion conductor 9 is attached to the surface of the conductive powder 1, and further, the catalyst material is applied to the surface of the ion conductor 9 by the physical vapor deposition means such as sputtering. It is also possible to attach 8. In this case, since the catalyst material 8 is attached by the physical vapor deposition means, for example, it is not necessary to perform a heat treatment for improving the crystallinity of the catalyst material 8, and the performance of the ion conductor 9 is not impaired. 8 can be deposited.
[0034]
Each of the conductive catalyst particles of (A) and (B) shown in FIG. 2 exhibits 10 to 1000 weight of the catalyst substance 8 with respect to the conductive powder 1 in order to exhibit both catalytic ability and conductivity. The catalyst substance 8 is preferably a noble metal material such as Pt, Ir, Rh, Ru.
[0035]
The electric resistance of the conductive powder 1 is 10^-3Ω · m or less, preferably carbon, ITO (Indium tin oxide: Indium oxide doped with tin) and SnO₂It is preferable to use at least one of them.
[0036]
When carbon is used as the conductive powder 1, the specific surface area of this carbon is 300 m.²/ G or more, preferably 300 m²When it is less than / g, the characteristics as the conductive catalyst particles may be deteriorated.
[0037]
Further, when a gas diffusive catalyst electrode is produced using the conductive catalyst particles, gas permeability is an important performance. When carbon is used as the conductive powder 1, the oil absorption amount of the carbon is reduced to 200 ml / By setting it to 100 g or more, good gas permeability can be obtained.
[0038]
Example 2
  AboveWhen the conductive catalyst particles are manufactured using a manufacturing apparatus and the conductive catalyst particles are exposed to air when the conductive catalyst particles are taken out from the apparatus, the conductive catalyst particles may be burned. . For this reason, in the apparatus for producing conductive catalyst particles according to the present invention, at least the physical vapor deposition means and the storage container for storing the conductive powder are installed in a sealed container, and the physical sealing is performed at the time of physical vapor deposition. It is preferable that the inside of the container is evacuated and the inside of the sealed container is an inert gas (for example, nitrogen gas) atmosphere after physical vapor deposition.
[0039]
In addition, there is a closing means capable of closing the upper opening of the container, and the introduction of the inert gas into the sealed container and the blocking while maintaining the sealed state in the sealed container after the physical vapor deposition. It is preferable that the container can be closed by the means.
[0040]
The catalytic material having high activity may burn in the air even after sufficient cooling. However, according to the manufacturing apparatus based on the present invention, the conductive catalyst particles are taken out in the inert gas atmosphere such as nitrogen gas. Therefore, the conductive catalyst particles having high activity can be produced.
[0041]
FIG. 3 is a schematic cross-sectional view of an apparatus for producing conductive catalyst particles according to the present invention configured to be able to take out the conductive catalyst particles in the inert gas atmosphere.
[0042]
As shown in FIG. 3 (a), the manufacturing apparatus according to the present invention is a cooling means comprising the physical vapor deposition means by the sputtering method using the catalyst substance as a target 7 and the refrigerant passage 4 provided in the substrate 3. 5 and a container 6 for storing the conductive powder 1 are installed in a sealed container 11 and can be expanded and contracted around the body 11a and the lid 11b of the sealed container 11, for example, a polymer film A telescopic member 12 made of metal is provided. Further, a lid member 14 is disposed as the closing means capable of closing the upper opening 13 of the storage container 6. The structures of the vibration means 2 and the cooling means 5 are the same as described above with reference to FIG.
[0043]
First, during the physical vapor deposition, the inside of the sealed container 11 is evacuated. After the physical vapor deposition, an inert gas (for example, nitrogen gas) 34 is introduced from the inert gas inlet 15 while maintaining a sealed state, and the inside of the sealed container 11 is made an inert gas atmosphere.
[0044]
Next, as shown in FIG. 3B, after the inside of the sealed container 11 is made an inert gas atmosphere, the lid 11b is detached from the main body 11a under the extension of the elastic member 12 while maintaining the sealed state. (In the direction of the arrow 35 in the figure), and in this detached state, the lid member 14 as the closing means is moved to the position of the upper opening 13 of the storage container 6 indicated by the phantom line, and the storage container 6 is closed. Here, as shown in the figure, the expansion member 12 is provided with, for example, a globe 16. By using the globe 16, the lid member 14 is maintained while maintaining an inert gas atmosphere in a sealed state in the sealed container 11. Can be moved.
[0045]
Then, the electrically conductive catalyst particles are formed by removing the elastic member 12 and detaching the lid portion 11b from the main body portion 11a, opening the sealed container 11 and adhering the catalyst substance to the surface of the conductive powder 1. The accommodated container 6 can be taken out. At this time, since the container 6 is in a state where the upper opening 13 is closed by the lid member 14, the inert gas atmosphere is maintained inside.
[0046]
The catalytic material having high activity may burn in the air even after sufficient cooling. However, according to the manufacturing apparatus based on the present invention, the conductive catalyst particles are taken out in the inert gas atmosphere such as nitrogen gas. Therefore, the conductive catalyst particles having high activity can also be produced.
[0047]
Example 3
  When high frequency sputtering is used as the physical vapor deposition means, positive charges and negative charges are applied alternately, so Ar⁺And so on, not only the target but also flying in multiple directions. However, since the container side containing the conductive powder is substantially in a positive potential state due to particles from the target, it is possible to reduce damage caused by the cations colliding with the conductive powder. .
[0048]
In the apparatus according to the present invention, when the vibration means is grounded, the vibration means, the storage container, and the cooling means are provided to hold the storage container and the cooling means in the above-described positive potential state. It is preferably electrically insulated.
[0049]
That is, in the apparatus according to the present invention, as shown in FIG. 4, it is preferable that at least a part of the connecting means 17 that connects the vibrating means 2 and the base 3 is formed of the insulating material 18. Further, it is preferable that at least a part of the refrigerant passage 4 provided in the base 3 is also formed of the insulating material 18. Thereby, the storage container 6 and the cooling means 5 can be hold | maintained in the state of the above-mentioned positive potential, and the said physical vapor deposition by the said high frequency sputtering can be performed more efficiently.
[0050]
Example 4
  In the apparatus according to the present invention, it is preferable that a vibration amplifying means is provided in the container. Thereby, the catalyst substance can be attached to the surface of the conductive powder by the physical vapor deposition means while simultaneously vibrating the conductive powder and the vibration amplification means by the vibration means, The conductive powder is more thoroughly vibrated and mixed, and does not stay in one place of the container. Therefore, the conductive powder is not only on the surface of the powder layer, but also the inside is exposed to the surface, and the catalyst substance is more easily and uniformly attached to all the conductive powder. Can do.
[0051]
  Here, as the vibration amplification means, as shown in FIG. 5, a ball 19 having a smooth surface can be used. Further, the vibration frequency applied to the conductive powder 1 and the ball 19 as the vibration amplification means by the vibration means 2 is 5 to 200 Hz in order to mix the conductive powder 1 sufficiently. The amplitude of the vibration is preferably ± (0.5-20) mm for the same reason (othersExampleThe same is true for.
[0052]
In this case, the ball 19 is preferably a ceramic or metal ball having a diameter of 1 to 10 mm.
[0053]
If the catalyst material is attached to the surface of the conductive powder 1 by, for example, the sputtering method under the environment within each preferable range of conditions as described above, the conductive powder 1 is further improved. Therefore, the catalyst substance can be more uniformly attached to the surface of the conductive powder 1. When deviating from the above ranges, that is, when the diameter of the ball 19 is less than 1 mm or more than 10 mm, when the frequency is less than 5 Hz or more than 200 Hz, or when the amplitude is less than ± 0.5 mm In such a case, the conductive powder 1 cannot vibrate satisfactorily, and the conductive powder 1 that does not flow and remains in the bottom of the container 6 is likely to be formed, and uniform film formation is possible. It may not be possible. On the other hand, when the amplitude exceeds 20 mm, the conductive powder 1 may jump out and the yield may be reduced.
[0054]
As shown in the schematic view of the container 6 in which the conductive powder 1 and the ball 19 as the vibration amplifying means are arranged in FIG. 6, the total area of the balls 19 with respect to the area S of the distribution region of the conductive powder 1 The ratio of A is preferably 30 to 80%. If this ratio is too small, the mixing of the conductive powder 1 tends to be insufficient, and if it is too large, the ratio of the conductive powder 1 tends to be small, and the adhesion efficiency of the catalyst substance by sputtering tends to deteriorate, In some cases, the production efficiency of the conductive catalyst particles to which the catalyst substance is adhered becomes insufficient.
[0055]
FIG. 7 shows a partially enlarged schematic cross-sectional view of the container 6 in which the conductive powder 1 and the ball 19 as the vibration amplifying means are arranged, with respect to the layer thickness t formed by the conductive powder 1. It is preferable that the diameter R of the ball 19 as the vibration amplification means is 10 to 70%. If the diameter is out of the range, it tends to be disadvantageous for the same reason as in the case of the area ratio.
[0056]
  Manufacturing according to the present inventionapparatusIn place of the ball, the vibration amplifying means uses a part integrally formed so that the wire forms a substantially spiral, substantially concentric or substantially folded pattern when seen in a plan view. Installed on this part at least partially on the bottom surface of the container (this non-fixed state is a state that itself vibrates freely in three dimensions: the same applies hereinafter) The conductive powder may be disposed and the vibration may be applied.
[0057]
FIG. 8 is a schematic view of a vibration device according to the present invention using, as the vibration amplification means, a component 20 that is integrally formed so that a wire forms a spiral pattern when viewed in a plan view. However, the above-described refrigerant passage is not shown (the same applies hereinafter).
[0058]
FIG. 9 shows a vibration according to the present invention using a component 21 integrally formed so that the wire forms a concentric pattern in plan view (that is, connected in a radial direction) as the vibration amplifying means. It is a schematic sectional drawing of an apparatus.
[0059]
FIG. 10 is a schematic cross-sectional view of a vibration device according to the present invention using, as the vibration amplification means, a component 22 that is integrally formed so that a wire forms a folded pattern when viewed in a plan view.
[0060]
In any case shown in FIGS. 8 to 10, the component 20, 21, or 22 is placed in an unfixed state on the bottom surface of the container 6, and the conductive powder 1 is placed on the component 20, 21, or 22. When placed and subjected to the vibration, the shape of the component 20, 21 or 22 vibrates while being held, so that the conductive powder 1 can be further vibrated and flow better. At this time, if the catalyst material is attached to the surface of the conductive powder 1 by the physical vapor deposition means such as the sputtering method, the conductive powder 1 in the container 6 is not only the surface but also the inside. The catalyst material can be uniformly deposited over the entire surface.
[0061]
In obtaining such an effect, the wire formed in a spiral, concentric or folded pattern is a metal wire having a diameter of 1 to 10 mm, and is formed in a spiral, concentric or folded pattern. It is preferable that the outer diameter of the component is about 5 mm smaller than the inner diameter of the container, and the pattern pitch is 5 to 15 mm. When the conditions deviate from these values, the mixing of the conductive powder 1 tends to be insufficient, and the adhesion efficiency of the catalyst substance tends to decrease.
[0062]
Further, for the same reason as the case of using the above-described ball, the wire as the vibration amplifying means has a spiral shape, a concentric shape, or a folded shape as viewed in a plane with respect to the layer thickness formed by the conductive powder. It is preferable that the thickness of the parts integrally formed so as to form a pattern is 10 to 70%.
[0063]
The conductive catalyst particles obtained using the production apparatus according to the present invention can themselves form a catalyst layer by press working or the like. However, when the conductive catalyst particles are formed by binding with a resin, the conductive catalyst particles are made porous. For example, it is more preferable when manufacturing a gas-diffusible catalyst electrode.
[0064]
The conductive catalyst particles produced using the production apparatus according to the present invention are used as a constituent material of the gas diffusible catalyst electrode as described above, and the gas diffusible catalyst electrode is configured as a fuel cell, for example. It can be applied to electrochemical devices.
[0065]
That is, in a basic structure composed of a first pole, a second pole, and an ionic conductor sandwiched between the two poles, at least the first pole of the first pole and the second pole is the present invention. The gas diffusive catalyst electrode containing the conductive catalyst particles produced using a manufacturing apparatus based on the above can be applied.
[0066]
FIG. 11 shows a fuel cell of a specific example using the gas diffusive catalyst electrode. Here, in the catalyst layer 23 in FIG. 11, the catalyst substance (for example, platinum) adheres only to the surface of the conductive powder (for example, carbon powder) manufactured using the manufacturing apparatus according to the present invention. In addition to the conductive catalyst particles, the ionic conductor, water-repellent resin (for example, fluorine-based) and pore-forming agent (CaCO_Three). The gas diffusive catalyst electrode is a porous gas diffusible catalyst electrode comprising a catalyst layer 23 and, for example, a carbon sheet 24 as a porous gas permeable current collector. However, in a narrow sense, only the catalyst layer 23 may be referred to as a gas diffusing catalyst electrode. An ion conducting portion 25 is sandwiched between a first electrode using the gas diffusible catalyst electrode and a second electrode.
[0067]
This fuel cell has a negative electrode (fuel electrode or hydrogen electrode) 27 with a terminal 26 and a positive electrode (oxygen electrode) 29 with a terminal 28 facing each other, and an ion conducting portion 25 is sandwiched between these two electrodes. Has been. In use, H on the negative electrode 27 side₂Hydrogen is passed through the flow path 30. Fuel (H₂) Generate hydrogen ions while passing through the flow path 30, and these hydrogen ions move to the positive electrode 29 side together with the hydrogen ions generated at the negative electrode 27 and the hydrogen ions generated at the ion conducting portion 25, where O₂It reacts with oxygen (air) passing through the flow path 31, and thereby a desired electromotive force is taken out.
[0068]
In such a fuel cell, the gas diffusive catalyst electrode containing the conductive catalyst particles produced using the production apparatus according to the present invention constitutes the first electrode and the second electrode. In addition, the catalyst material and gas (H₂) Is sufficiently secured, the specific surface area of the catalyst substance contributing to the reaction is increased, the catalytic ability is improved, and good output characteristics are obtained.
[0069]
In the gas diffusible catalyst electrode containing the conductive catalyst particles produced by using the production apparatus according to the present invention, or between both electrodes of the first electrode and the second electrode constituting the electrochemical device Examples of ionic conductors that can be used in the ionic conductive portion sandwiched between the two include general Nafion (registered trademark) (perfluorosulfonic acid resin manufactured by DuPont).
[0070]
【Example】
Hereinafter, the present invention will be specifically described based on examples.
[0071]
Example 1
First, a flexible pipe serving as the refrigerant passage was provided on the base body as the cooling means, and the cooling means and the vibration means were connected using the connection means. Next, the container containing the carbon powder as the conductive powder was detachably installed on the base with a chuck in a state of good heat conduction.
[0072]
A part of the connection means for connecting the base and the vibration means is formed of an insulating material, the cooling means including the container is electrically insulated from the ground, and the vibration means is in an electrically floating state. Was sputtered while generating vibration with an amplitude of ± 5 mm and a vibration frequency of 36 Hz.
[0073]
Sputtering power is 2 W / cm²As a result, platinum was adhered to the carbon powder to produce a platinum-supported carbon powder. When the temperature of the container during sputtering was measured, it was about 70 ° C.
[0074]
Then, after the sputtering was completed, water cooling was continued. After 20 minutes, the temperature of the storage container was cooled to 30 ° C. or less, and the storage container in which the platinum-supported carbon powder was stored was taken out.
[0075]
Further, as shown in FIG. 3, the apparatus of the present embodiment is configured so that the containing container can be taken out from the sealed container in a nitrogen gas atmosphere so that the produced platinum-supported carbon powder does not come into contact with oxygen (air). I made it. The obtained platinum-supported carbon powder was lightly kneaded with water so as not to burn in air, and then a catalyst ink was produced in the air.
[0076]
The platinum-supported carbon powder obtained as described above is kneaded with perfluorosulfonic acid as a binder and nPA (normal propyl alcohol) as an organic solvent, and this mixed liquid is mixed with carbon powder and water-repellent resin. A gas diffusive catalyst electrode was produced by applying and drying on the coated carbon sheet. This gas diffusive catalyst electrode was disposed on both sides of an ion exchange membrane (perfluorosulfonic acid), a fuel cell as shown in FIG. 11 was produced, and the output was measured. The output obtained in this example (unit: mW / cm²) As a relative value, which was 100%.
[0077]
Comparative Example 1
Except that the cooling means was not installed, the sputtering input power was 2 W / cm in the same manner as in the above example.²Sputtering was performed to produce platinum-supported carbon powder. As a result, the temperature of the container during sputtering was raised to 300 ° C., and 3 hours were required for cooling to 30 ° C. after the completion of sputtering. Furthermore, because of the overheated state, the catalyst capacity was reduced, and the output of the fuel cell produced in the same manner as described above using the obtained platinum-supported carbon powder was about 90% with respect to the above example. became.
[0078]
  In addition,A platinum-supported carbon powder was produced by sputtering in the same manner as in the above example except that the base and the vibrating means were not electrically insulated and the carbon powder was at ground potential. In this case, when the output of the fuel cell was measured, it was 90% with respect to the above example. This is presumably because the catalyst particles were disturbed by reverse sputtering.
[0079]
  Also,A platinum-carrying carbon powder was produced in the same manner as in the above example, except that when the produced platinum-carrying carbon powder was taken out of the chamber, the chamber was opened in an air atmosphere instead of a nitrogen gas atmosphere. In this case, the catalyst ink could be produced without burning up to about 40% by weight of platinum, but in the region exceeding 40% by weight, it was burned by oxygen in the atmosphere even after sufficient cooling to produce a catalyst ink. I couldn't.
[0080]
While the present invention has been described with reference to the embodiments and examples, the above examples can be variously modified based on the technical idea of the present invention.
[0081]
For example, in the conductive catalyst particle manufacturing apparatus and the vibration apparatus according to the present invention, the shape, configuration, material, and the like can be appropriately selected without departing from the present invention.
[0082]
  Moreover, although the said electroconductive catalyst particle was produced using the manufacturing apparatus based on this invention, and the said fuel cell using the said gas diffusible catalyst electrode formed by containing the said electroconductive catalyst particle was demonstrated, The gas diffusive catalyst electrode can also be applied to a hydrogen production apparatus which is a reverse reaction of the fuel cell.
[0083]
[Effects of the invention]
  According to the present invention, since the cooling means for cooling the conductive powder includes the cooling means provided on the base body on which the container is disposed, the conductive powder is used by using the physical vapor deposition means. Even if heat is generated when the catalyst material is adhered to the surface of the metal, problems such as sintering of the catalyst material and thermal deformation of the container do not occur. Therefore, the input power to the physical vapor deposition means can be increased, and the production time of the conductive catalyst particles can be shortened. Moreover, the cooling time before exposing the produced electroconductive catalyst particle to air can be shortened.
  In addition, at least the physical vapor deposition means and the container for housing the conductive powder are installed in a sealed container, and the inside of the sealed container is evacuated during physical vapor deposition, and the sealed after physical vapor deposition. The container has an inert gas atmosphere, and has a closing means capable of closing the upper opening of the container, and maintains the sealed state in the sealed container after the physical vapor deposition, Since the introduction of the active gas and the closing of the container by the closing means can be performed, the highly active catalytic substance may be burned in air even after sufficient cooling. The conductive catalyst particles can be taken out in the inert gas atmosphere such as gas, and the conductive catalyst particles having high activity can be produced.
[0084]
  In addition, the vibration means for vibrating the conductive powder, the catalyst substance is attached to the surface of the conductive powder by the physical vapor deposition means while vibrating the conductive powder. The conductive powder is sufficiently mixed and does not stay in one place. Accordingly, not only the surface of the powder layer but also the inside of the conductive powder comes to the surface, and the catalyst substance can be uniformly attached to all the conductive powders.
  In addition, since at least a part of the connecting means for connecting the vibrating means and the base is formed of an insulating material, the container can be held in a positive potential state, and physical vapor deposition by high frequency sputtering can be further performed. Can be done efficiently.
[0085]
Further, since the catalyst substance is adhered to the surface of the conductive powder by the physical vapor deposition means, the catalyst substance having good crystallinity is applied only to the surface of the conductive powder at a low temperature (that is, the The conductive catalyst particles obtained can adhere to the surface of the conductive powder (without entering the inside through the pores) and exhibit good catalytic action in a smaller amount, and the catalyst substance and gas Is sufficiently secured, the specific surface area of the catalytic material contributing to the reaction is increased, and the catalytic performance is also improved.
[Brief description of the drawings]
FIG. 1 shows an embodiment of the present invention.For explainingOf conductive catalyst particlesManufacturingIt is a schematic sectional drawing of an example of an apparatus.
FIG. 2 is a schematic cross-sectional view showing conductive catalyst particles obtained using the production apparatus.
FIG. 3 is a schematic sectional view of an example of an apparatus according to the present invention.
FIG. 4 is a schematic sectional view of another example of the apparatus according to the present invention.
FIG. 5 is a schematic cross-sectional view of a vibration device used in the manufacturing apparatus.
FIG. 6 is a partially enlarged schematic view of the container in the apparatus according to the present invention.
FIG. 7 is a partially enlarged schematic cross-sectional view of the vibration device according to the present invention.
FIG. 8 is a schematic cross-sectional view of another vibration device.
FIG. 9 is a schematic cross-sectional view of still another vibration device.
FIG. 10 is a schematic sectional view of the vibration device according to the present invention.
FIG. 11 is a schematic configuration diagram of a fuel cell using a gas diffusive catalyst electrode containing conductive catalyst particles obtained by using the production apparatus according to the present invention.
FIG. 12 is a schematic sectional view of a conductive catalyst particle producing apparatus according to a conventional example.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Conductive powder, 2 ... Vibrating means, 3 ... Base | substrate, 4 ... Refrigerant passage, 5 ... Cooling means,
6 ... Container, 7 ... Target, 8 ... Catalyst substance, 9 ... Ion conductor,
DESCRIPTION OF SYMBOLS 10 ... Refrigerant, 11 ... Sealed container, 11a ... Main-body part, 11b ... Cover part,
12 ... telescopic member, 13 ... upper opening, 14 ... lid material, 15 ... inert gas inlet,
16 ... Globe, 17 ... Connection means, 18 ... Insulating material, 19 ... Ball,
20, 21, 22 ... vibration amplification means, 23 ... catalyst layer, 24 ... gas permeable current collector,
25 ... Ion conduction part, 26, 28 ... Terminal, 27 ... Negative electrode, 29 ... Positive electrode,
30 ... H₂Channel, 31 ... O₂Flow path, 34 ... inert gas

Claims

Vibrating means for vibrating the conductive powder, cooling means for cooling the conductive powder, and physical vapor deposition means for adhering a catalytic substance to the surface of the conductive powder, the conductive powder A storage container for accommodating vibrations by the vibration means, the cooling means is provided on the base, and at least the physical vapor deposition means and the conductive powder for containing the conductive powder. Is installed in a sealed container, and the inside of the sealed container is in a vacuum state at the time of physical vapor deposition, and the inside of the sealed container is an inert gas atmosphere after physical vapor deposition ,
Has closable closing means the upper opening of the container, while maintaining the sealed state of the sealed vessel after said physical vapor deposition, introducing said closing infarction means of the inert gas into the closed vessel Configured to be able to perform the closure of the container according to,
An apparatus for producing conductive catalyst particles .

An expandable / contractible member is provided between the body portion and the lid portion of the sealed container, and the lid is extended under the stretchable member while maintaining a sealed state in the sealed container after the physical vapor deposition. The body part is detached from the main body part, and in this detached state, the inert gas can be introduced into the sealed container and the container can be closed by the closing means. An apparatus for producing the described conductive catalyst particles.

The apparatus for producing conductive catalyst particles according to claim 1, wherein the base and the container are configured to be detachable.

The apparatus for producing conductive catalyst particles according to claim 1, wherein the cooling means includes a refrigerant passage provided in the substrate.

The apparatus for producing conductive catalyst particles according to claim 1, wherein at least a part of connection means for connecting the vibration means and the substrate is formed of an insulating material.

2. The production of conductive catalyst particles according to claim 1, wherein the container is provided with vibration amplification means, and the vibration frequency applied to the conductive powder and the vibration amplification means by the vibration means is 5 to 200 Hz. apparatus.

2. The vibration amplifying means is provided in the container, and the amplitude of the vibration given to the conductive powder and the vibration amplifying means by the vibrating means is ± (0.5 to 20) mm. An apparatus for producing conductive catalyst particles.

2. The production of conductive catalyst particles according to claim 1, wherein an ion conductor is attached to a surface of the conductive powder, and further, the catalyst substance is attached to the surface of the ion conductor by the physical vapor deposition means. apparatus.

A vibration unit that vibrates the conductive powder; a cooling unit that cools the conductive powder; and a storage container that stores the conductive powder. The storage container transmits vibrations generated by the vibration unit. The vibration device is arranged on a base body, and the cooling means is provided on the base body, wherein at least a part of a connection means for connecting the vibration means and the base body is formed of an insulating material. Equipment .

The vibration device according to claim 9 , wherein the base body and the storage container are configured to be detachable.

The vibration device according to claim 9 , wherein the cooling unit includes a refrigerant passage provided in the base.

The container vibration amplifying means provided in the said frequency of vibration applied to the conductive powder and the vibration amplifying means by the vibration means is a 5～200Hz, vibration device according to claim 9.

The container vibration amplifying means is provided on the amplitude of vibration applied to the conductive powder and the vibration amplifying means by said vibrating means is ± (0.5 to 20) mm, and according to claim 9 Vibration device.