JP6088048B2 - 水分解用の通気性電極構造およびその方法並びにシステム - Google Patents
水分解用の通気性電極構造およびその方法並びにシステム Download PDFInfo
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Description
第1の多孔質膜を含むカソード、
第2の多孔質膜を含むアノード、
前記カソードと前記アノードを浸漬させる少なくとも1つの電解質、を有し、
前記カソードと前記アノードで実質的に気泡を形成させることなくガスを生成させ、該ガスは前記の多孔質膜から該セルの外に拡散する、水分解セルが提供される。
システムの効率の向上に付随する水分解反応からのガスを効率的に除去すること;
ガスの直接分離はセパレータを不要にすること;
高純度ガスの製造;
生成した水素がアノードで酸化されること、および生成した酸素がカソードで還元されることの可能性を減少させること;
触媒の作用のために、より好ましい環境を提供すること;
別の方法ではO2分圧の増加に伴い劣化するであろう不適当な触媒の使用を容易にする;
ガスの直接分離は、ガスのクロスオーバーを減少させ、それによりクーロン効率を向上させること;および
本発明の電極と、最適化された触媒および光触媒との組み合わせは、よりコスト効率の高い電解装置の製造の機会を提供すること。
PTFE膜(ゴアテックス(登録商標))はゴア社から入手し、マイテックス(登録商標)(10μm)はミリポアから入手した。Auマイラ(2.5Ω/□)はCPフィルム社から購入した。無水マレイン酸はシグマ−アルドリッチから入手した。Ptコーティングの前に行う、ゴアテックス(登録商標)、マイテックス(登録商標)、ポリエチレン(PE)およびポリプロピレン(PP)膜の作製は、サイエンス 2008;321:671−4の題名が「気相重合PEDOT電極上での酸素の高速還元」である、Winther−Jensenらの以前の研究と同様である。金伝導層に強く結合させるために、膜の疎水性表面に無水マレイン酸をプラズマ重合を用いてグラフトするが、そのプラズマ重合については、前述の文献およびAdemovicらのPlasma Processes Polym 2005;2:53−63に記載の題名が「タンパク質の吸着を防止することを目的とする、パルスACプラズマ重合を用いるPETフィルムの表面改質」である文献に報告されている。金がプラズマ処理された膜の上にスパッタされ、その厚さは、表面抵抗が、〜5Ω/□となるように最適化された。次に、金層の上に28〜30mA、60秒でPtをスパッタした。従来のGDEも比較のため検討したが、E−TEKからアイオノマーフリー(VulcanXC−72上にLT−140EW−30%Pt、0.5mgcm−2)を入手し、そのまま用いた。SEM画像は、JEOL7100F電界放出銃走査型電子顕微鏡を用いて5kVで得た。
従来のラミネーターを用いて膜を金のストリップで挟んだ。ラミネートの0.7cm2の窓は、両面粘着テープで試験セルに取り付けられ時に、膜のPt被覆面に電解質が接触すること、およびガスが隣接室と通気できることを可能とする(図1)。
0.05MでpH4のナトリウムp−トルエンスルホン酸(シグマアルドリッチから)を、電解質として用いた。30mlの電解質を試験セル中に用い、電解質の上に30mlのガス空間を設けた。飽和カラメル参照電極(SCE)およびカーボンロッドまたはPt対極を用いて3電極セルを組み立てた。マルチチャンネルポテンショスタット(プリンストンアプライドリサーチのVMP2)を定電流電解に用いた。電極間の距離は1.5cmであり、全ての作用電極の動作時の電位は、典型的には〜2−2.4Vvs.SCEであった。
Pt被覆Au/ゴアテックス(登録商標)電極をアノードとカソードの両方に用いた場合、セルから両方のガスが除去され、ファラディ効率は92%に増加した。この実験で検出されたH2は、測定誤差の範囲内(±7%)で、2:1の化学量論比に近いことが見出された。これは、最適化されたセルとガス流の構成では、これらのセルでセパレータの使用を回避することが実用的であることを示唆している。
CdS/Ti/Au/ゴアテックスまたはTi/Au/ゴアテックス(0.5cm2)を積層し、2つのプラスチックボトルの間に挟んだ。前側のチャンバをpH6.5の0.05M NaPTSの30mlで満たした。酸素センサをガス室に配置した。DOプローブに直接光が当たるのを防ぐためにプラスチック室を覆うために黒色布を用いた。試料に光を照射するためにアサヒランプを用いた。以下の手順の後、各データ点を収集した:N2ガスを用いて約15分間またはベースラインが安定するまで電解質をパージし、同時に後室にO2をフラッシュし、N2を除去した後直ぐに(および穴を封止した)試料に光を7分間照射し、さらに光を5分間照射しながらO2を除去した(および穴を封止した)。このプロセスを39回繰り返した。増加したO2をモニターし、典型的なグラフを図6に示す。
,Int J Hydrogen Energy 2011;36:15089−104)。
その多くが酸素気泡の存在に敏感である光活性電極触媒の寿命を向上させるために、この方法は用いることもできる。
Claims (25)
- 多孔質膜を含む少なくとも1つの電極を有する水分解セルであって、該多孔質膜は、少なくともその一部が疎水性であり、該少なくとも1つの電極で生成したガスが、該多孔質膜を介して該セルの外に拡散する、該水分解セル。
- 前記少なくとも1つの電極で生成したガスの90%を超える量が、前記多孔質膜を横切って除去される、請求項1記載の水分解セル。
- 前記少なくとも1つの電極で生成したガスの95%を超える量が、前記多孔質膜を横切って除去される、請求項1記載の水分解セル。
- 前記少なくとも1つの電極で生成したガスの99%を超える量が、前記多孔質膜を横切って除去される、請求項1記載の水分解セル。
- 前記の生成したガスは、実質的に気泡を形成することなく、前記少なくとも1つの電極から分離される、請求項1記載の水分解セル。
- 前記の生成したガスは、125μmよりも小さい気泡を形成する、請求項1記載の水分解セル。
- 前記の生成したガスは、100μmよりも小さい気泡を形成する、請求項1記載の水分解セル。
- 前記の生成したガスは、50μmよりも小さい気泡を形成する、請求項1記載の水分解セル。
- 多孔質膜を含むカソードを有し、該カソードで生成するH2ガスが該多孔質膜を介して該セルの外に拡散し、気泡を形成させることなく、カソード反応で生成するH2ガスを分離する、請求項1記載の水分解セル。
- 多孔質膜を含むアノードを有し、該アノードで生成するO2ガスが該多孔質膜を介して該セルの外に拡散し、気泡を形成させることなく、アノード反応で生成するO2ガスを分離する、請求項1記載の水分解セル。
- 前記多孔質膜が、薄膜被膜を有する、請求項1記載の水分解セル。
- 前記薄膜被膜が、疎水性である、請求項11記載の水分解セル。
- 前記薄膜被膜が、シリコーン−フルオロポリマー、ポリジメチルシロキサン(PDMS)またはフルオロモノマーとのコポリマー、PDD−TFE(テトラフルオロエチレンとパーフルオロ−2,2−ジメチル−1,3−ジオキソール)、ポリフッ化ビニル、ポリ塩化ビニル、ナイロン8,8、ナイロン9,9、ポリスチレン、ポリフッ化ビニリデン、ポリn−ブチルメタクリレート、ポリトリフルオロエチレン、ナイロン10,10、ポリブタジエン、ポリエチレン、ポリクロロトリフルエチレン、ポリプロピレン、ポリジメチルシロキサン、ポリt−ブチルメタクリレート、フッ素化エチレンプロピレン、ヘキサトリアコンタン、パラフィン、ポリテトラフルオロエチレン、ポリ(ヘキサフルオロプロピレン)、ポリイソブチレン、またはこれらの組み合わせからなる群から選択される、請求項11記載の水分解セル。
- 前記多孔質膜が、導電性カーボン材料を含む、請求項11記載の水電解セル。
- 前記多孔質膜が、0.5μm未満の空孔寸法を有する、請求項11から13のいずれか1項に記載の水分解セル。
- 前記多孔質膜が、0.1μm未満の空孔寸法を有する、請求項11から13のいずれか1項に記載の水分解セル。
- 前記多孔質膜が、0.05μm未満の空孔寸法を有する、請求項11から13のいずれか1項に記載の水分解セル。
- 前記多孔質膜に伴う触媒をさらに含む、請求項1から17のいずれか1項に記載の水分解セル。
- 前記触媒が、Pt、Au、Pd、Ru、Ir、Mn、Fe、Ni、Co、NiOx、Mn錯体、Fe錯体、MoSx、CdS、CdSe、およびGaAsからなる群から選択される、請求項18記載の水分解セル。
- 少なくとも一部が疎水性である第1の多孔質膜を含むカソード、
少なくとも一部が疎水性である第2の多孔質膜を含むアノード、
前記カソードと前記アノードを浸漬させる少なくとも1つの電解質、を有し、
前記カソードと前記アノードで実質的に気泡を形成させることなくガスを生成させ、該ガスは前記の多孔質膜から該セルの外に拡散する、請求項1記載の水分解セル。 - 水分解セルを用いる水分解方法であって、
少なくとも一部が疎水性である第1の多孔質膜を含むカソードを用意すること、
少なくとも一部が疎水性である第2の多孔質膜を含むアノードを用意すること、
前記カソードと前記アノードを少なくとも1つの電解質に浸漬すること、および
前記アノードと前記カソードに通電すること、を含み、
前記アノードで生成したO2ガスが第2の多孔質膜を介して該セルの外に拡散し、
前記カソードで生成したH2ガスが第1の多孔質膜を介して該セルの外に拡散する、該水分解方法。 - 水電解セル中での水素発生方法であって、
第1の多孔質膜を含む第1の電極で水素ガスを生成させること、
少なくとも一部が疎水性である前記第1の多孔質膜を介して該水素ガスを該セルの外に拡散させること、および
実質的に気泡を形成させることなく、生成した該水素ガスを分離すること、を含む、該水素発生方法。 - 水電解セル中での酸素発生方法であって、
第2の多孔質膜を含む第2の電極で酸素ガスを生成させること、
少なくとも一部が疎水性である前記第2の多孔質膜を介して該酸素ガスを該セルの外に拡散させること、および
実質的に気泡を形成させることなく、生成した該酸素ガスを分離すること、を含む、該酸素発生方法。 - 触媒表面に隣接する前記の多孔質膜を横切って前記のガスを輸送することにより、前記のガスの90%を超える量が前記の電極で分離される、請求項22または23に記載の方法。
- 前記のガスが、125μmを超える気泡を形成させることなく分離される、請求項22または23に記載の方法。
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KR20150032691A (ko) | 2012-06-12 | 2015-03-27 | 모나쉬 유니버시티 | 기체 투과성 전극 및 제조 방법 |
AU2012382382A1 (en) | 2012-06-12 | 2015-01-15 | Aquahydrex Pty Ltd | Breathable electrode and method for use in water splitting |
EP2765224B1 (de) * | 2013-02-12 | 2018-04-11 | Airbus Defence and Space GmbH | Verfahren zum Betrieb einer Elektrolysezelle |
MX2016001378A (es) | 2013-07-31 | 2016-08-18 | Aquahydrex Pty Ltd | Celdas electroquimicas modulares. |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10760167B2 (en) | 2017-11-15 | 2020-09-01 | Kabushiki Kaisha Toshiba | Electrolytic cell and hydrogen production apparatus |
US11339480B2 (en) | 2019-03-06 | 2022-05-24 | Kabushiki Kaisha Toshiba | Electrolytic cell and hydrogen production apparatus |
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Publication number | Publication date |
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MX2014015168A (es) | 2015-08-14 |
WO2013185163A1 (en) | 2013-12-19 |
AU2018200988A1 (en) | 2018-03-01 |
RU2014152642A (ru) | 2016-08-10 |
KR20150023666A (ko) | 2015-03-05 |
US10577700B2 (en) | 2020-03-03 |
JP2015527482A (ja) | 2015-09-17 |
US20190093244A1 (en) | 2019-03-28 |
RU2603772C2 (ru) | 2016-11-27 |
CA2876236A1 (en) | 2013-12-19 |
US20150167185A1 (en) | 2015-06-18 |
BR112014031220A2 (pt) | 2017-06-27 |
US10087536B2 (en) | 2018-10-02 |
AU2012382382A1 (en) | 2015-01-15 |
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