JP6695867B2 - モノリシック2次元材料およびイオノマーを含むプロトン伝導膜、その作製方法、ならびに燃料電池および水素ガスセンサにおけるその使用法 - Google Patents
モノリシック2次元材料およびイオノマーを含むプロトン伝導膜、その作製方法、ならびに燃料電池および水素ガスセンサにおけるその使用法 Download PDFInfo
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Description
2次元材料のモノレイヤと、
2次元材料の少なくとも片面に設けられたイオノマー被膜と、
必要に応じて基体とを具えるプロトン伝導膜が提供される。
モノレイヤまたは2〜5層のモノリシックな2次元材料と、
2次元材料の少なくとも片面に設けられたイオノマー被膜と、
必要に応じて基体とを具えるプロトン伝導膜に関する。
2次元材料のモノレイヤと、
2次元材料の少なくとも片面に設けられたイオノマー被膜と、
必要に応じて基体とを具えるデューテロン伝導膜が提供される。
2次元材料のモノレイヤを設ける工程と、
2次元材料の少なくとも片面をイオノマーで被覆して該イオノマーの片面が2次元材料と接触し、他方の面が露出するようにする工程、またはイオノマーおよび非導電性構成成分を含む材料の層を2次元材料の片面に塗布する工程のいずれかと、
必要に応じて、少なくとも1つのイオノマー被膜の露出面に接して基体を設ける工程とを備える。
2次元材料のモノレイヤを設ける工程と、
2次元材料の少なくとも片面をイオノマーで被覆して該イオノマーの片面が2次元材料と接触し、他方の面が露出するようにする工程、またはイオノマーおよび非導電性構成成分を含む材料の層を2次元材料の片面に塗布する工程のいずれかと、
必要に応じて、少なくとも1つのイオノマー被膜の露出面に接して基体を設ける工程とを備える。
2次元材料のモノレイヤであって、除去可能な層の片面に配置され、その層の不連続部に位置関係を合わせたモノレイヤと、
除去可能な層の他方の面に設けられたエッチング可能な基体とを具える集合体が提供される。
除去可能な基体であって、その2表面がそれぞれ不連続の除去可能な層に覆われた、基体と、
2次元材料のモノレイヤであって、除去可能な層のうちの1つの上に配置され、その層およびその下に位置する基体の不連続部に位置関係を合わせたモノレイヤと、
基体の各面に設けられたイオノマー被膜と、
各イオノマー被膜と接する電極とを具え、
各電極をそれぞれの下に位置する除去可能な層および次元材料から離隔させるよう、除去可能な層のそれぞれおよび2次元材料がそれぞれのイオノマー被膜に覆われた、プロトン/デューテロン伝導膜デバイスが提供される。
エッチング可能な基体を含み、2表面が除去可能な層で覆われた集合体の1表面を部分的にマスキングして、除去可能な層の少なくとも一部を露出させたままとするマスキング工程と、
下に位置する基体が露出された領域に現れるパターンを形成するために、マスキングされた表面に光線またはプラズマを照射する工程と、
マスクを除去する工程と、
パターンに対応する領域から基体をエッチングする工程と、
他方の除去可能な層の表面に不連続部を導入する工程とを備える。
周期表の第8〜10族から選択された1つまたは複数の遷移金属から形成された不連続膜で装飾された、グラフェンおよびhBNから選択された2次元材料のモノレイヤまたはグラフェン、hBN、MoS2およびWS2から選択された2次元材料のモノレイヤを不連続部が導入された除去可能な層上に不連続部に位置関係を合わせて設ける工程と、
除去可能な層を担持する基体の両面のそれぞれをイオノマーで被覆する工程と、
各イオノマー層と接する電極を設ける工程とが行われる。
式中、x=5、y=1000、z=3(Nafionの場合)である。同様の適切な材料は、Schultz et al, Chemical engineering and technology, 24(12), p1223-1233 (2001)に記載されており、同論文の開示内容を、特に適切な導電性ポリマーに関連して本明細書に組み込む。
式中、x=6、y=1、z=1(Nafionの場合)、x=3−10、y=0.1、z=0−3(AGCのFlemion:フレミオン(登録商標)の場合)、またはx=2〜14、y=0.3、z=1〜2(Aciplex−S:アシプレックス(登録商標)の場合)である。この場合もまた、同様の適切な材料は、T.S Zhao, Micro fuel cells, principles and applications, p10 (2009)に記載されており、同論文の開示内容を、特に適切な導電性ポリマーに関連して本明細書に組み込む。
図4は微細加工工程を説明する。まず、両面が500nmのSiNxで被覆された市販のSiウェハから自立窒化ケイ素(SiNx)膜を用意する。エッチングマスクをフォトリソグラフィにより作製する。SiNx層の1つから1×1mm2の部分を反応性イオンエッチング(RIE)を用いて除去する(図4の工程1および2)。下に位置するSiウェハは、ウェハをKOH溶液に暴露することによってSiをエッチング除去して典型的にサイズ300×300μm2の自立SiNx膜を残す湿式化学によってエッチング除去される(工程3)。工程4の間、工程1および2と同じ手順を用いたRIEによって、SiNx膜に貫通する円形の穴を設ける。次に、2次元結晶(グラフェン、hBNまたはMoS2)を標準的な微細(micro)機械的剥離法により生成し、湿式または乾式のいずれかの技術を用いて膜上に転写してSiNxの開口を被覆する(工程5)。
上述のデバイスを、フォーミングガス(アルゴン中10%H2)が充填され、100%相対湿度を得るよう液体水を含むチャンバ内に配置した。I−V曲線をDC測定を用いて記録した。最大0.5V/minの掃引速度で、典型的に1Vまでの範囲で電圧を変化させた。これらの条件下で、曲線はヒステリシスがなく、再現性が高かった。デバイスは乾燥させなければ、何週間にもわたり安定した状態を保った。
SEMでの膜の目視検査により、10nm未満までのサイズの空孔およびクラックを確実に排除することができる(図5b参照)。SEMを用いて検査された本発明の2次元プロトン伝導体では、これらの種類の欠陥のいずれも観察されなかった。図5bに示すような時折生じるクラックは、故意に導入されるか、処理工程中に重大な失敗を犯した場合のみに観察され得る。
本発明の2次元プロトン伝導体を通る電流がプロトンにより運ばれることを端的に示すために、図10aに詳しく示された装置を用いた。グラフェン内を移動するプロトンは、それらが再結合して水素分子を形成する(2H++2e−>H2)Pt触媒層で捕集される。その後、水素流を、質量分析器で測定する。電流Iは、グラフェン膜を通過するプロトンの数によって決まるため、水素流Fは通過電流Iに直接関係する。
異なる2次元結晶により生じる電子雲を考慮することにより本実験結果を理解することが可能である。これらの電子雲は、2次元膜を通るプロトンの通過を妨げる。図1bのグラフェンおよびhBNのモノレイヤについての電子密度のグラフに加え、図11は、グラフェンおよびhBNの結晶格子のボールアンドスティックモデルを用いて、C、BおよびNの原子と重畳する位置におけるこれらの雲についての同様のグラフを示す。さらに図11は、モノレイヤMoS2についての電子密度をグラフ化している。後者の雲がhBNおよびグラフェンのモノレイヤの雲よりも大幅に密度が高いことが一目瞭然であり、これはMoS2モノレイヤを通るプロトン輸送がないことを示している。
定量分折について、以前より、第一原理分子動力学シミュレーション(AIMED)およびClimbingImageNudgedElasticBand(CI−NEB)法の両方を用いてグラフェンを通るプロトンの浸透について研究がなされてきたことをまず指摘する(S. P. Koenig, L. Wang, J. Pellegrino, J. S. Bunch,"Selective molecular sieving through porous graphene", Nat. Nanotechnol, 7, 728-732 (2012)、W. L. Wang, E. Kaxiras, "Graphene hydrate: Theoretical prediction of a new insulating form of graphene", New J. Phys. 12, 125012 (2010)および M. Miao, M. B. Nardelli, Q. Wang, Y. Liu, "First principles study of the permeability of graphene to hydrogen atoms", Phys. Chem. Chem. Phys., 15,16132-16137 (2013)参照)。これらの研究は、グラフェン中プロトン輸送障壁Eが約1.17eV〜2.21eVの範囲であると想定している。グラフェンについてのこれらの結果を再現し、モノレイヤhBNに拡大適用した。
本研究では、安定性および扱いの利便性によりNafionを材料として選択したが、本研究の結果の一般性を示すために、水溶液に浸漬させた2次元結晶のプロトン伝導率について調査した。これによっても、本発明のデバイスが、ある種の燃料電池および電気化学セルにみられるような液体環境でも動作することが示された。
Claims (15)
- 単結晶から形成された2次元材料のモノリシックな連続層と、
前記2次元材料の少なくとも片面に設けられたイオノマー被膜と、を具え、
前記2次元材料が、モノレイヤのグラフェン、及び、モノレイヤの及び2層のhBNからなる群から選択され、
前記2次元材料は、周期表の第8〜10族元素から選択された金属の不連続な被膜を有する、プロトン伝導膜。 - 前記イオノマーがプロトン伝導性ポリマーである、請求項1に記載の膜。
- 前記ポリマーがスルホン化ポリマーである、請求項2に記載の膜。
- 前記スルホン化ポリマーがNafionである、請求項3に記載の膜。
- 前記イオノマーが、前記2次元材料の片面に設けられるか、あるいは前記2次元材料の両面に設けられる、請求項1〜4のいずれか一項に記載の膜。
- 基体をさらに具える、請求項1〜5のいずれか一項に記載の膜。
- 前記イオノマーおよび基体が単一要素として設けられる、請求項6に記載の膜。
- プロトン伝導体としての請求項1〜7のいずれか一項に記載の膜の使用。
- 前記膜は、水素の分離装置に用いられる、請求項8に記載の使用。
- プロトンの濃度勾配は、前記2次元材料の異なる面間に存在する、請求項8又は9に記載の使用。
- 前記膜に電位が印加される、請求項8又は9に記載の使用。
- プロトンを他の材料から分離する方法であって、
該方法は、前記プロトンに、請求項1〜7のいずれか一項に記載の膜を通過される工程を含む、方法。 - プロトンの濃度勾配は、前記2次元材料の異なる面間に存在する、請求項12に記載の方法。
- 前記膜に電位が印加される、請求項13に記載の方法。
- 単結晶から形成された2次元材料のモノリシックな連続層を設ける工程であって、前記2次元材料が、モノレイヤのグラフェン、及び、モノレイヤの及び2層のhBNからなる群から選択された、工程と、
前記2次元材料の少なくとも片面をイオノマーで被覆して該イオノマーの片面が前記2次元材料と接触し、前記2次元材料の他方の面が露出するようにする工程、またはイオノマーおよび非導電性構成成分を含む材料の層を前記2次元材料の前記片面に塗布する工程のいずれかと、を含み、
前記2次元材料に、触媒金属の不連続な被膜を付与する工程であって、前記触媒金属は、周期表の第8〜10族元素から選択された、工程をさらに含む、請求項1〜7のいずれか一項に記載のプロトン伝導膜の作製方法。
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