JP2021519843A - アニオン交換膜並びにその製造方法及び使用方法 - Google Patents
アニオン交換膜並びにその製造方法及び使用方法 Download PDFInfo
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Abstract
Description
本願は、米国特許法第119条(e)の下で、2018年3月27日出願の米国仮特許出願第62/648,508号及び2018年8月16日出願の米国仮特許出願第62/764,912号明細書の利益を主張するものであり、その両方は、それらの全体が参照によって本明細書中に組み込まれる。
本発明は、アメリカ合衆国エネルギー省によって授与された認可番号DE−AR0000769の下で政府支援を受けた。政府は本発明においてある一定の権利を有する。
R2及びR3は、独立して、H、結合(結合であるとは何を意味するかは定かでない)、及び分岐状若しくは非分岐状の飽和C1〜C20アルキル又はハロゲン化アルキル鎖から選択され、
xは、約10〜約1,000の整数である。
R4は、分岐状又は非分岐状の飽和C1〜C20アルキル鎖であり、
R1は、分岐状又は非分岐状の飽和C2〜C20アルキル鎖であり、
Xは、カチオン荷電のヘテロ原子を含むカチオン性ヘッド基(例えば、+N(CH3)2)であり、
R5は、分岐状又は非分岐状の飽和C2〜C10アルキル鎖を含む架橋剤であり、
n、m、o、及びpは、約10〜約1,000から独立して選択される整数である。
R4は、分岐状又は非分岐状の飽和C1〜C20アルキル鎖であり、
R1は、分岐状又は非分岐状の飽和C2〜C20アルキル鎖であり、
Xは、カチオン荷電のヘテロ原子を含むカチオン性ヘッド基(例えば、+N(R)2)であり、ここで、Rは、分岐状又は非分岐状のC1〜C10アルキル鎖(例えば、−CH3)である、
R5は、分岐状又は非分岐状の飽和C2〜C10アルキル鎖を含む架橋剤であり、
n、m、o、及びpは、約1〜約1,000から独立して選択される整数である。
以下の実施例は、本明細書において特許請求される化合物、組成物、物品、デバイス及び/又は方法がどのように製造され、評価されるかについての完全な開示及び説明を当業者に提供するように記載され、本発明を純粋に例示することを企図され、本発明者等が本発明者等の本発明とみなすものの範囲を制限することを企図されない。しかしながら当業者は、開示される具体的な実施態様に多くの変更が加えられることを、本開示に照らして理解するはずであり、その上で、本発明の趣旨及び範囲から逸脱することなく同様の又は類似の結果を得ることができる。
ノルボルネンのビニル付加重合に基づくアニオン性マルチブロックコポリマー膜:アニオン交換膜燃料電池における適用
材料:1−ヘキセン、5−ブロモ−1−ペンテン及びジシクロペンタジエンは、Alfa Aesarから購入され、受け取ったまま使用された。モノマーであるブチルノルボルネン(BuNB)及びブロモプロピルノルボルネン(BPNB)は、公開手順に従って、高温でディールス−アルダー反応によって合成された(Martinez-Arranz, S. et al., Macromolecules 43 (2010) 7482-7487)。重合の前に、モノマーは、ナトリウム上で蒸留することによって精製され、3回の凍結脱気サイクルによって脱気された。全ての重合反応は、グローブボックス内で、乾燥アルゴン雰囲気下で湿気及び空気が入らないように厳重に注意しながら実施された。トルエンは、ナトリウム及びベンゾフェノン上で6時間加熱還流させることによって乾燥させられた。トルエンは、使用前に新しく蒸留された。トリイソプロピルホスフィン及び[(η3−アリル)Pd(Cl)]2は、Sigma−Aldrichから購入され、受け取ったまま使用された。触媒である(アリル)パラジウム(トリイソプロピルホスフィン)クロリド((η3−アリル)Pd(iPr3P)Cl)は、既に公開されている報告に従って調製された(Lipian, J. et al., Macromolecules 35 (2002) 8969-8977)。リチウムテトラキス(ペンタフルオロフェニル)−ボレート・(2.5Et2O)(Li[FABA])は、Boulder Scientific Co.から購入され、受け取ったまま使用された。α,α,α−トリフルオロトルエン(TFT)、無水、≧99%及びテトラヒドロフラン(THF)は、Sigma−Aldrichから購入され、受け取ったまま使用された。
架橋ポリ(ノルボルネン)に基づく高伝導性アニオン交換膜:ビニル付加重合
燃料電池は、化石燃料の使用を低減する潜在可能性を有する、クリーンなエネルギー変換技術である(Mekhilef, S. et al., Renewable Sustainable Energy Rev. 2012, 16, 981-989)。燃料電池は、固定発電、携帯式電子機器、及び輸送に使用されることができる(Carrette, L. et al., Fuel Cells 2001, 1, 5-39;Winter, M. et al., Chem. Rev. 2004, 104, 4245-4269)。更に、燃料電池は、環境に優しく、燃料補給されやすく、高エネルギー変換効率を有することができる(Steele, B. C. et al., Nature 2001, 414, 345-352)。固体高分子電解質膜、例えばアニオン交換膜(AEM)及びプロトン交換膜(PEM)、は、液体電解質デバイスのように液体/気体圧のバランスが保たれる必要がないので、三相境界を有する電極の製造を簡素化する。高pHのAEMは、酸伝導PEMと比較して容易な酸素反応動態を有し、非貴金属触媒の使用機会を提供し、燃料クロスオーバーを低減する(Varcoe, J. R. et al., Energy Environ. Sci. 2014, 7, 3135-3191;Lu, S. et al., Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 20611-20614;Yu, E. H. et al., Energy Environ. Sci. 2012, 5, 5668-5680;Hickner, M. A. et al., J. Polym. Sci. Part B: Polym. Phys. 2013, 51, 1727-1735;Zhou, J. et al., J. Electrochem. Soc. 2013, 160, F573-F578)。しかしながら、初期の膜は、低いイオン伝導率、高pHでの低い化学的安定性、及び高い水の取り込みに悩まされた(Mohanty, A. D. et al., J. Mater. Chem. A 2014, 2, 17314-17320;Liu, L. et al., J. Mater. Chem. A 2016, 4, 16233-16244;Mandal, M. et al., J. Membr. Sci. 2019, 570-571, 394-402;Mohanty, A. D. et al., J. Electrochem. Soc. 2017, 164, F1279-F1285)。より最近になって、Argesによって総説される通り、数人の研究者によってより高い伝導率(例えば、80℃で100mS/cm)及び化学的安定性(1MのNaOH中、80℃における)が達成された(Arges, C. G. et al. ACS Appl. Energy Mater. 2018, 1, 2991-3012)。この著しい進歩は、過去のAEMの欠陥に対処する為に、ある特定の構造部分が使用されることができるということを示している。
架橋ポリ(ノルボルネン)に基づく高伝導性アニオン交換膜:開環メタセシス重合
様々なモノマーがディールス−アルダー反応によって合成されることができるので、ポリ(ノルボルネン)は、AEMの魅力的なポリマー骨格である(Yang, Z. et al., Polymer 2008, 49, 5128-5136)。ノルボルネンモノマーの低分子量は、高IECを可能にする。ノルボルネンは、ビニル付加重合又は開環メタセシス重合(ROMP)によって重合化されることができる。Coates等は、20℃で18mS/cmの水酸化物イオン伝導率及び1.4meq/gのIECを有するAEMを合成する為に、ジシクロペンタジエン及びテトラアルキルアンモニウム官能化ノルボルネンのROMPを行った(Clark, T. J. et al., J. Am. Chem. Soc. 2009, 131, 12888-12889)。ポリマーは、ビス(ターピリジン)Ru(II)複合体を使用して、金属カチオンに基づく経路を介して架橋された。得られた水酸化物イオン伝導率は、30℃で28.6mS/cmであり、IECは1.4meq/gであった(Zha, Y. et al., J. Am. Chem. Soc. 2012, 134, 4493-4496;Wang, C. et al., J. Membr. Sci. 2018, 556, 118-125)。伝導率を増大する研究では、IECが増大され、その特性を増強する為に架橋が導入された。Wang等は、2.89meq/gのIECを有し、その結果25℃で64.79mS/cmの水酸化物イオン伝導率を有するアルキル架橋AEMを報告したが、長期的アルカリ安定性は示されなかった。2.79meq/gのIEC及び30℃で40mS/cmのOH−伝導率を有するジフェニルオキシド架橋AEMは、材料の脆さと共に、低いアルカリ安定性を有していた(2MのNaOHに50℃で16日間浸漬させた後、34%の伝導率喪失)(Wang, C. et al., Macromol. Mater. Eng. 2018, 303, 1700462)。エーテル連結及び可撓性テザーを有する別の水素化ポリ(ノルボルネン)膜が、Price等によって調製された(Price, S. C. et al., Polym. Chem. 2017, 8, 5708-5717)。得られた伝導率は、20℃で69mS/cmであり、80℃で133mS/cmであった。しかしながら、0.1MのNaOHに90℃で239時間浸した後、伝導率は約50%低減した。要約すると、ROMPによって調製されたポリ(ノルボルネン)に基づく最先端のAEMは、一般に伝導率が低く、且つ/又は長期的アルカリ安定性が低かった。
3.4W/cm2のアルカリポリマー燃料電池の達成:高い出力、耐久性及び水の管理の為の複合架橋ポリ(ノルボルネン)アニオン伝導性膜
固体ポリマー電解質を使用するエネルギー変換デバイス、例えば燃料電池及び電解槽、は、高い熱力学的効率を有し、固体状態で設計されるので、クリーンエネルギーの生成及び保管に有望な選択肢である(Steele, B. C. et al., Nature 2001, 414, 345)。これらのデバイスは、拡張可能でもあり、電力の輸送、遠隔及び分散、並びに電気及び水素生成の為の大規模施設の為に使用されることができる。
Claims (42)
- ノルボルネンに基づく1以上の親水性ブロックと1以上の疎水性ブロックとを含むマルチブロックコポリマー。
- 前記1以上の疎水性ブロックが、ノルボルネンに基づく疎水性ブロック及びアルケンに基づく疎水性ブロックから選択される、請求項1に記載のマルチブロックコポリマー。
- R1が、C4〜C10のアルキル鎖である、請求項3に記載のマルチブロックコポリマー。
- 前記カチオン性ヘッド基が、第四級アンモニウムヘッド基(例えば、−+N(R)3)であり、ここで、Rは、分岐状又は非分岐状の飽和C1〜C10アルキル鎖(例えば、−CH3)である、請求項6に記載のマルチブロックコポリマー。
- 前記カチオン性ヘッド基が、末端第四級アンモニウムヘッド基(例えば、−+N(R)3)であり、ここで、Rは、分岐状又は非分岐状の飽和C1〜C10アルキル鎖(例えば、−CH3)である、請求項5又は6に記載のマルチブロックコポリマー。
- R4が、飽和のC3又はC4アルキル鎖である、請求項6〜8のいずれか1項に記載のマルチブロックコポリマー。
- 前記コポリマーが2〜8個のブロックを含む、請求項1〜9のいずれか1項に記載のマルチブロックコポリマー。
- 前記コポリマーが4個のブロックを含む、請求項1〜10のいずれか1項に記載のマルチブロックコポリマー。
- 前記1以上の疎水性ブロックのモルパーセントが約30%〜約40%である、請求項1〜11のいずれか1項に記載のマルチブロックコポリマー。
- 前記親水性ブロックのモルパーセントが約60%〜約70%である、請求項1〜12のいずれか1項に記載のマルチブロックコポリマー。
- 前記疎水性ブロックのモルパーセントが約10〜約30%である、請求項1〜13のいずれか1項に記載のマルチブロックコポリマー。
- 前記1以上の親水性ブロックのモルパーセントが約70〜約90%である、請求項1〜14のいずれか1項に記載のマルチブロックコポリマー。
- 請求項1〜15のいずれか1項に記載のマルチブロックコポリマーを含むアニオン交換膜(AEM)。
- 前記1以上の親水性ブロックが、架橋剤で架橋されている、請求項18に記載のAEM。
- 前記架橋剤が、分岐状又は非分岐状の飽和C2〜C10アルキル鎖である、請求項17に記載のAEM。
- 前記架橋剤が、飽和C6アルキル鎖である、請求項18に記載のAEM。
- 前記架橋剤が、分岐状又は非分岐状の飽和C2〜C10アルキル鎖を含むアルキルジアミンテザーである、請求項17〜19のいずれか1項に記載のAEM。
- 前記架橋剤が、少なくとも2個のアミン官能基を有する分岐状又は非分岐状の飽和C2〜C10アルキル鎖を含むマルチアミンアルキルテザーである、請求項17〜20のいずれか1項に記載のAEM。
- 前記マルチブロックコポリマー内の前記1以上の親水性ブロックの1以上のカチオン性ヘッド基が、前記架橋剤を介して互いに架橋されている、請求項17〜21のいずれか1項に記載のAEM。
- 架橋剤の濃度が、約5モル%〜50モル%である、請求項17〜22のいずれか1項に記載のAEM。
- 安定剤をさらに含む、請求項17〜24のいずれか1項に記載のAEM。
- 前記安定剤が、パーフッ素化されたテトラフルオロエチレン(PFTE)又はポリオレフィン(PO)である、請求項25に記載のAEM。
- 1以上のアニオン伝導チャネルを含む、請求項17〜26のいずれか1項に記載のAEM。
- 約10〜約500MPaの引張強度を有する、請求項17〜27のいずれか1項に記載のAEM。
- 約10%〜約200%の破断パーセンテージを有する、請求項17〜28のいずれか1項に記載のAEM。
- 約0.005〜約1GPaのヤング率を有する、請求項17〜29のいずれか1項に記載のAEM。
- 約1.5〜約4.5meq./gのイオン交換能を有する、請求項17〜30のいずれか1項に記載のAEM。
- 80℃で、約35〜約250mS/cmの水酸化物イオン伝導率を有する、請求項17〜31のいずれか1項に記載のAEM。
- 約10%〜約70%の水の取り込みパーセンテージを有する、請求項17〜32のいずれか1項に記載のAEM。
- 約6〜約30の水和数λを有する、請求項17〜33のいずれか1項に記載のAEM。
- ビニル付加重合を含む、請求項1〜16のいずれか1項に記載のマルチブロックコポリマーを製造する方法。
- 開環メタセシス重合(ROMP)を含む、請求項1〜17のいずれか1項に記載のコポリマー組成物を製造する方法。
- 請求項1〜16のいずれか1項に記載のマルチブロックコポリマー中の1以上の親水性ブロックを、1以上の架橋剤で架橋することを含む、架橋されたマルチブロックコポリマーを製造する方法。
- 前記架橋剤が、少なくとも2個のアミン官能基を有する分岐状又は非分岐状の飽和C2〜C10アルキル鎖を含むマルチアミンアルキル鎖である、請求項37に記載の方法。
- 前記架橋剤が、分岐状又は非分岐状の飽和C2〜C10アルキル鎖を含むアルキルジアミンである、請求項37又は38に記載の方法。
- 請求項1〜16のいずれか1項に記載のマルチブロックコポリマー及び/又は請求項17〜37のいずれか1項に記載のアニオン交換膜アニオン交換膜(AEM)を含むデバイス。
- 電気化学的デバイスである、請求項40に記載のデバイス。
- 前記電気化学的デバイスが、燃料電池、電解槽、及びレドックスフロー電池から選択される、請求項41に記載のデバイス。
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