低相对湿度下质子交换膜燃料电池中的全氟磺酰亚胺与全氟磺酸离聚物。,ChemSusChem

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低相对湿度下质子交换膜燃料电池中的全氟磺酰亚胺与全氟磺酸离聚物。
ChemSusChem ( IF 7.5 ) Pub Date : 2020-01-07 , DOI: 10.1002/cssc.201902875
Huu-Dat Nguyen ₁ , Regis Porihel ₂ , Jean-Blaise Brubach ₂ , Emilie Planes ₁ , Priscillia Soudant ₁ , Patrick Judeinstein ₃ , Lionel Porcar ₄ , Sandrine Lyonnard ₅ , Cristina Iojoiu ₁

Affiliation

在质子交换膜燃料电池中，在高温和低相对湿度下设计高导电性离聚物是一项挑战。由于全氟磺酰基酰亚胺离聚物具有出色的酸度和出色的热稳定性，因此被认为可以实现这一目标。尽管具有相似的膜微结构，但全氟磺酰基酰亚胺离聚物的导电性低于类似的全氟磺酸。在这项研究中，通过水合作用的原位同步加速器红外光谱分析可以合理化独特的行为。对于两个不同的膜家族，质子化机理，质子部分的形成和水团簇完全不同。由全氟磺酰基酰亚胺离聚物的反式至顺式构象转变介导的电离不伴随有水合氢离子的形成。相比之下，Zundel离子实体被确定为基本质子复合物，在水合作用范围内稳定。周围水分子的H键网络似乎连接较少，质子仍保持高度局部化，无法进行有效的结构传输。质子的离域及其与周围介质的相互作用减弱是对电导率产生负面影响的显着影响。

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Perfluorosulfonyl Imide versus Perfluorosulfonic Acid Ionomers in Proton-Exchange Membrane Fuel Cells at Low Relative Humidity.

Designing highly conductive ionomers at high temperature and low relative humidity is challenging in proton-exchange membrane fuel cells. Perfluorosulfonyl imide ionomers were believed to achieve this goal, owing to their exceptional acidity and excellent thermal stability. Perfluorosulfonyl imide ionomers are less conductive than the analogous perfluorosulfonic acids despite similar membrane microstructure. In this study, the distinct behavior is rationalized by in situ synchrotron infrared spectroscopy during hydration. The protonation mechanism, formation of the protonic moiety and water clustering are totally different for the two different families of membranes. The ionization mediated by trans-to-cis conformational transition of the perfluorosulfonyl imide ionomer is not accompanied by the formation of hydronium ions. In contrast, Zundel-ion entities were identified as the elementary protonic complex, which is stable over the hydration range. The H-bond network of surrounding water molecules appears to be less connected and the protons remain highly localized and unavailable for efficient structural transport. The delocalization of protons and their mitigated interaction with the surrounding medium are prominent effects that negatively impact conductivity.

更新日期：2020-01-07

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