基于疏水胍盐的新型高温燃料电池质子导电电解质

S. Rogalsky, O. Tarasyuk, V. Povazhnyi, T. Cherniavska, S. Makhno
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引用次数: 1

摘要

胍盐是一种很有前途的质子导体,因为在胍离子中含有大量的可解离质子,确保质子沿质子供体和质子受体位点形成的氢键网络有效转移。然而,大多数胍盐的高熔点是其作为质子导电电解质应用的一个严重缺陷。通过在烷基自由基上取代氢原子来降低胍离子的对称性,降低了熔点,但也导致质子电导率降低。本研究采用简单的两步法合成了单取代胍盐n -丁基胍双(三氟甲基磺酰基)亚胺(BG-TFSI)。它是一种室温不与水混溶的质子离子液体。核磁共振波谱和红外波谱证实了BG-TFSI的结构。热重分析数据表明,该离子液体的热降解点(失重5%)为348℃,表明其具有良好的热稳定性,可用于高温燃料电池。电化学阻抗法测得BG-TFSI在室温下的离子电导率为9·10-4 S/cm。该值在100°C以上几乎增加了一个数量级,从而达到燃料电池使用的可接受水平。根据阿伦尼乌斯图计算出BG-TFSI的活化能Ea为16.4 kJ/mol,与其他胍盐的活化能相似。根据所获得的结果,可以假设BG-TFSI中的质子输运以grotthus型(跳跃)机制为主。研究结果表明,BG-TFSI是一种很有前途的质子导电电解质,可用于无水条件下的高温燃料电池。离子液体的疏水性是一个重要的优势,因为它可以防止其在燃料电池运行过程中从聚合物电解质膜中浸出。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
New promising proton conducting electrolyte for high-temperature fuel cells based on hydrophobic guanidine salt
Guanidine salts are promising proton conductors due to the high content of dissociable protons in guanidinium cation that ensure an efficient proton transfer along hydrogen-bonded network formed by proton donor and proton acceptor sites. However, the high melting point of most guanidine salts is a serious drawback for their application as proton conducting electrolytes. Reducing the symmetry of guanidinium cations by the substitution of hydrogen atoms on alkyl radicals reduces the melting points but also leads to decreased proton conductivity. In this study, monosubstituted guanidine salt, N-butylguanidinium bis(trifluoromethylsulfonyl)imide (BG-TFSI), has been synthesized by a simple two-step method. It is water immiscible room temperature protic ionic liquid. The structure of BG-TFSI was confirmed by nuclear magnetic resonance spectroscopy, as well as infrared spectroscopy. According to thermal gravimetric analysis data, the ionic liquid has the thermal degradation point (5% weight loss) of 348 °C which indicates its excellent thermal stability for use in high-temperature fuel cells. The ionic conductivity of BG-TFSI determined by the electrochemical impedance method was found to be 9·10-4 S/cm at room temperature. This value increased by almost one order of magnitude above 100 °C thus reaching an acceptable level for use in fuel cells. The activation energy Ea calculated from the Arrhenius plot for BG-TFSI is found to be 16.4 kJ/mol which is similar to those reported for other guanidine salts. Based on the obtained results one can assume that the proton transport in BG-TFSI is dominated by Grotthus-type (hopping) mechanism. The results of this study indicated that BG-TFSI is a promising proton conducting electrolyte for fuel cells operating at elevated temperatures in water-free conditions. The hydrophobicity of the ionic liquid is an important advantage since it can prevent its leaching from the polymer electrolyte membrane during the operation of a fuel cell.
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