Pyrrolidinium-based organic ionic plastic crystals: Relationship between side chain length and properties
Pyrrolidinium-based organic ionic plastic crystals: Relationship between side chain length and properties
复制标题
吡咯烷鎓基有机离子塑料晶体：侧链长度与性能的关系
DOI：
10.1016/j.electacta.2019.02.076
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发表时间：
2019
影响因子：
6.6
通讯作者：
Yoshizawa-Fujita Masahiro
中科院分区：
文献类型：
--
作者：
Yamada Hiromasa;Miyachi Yukari;Takeoka Yuko;Rikukawa Masahiro;Yoshizawa-Fujita Masahiro
有机离子塑料晶体(OIPC)因其良好的不燃性、可塑性和离子导电性而被作为固体电解质进行研究。然而，它们的导电塑料晶相的温度范围较窄。我们以前报道过N-乙基-N-甲基吡咯烷双(氟磺酰基)酰胺([C2mpyr][FSA])在室温下表现出较宽的塑性结晶行为和较高的离子电导率。本文研究了吡咯烷的侧链结构与其与FSA形成的化合物的物理化学性质之间的关系。引入两个乙基后，N，N-二乙基吡咯烷胺([C2epyr][FSA])在保持足够的塑性晶相温度范围的同时，表现出比[C2mpyr][FSA]更高的离子电导率。在[C2epyr][FSA]中加入5 摩尔%的LiFSA，进一步提高了[C2epyr][FSA]的离子电导率。对于复合了5 %LiFSA的[C2epyr][FSA]，在60 °C下测得锂的迁移数为0.27 。在循环伏安测量中，在镍电极上观察到可逆的锂电镀/剥离反应。具有较长烷链的对称吡咯烷阳离子(最多两个碳)在较宽的温度范围内显示出导电的塑料固相，并具有较高的锂迁移数。
Organic ionic plastic crystals (OIPCs) have been studied as solid-state electrolytes because of their desirable properties such as non-flammability, plasticity, and ionic conductivity. However, the temperature range of their conductive plastic crystal phase is narrow. We previously reported thatN-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)amide ([C2mpyr][FSA]) exhibited a wide temperature range of plastic crystal behavior and high ionic conductivity at room temperature. In this study, the relationship between the side chain structure of pyrrolidinium and the physicochemical properties of their compounds with FSA was investigated. With two introduced ethyl groups,N,N-diethylpyrrolidinium bis(fluorosulfonyl)amide ([C2epyr][FSA]) showed higher ionic conductivity than [C2mpyr][FSA], while maintaining a sufficient temperature range of plastic crystal phase. The ionic conductivity of [C2epyr][FSA] was further improved by the addition of 5 mol% LiFSA. For the [C2epyr][FSA] composited with 5 mol% LiFSA, the lithium transference number was determined to be 0.27 at 60 °C. Reversible lithium plating/stripping reaction was observed on a Ni electrode in the CV measurement. Symmetric pyrrolidinium cation with a longer alkyl chain (up to two carbons) showed conductive plastic solid phase in a wide temperature range and a higher lithium transference number.