Design of Highly Conductive PILs by Simple Modification of Poly(epichlorohydrin-co-ethylene oxide) with Monosubstituted Imidazoles

IF 4.7 Q1 POLYMER SCIENCE
Daniil R. Nosov, Elena I. Lozinskaya, Dmitrii Y. Antonov, Denis O. Ponkratov, Andrey A. Tyutyunov, Malak Alaa Eddine, Cédric Plesse, Daniel F. Schmidt* and Alexander S. Shaplov*, 
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引用次数: 0

Abstract

High ionic conductivity poly(ionic liquid)s (PILs) are of growing interest for their thermal and electrochemical stability, processability, and potential in safe, flexible all-solid-state electrochemical devices. While various approaches to enhance the ionic conductivity are reported, the influence of cation substituents is rarely addressed. Moreover, some of the asymmetric anions recently developed for high-conductivity ionic liquids were never tested in PILs. We report the design and synthesis of twelve novel cationic PILs prepared via quaternization of N-substituted imidazoles by commercially available poly(epichlorohydrin-co-ethylene oxide) (poly(EPCH-r-EO)) with subsequent ion metathesis. They differ by imidazolium side chain length (C1–C6 alkyl) and presence of heteroatoms (silyl, siloxane, and fluoroalkyl) and by anion type (bis(trifluoromethylsulfonyl)imide (TFSI), 2,2,2-trifluoromethylsulfonyl-N-cyanoamide (TFSAM), tetrafluoroborate (BF4), trifluoro(trifluoromethyl)borate (BF3CF3), and tricyanofluoroborate (BF(CN)3)). TFSI-based PILs with alkyl side chains gave lower glass transition temperatures (Tg) and higher ionic conductivities than those bearing heteroatomic substituents, with n-butyl side chains providing a conductivity of 4.7 × 10–6 S cm–1 at 25 °C under anhydrous conditions. This increased to 1.0 × 10–5 and 4.5 × 10–4 S cm–1 at 25 and 70 °C, respectively, when the TFSI anion was replaced with BF(CN)3. All PILs showed good electrochemical (>3.2 V vs Ag+/Ag) and thermal (>185 °C) stability, making them excellent candidates for solid-state electrolytes in electrochemical devices.

单取代咪唑对聚环氧氯丙烷-环氧乙烷的简单改性设计高导电性药粒
高离子电导率的聚离子液体(pil)因其热稳定性、电化学稳定性、可加工性以及在安全、柔性全固态电化学器件中的潜力而日益受到人们的关注。虽然有各种提高离子电导率的方法被报道,但阳离子取代基的影响很少得到解决。此外,最近开发的一些用于高导电性离子液体的不对称阴离子从未在pil中进行过测试。本文报道了用市售聚(环氧氯丙烷-环氧乙烷)(聚(EPCH-r-EO))对n-取代咪唑进行季铵盐化制备的12种新型阳离子吡啶醇的设计和合成。它们的区别在于咪唑侧链长度(C1-C6烷基)和是否存在杂原子(硅氧烷、硅氧烷和氟烷基)以及阴离子类型(二(三氟甲基磺酰基)亚胺(TFSI)、2,2,2-三氟甲基磺酰基- n -氰酰胺(TFSAM)、四氟硼酸盐(BF4)、三氟(三氟甲基)硼酸盐(BF3CF3)和三氰氟硼酸盐(BF(CN)3)))。与杂原子取代基相比,带有烷基侧链的tfsi基pls具有更低的玻璃化转变温度(Tg)和更高的离子电导率,其中正丁基侧链在25℃无水条件下的电导率为4.7 × 10-6 S cm-1。用BF(CN)3代替TFSI阴离子后,在25°C和70°C温度下,分别增加到1.0 × 10-5和4.5 × 10-4 S cm-1。所有pil均表现出良好的电化学稳定性(>3.2 V vs Ag+/Ag)和热稳定性(>185℃),使其成为电化学器件中固态电解质的优秀候选者。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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CiteScore
2.50
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