We present a theoretical study combining molecular dynamics (MD) simulations with an analytical lithium ion transport model [Maitra and Heuer, Phys. Rev. Lett. 2007, 98, 227802] to highlight a novel strategy to increase the lithium mobility in polymer electrolytes based on poly(ethylene oxide) (PEO). This is achieved by using a pyrrolidinium-based ionic liquid (IL) where the cation has been chemically functionalized by a short oligoether side chain [von Zamory et al., Phys. Chem. Chem. Phys. 2016, 18(31), 21539] as an additive. Since the oligoether moieties at the pyrrolidinium cations form pronounced coordinations to the lithium ions for sufficiently long side chains, the ions can be detached from the PEO backbone. In this way, a fundamentally new lithium ion transport mechanism is established (shuttling mechanism), in which the lithium dynamics is decoupled from the polymer dynamics, the latter typically being slow under experimental conditions. Based on our simulations, we incorporate this novel mechanism into our existing model, which accurately reproduces the observed lithium dynamics. We demonstrate that the use of oligoether-functionalized IL additives significantly increases the lithium diffusivity. Finally, we show that for experimentally relevant electrolytes containing long polymer chains, an even stronger increase of the lithium mobility can be expected. © The Author(s) 2017. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/2.0271711jes] All rights reserved.

中文翻译：

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通过功能化离子液体添加剂改善聚合物电解质中的锂离子传输：模拟和建模

我们提出了一项将分子动力学 (MD) 模拟与分析锂离子传输模型相结合的理论研究 [Maitra and Heuer, Phys. 牧师莱特。2007, 98, 227802] 强调了一种提高基于聚（环氧乙烷）（PEO）聚合物电解质中锂迁移率的新策略。这是通过使用基于吡咯烷鎓的离子液体 (IL) 实现的，其中阳离子已被短的低聚醚侧链化学官能化 [von Zamory 等人，Phys. 化学 化学 物理。2016, 18(31), 21539] 作为添加剂。由于吡咯烷鎓阳离子处的低聚醚部分与足够长的侧链的锂离子形成明显的配位，离子可以从 PEO 主链上分离。这样，从根本上建立了一种全新的锂离子传输机制（穿梭机制），其中锂动力学与聚合物动力学分离，后者在实验条件下通常很慢。基于我们的模拟，我们将这种新颖的机制纳入我们现有的模型中，该模型准确地再现了观察到的锂动力学。我们证明了使用低聚醚功能化的 IL 添加剂显着增加了锂的扩散率。最后，我们表明，对于含有长聚合物链的实验相关电解质，可以预期锂迁移率的增加甚至更大。© The Author(s) 2017. 由 ECS 出版。这是一篇根据知识共享署名 4.0 许可（CC BY，http://creativecommons.org/licenses/by/4.0/）条款分发的开放获取文章，它允许在任何媒体中不受限制地重复使用作品，只要原著被正确引用。[DOI: 10.1149/2.0271711jes] 版权所有。