从理论上揭示了控制锂基聚合离子液体和玻璃中活性离子迁移率的因素
Theoretically Unveiling the Factors That Control Activated Ion Mobility in Lithium-Based Polymerized Ionic Liquids and Glasses.
摘要(中文译文)
理解离子在纯聚合物液体和玻璃态中的活化输运是材料、聚合物和物理化学领域的一个基础科学问题，且与多种储能应用高度相关。尤其值得关注的是基于阳离子的单离子导体，即“聚合离子液体”（PolyILs）。我们结合了多尺度结构、离子跳跃和聚合物链段动力学的微观统计力学理论的近期三项进展，以探讨结构关联、热力学状态以及阴离子-阳离子缔合强度如何决定离子输运的温度依赖性活化能垒及其与聚合物运动的耦合。关键在于一种新的映射方法，将分子复杂性映射到粗粒化模型，该模型编码了化学特异性的玻璃化转变温度、聚合物持续长度、玻璃化密度以及阴离子-阳离子吸引强度。本文给出了与具有三氟甲磺酰亚胺（TFSI）阴离子的PolyILs的可移动Li离子弛豫时间的定量比较，以及对具有较低玻璃化转变温度和库仑吸引力的理论设计模型的预测。新的核心结果包括：离子活化运动的启动需要临界库仑强度；基于温度依赖性有效阴离子-阳离子缔合能（该能量编码了聚合物柔性、库仑强度、温度和密度的变化）的跳跃速率在超过15个数量级上遵循主曲线。相关聚合物动力学涨落在促进离子跳跃中的重要作用得到了确立。
Abstract
Understanding the activated transport of ions in neat polymeric liquids and glasses is a fundamental scientific problem in materials, polymer, and physical chemistry, and it is highly relevant for diverse energy storage applications. Of special interest are cation-based single ion conductors, "polymerized ionic liquids" (PolyILs). We combine three recent advances in microscopic statistical mechanical theory for multiscale structure, ion hopping, and polymer segmental dynamics to address how structural correlations, thermodynamic state, and anion-cation association strength determine the temperature-dependent activation barrier for ion transport and its coupling with polymer motion. The key is a new mapping of molecular complexity to a coarse grained model that encodes the chemically specific glass transition temperature, , polymer persistence length, vitrification density, and anion-cation attraction strength. Quantitative comparisons with the mobile Li ion relaxation times of PolyILs with a Triflouromethane Sulfonimide (TFSI) anion, and predictions for a theoretically designed model with a lower and Coulomb attraction, are presented. New core results include a critical Coulomb strength being required for the onset of ion activated motion and a master curve over 15 decades of hopping rate based on a temperature-dependent effective anion-cation association energy that encodes variations of polymer flexibility, Coulomb strength, temperature, and density. The strong role of correlated polymer dynamical fluctuations in facilitating ion hopping is established.
如何引用
AMA
Ankita Das, Harmandeep Singh, Catalin Gainaru, Alexei P Sokolov, Kenneth S Schweizer. Theoretically Unveiling the Factors That Control Activated Ion Mobility in Lithium-Based Polymerized Ionic Liquids and Glasses.. ACS central science. 2026; doi:10.1021/acscentsci.6c00171.
APA
Ankita Das, Harmandeep Singh, Catalin Gainaru, Alexei P Sokolov, Kenneth S Schweizer (2026). Theoretically Unveiling the Factors That Control Activated Ion Mobility in Lithium-Based Polymerized Ionic Liquids and Glasses.. ACS central science. https://doi.org/10.1021/acscentsci.6c00171
GB/T 7714
Ankita Das, Harmandeep Singh, Catalin Gainaru, Alexei P Sokolov, Kenneth S Schweizer. Theoretically Unveiling the Factors That Control Activated Ion Mobility in Lithium-Based Polymerized Ionic Liquids and Glasses.[J]. ACS central science, 2026 doi:10.1021/acscentsci.6c00171.
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