Pranti Nazifa Jahan, Faraezi Sharifa, Ohba Tomonori, Karatrantos Argyrios V, Khan Md Sharif
Center for Interdisciplinary Chemistry Research (CICR) Dhaka Bangladesh
Graduate School of Science, Chiba University 1-33 Yayoi, Inage Chiba 263-8522 Japan.
RSC Adv. 2025 Apr 7;15(14):10851-10860. doi: 10.1039/d5ra00757g. eCollection 2025 Apr 4.
This study investigates the interplay between organic solvent geometry and divalent cation dynamics in liquid electrolytes, emphasizing their relevance for energy storage systems. Using classical molecular dynamics simulations, the structural and transport properties of Mg and Ca were evaluated in cyclic (ethylene carbonate, EC; propylene carbonate, PC) and linear (ethyl methyl carbonate, EMC) solvents in the presence of TFSI anions across a range of temperatures. The results reveal that Mg exhibits superior diffusion compared to Ca due to its smaller ionic radius and weaker ion-pair interactions. Diffusion increases with temperature, following the solvent trend EC > EMC > PC. Coordination analysis showed compact solvation shells for both cations, with Ca forming denser structures and demonstrating higher residence times compared to Mg. Solvent geometry significantly influenced solvation dynamics, with cyclic solvents enhancing ion coordination and linear solvents reducing solvation due to steric hindrance. These findings underscore the critical role of solvent structure and ion dynamics in optimizing divalent-ion battery performance, positioning Mg as a promising candidate for sustainable energy storage solutions.
本研究调查了液体电解质中有机溶剂几何结构与二价阳离子动力学之间的相互作用，强调了它们对储能系统的相关性。使用经典分子动力学模拟，在一系列温度下，在存在双（三氟甲基磺酰）亚胺（TFSI）阴离子的情况下，评估了镁（Mg）和钙（Ca）在环状（碳酸亚乙酯，EC；碳酸亚丙酯，PC）和线性（碳酸甲乙酯，EMC）溶剂中的结构和传输性质。结果表明，由于其较小的离子半径和较弱的离子对相互作用，Mg比Ca表现出更好的扩散性能。扩散随温度升高而增加，遵循溶剂趋势EC > EMC > PC。配位分析表明，两种阳离子都有紧密的溶剂化壳层，与Mg相比，Ca形成更致密的结构并表现出更长的停留时间。溶剂几何结构显著影响溶剂化动力学，环状溶剂增强离子配位，而线性溶剂由于空间位阻减少溶剂化。这些发现强调了溶剂结构和离子动力学在优化二价离子电池性能中的关键作用，使Mg成为可持续储能解决方案的有前途的候选者。
