Simon Bacon, Shumaila Babar, Matthew Dent, Allan Foster, Joseph Paul Baboo, Teng Zhang, John F. Watts and Constantina Lekakou
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引用次数: 0
摘要
本研究采用新型两相连续多孔模型拟合了极性电解质锂硫(Li-S)电池的反应动力学。连续两相模型考虑了液态电解质相和固态沉淀相的过程,其中锂+ 离子在溶剂软化固态中的扩散系数是通过分子动力学模拟确定的。溶解度实验得出了本研究采用的极性电解质中硫和硫化锂的饱和浓度。该模型描述了溶解的分子和离子物种在不同大小的孔隙中以溶解或去溶解的形式(取决于孔隙大小)进行的传输。本研究中的锂-S 反应模型针对 EC/DMC 中的 1 M LiPF6 电解质进行了验证。它包括阴极的七个氧化还原反应和两个循环非电化学反应,以及阳极的锂氧化还原反应。电化学反应假定发生在电解质溶液或固态中,循环反应假定只发生在液态电解质阶段。反应动力学参数的确定是通过将模型预测与循环伏安法周期的实验数据进行拟合,并结合操作中的紫外-可见光谱来实现的。
Reaction kinetics of lithium–sulfur batteries with a polar Li-ion electrolyte: modeling of liquid phase and solid phase processes
The present investigation fits the reaction kinetics of a lithium–sulfur (Li–S) battery with polar electrolyte employing a novel two-phase continuum multipore model. The continuum two-phase model considers processes in both the liquid electrolyte phase and the solid precipitates phase, where the diffusion coefficients of the Li+ ions in a solvent-softened solid state are determined from molecular dynamics simulations. Solubility experiments yield the saturation concentration of sulfur and lithium sulfides in the polar electrolyte employed in this study. The model describes the transport of dissolved molecular and ion species in pores of different size in solvated or desolvated form, depending on pore size. The Li–S reaction model in this study is validated for electrolyte 1 M LiPF6 in EC/DMC. It includes seven redox reactions and two cyclic non-electrochemical reactions in the cathode, and the lithium redox reaction at the anode. Electrochemical reactions are assumed to take place in the electrolyte solution or the solid state and cyclic reactions are assumed to take place in the liquid electrolyte phase only. The determination of the reaction kinetics parameters takes place via fitting the model predictions with experimental data of a cyclic voltammetry cycle with in operando UV-vis spectroscopy.
期刊介绍:
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