Molecular dynamics simulation to reveal the transport mechanism of LiPF6 in ethylene carbonate plus dimethylcarbonate binary solvent

T Kiyobayashi and S Uchida and H Ozaki and K Kiyohara, JOURNAL OF CHEMICAL PHYSICS, 159, 074501 (2023).

DOI: 10.1063/5.0164099

This paper presents the molecular dynamics simulation of 1 mol kg(-1) LiPF6 in a binary solvent of ethylene carbonate (EC) and dimethylcarbonate, which is a representative electrolyte solution for lithium-ion batteries. The simulation successfully reproduced the diffusion coefficient, ionic conductivity, and shear viscosity as functions of EC content at 300 K, which had been experimentally determined in our previous study. The Yukawa potential was adopted to model intercharge interactions to reduce computational costs, which consequently allowed us to precisely calculate the conductivity and viscosity by directly integrating time-correlation functions without explicitly modeling the molecular polarization. Breaking down microscopic current correlation functions into components revealed that, whereas the cation-anion attractive interaction dominantly impedes the conduction when the EC content is low, it is the cation-cation and anion-anion repulsive interactions that reduce the conductivity at a high EC content. An analysis of the pressure correlations revealed that all components positively contribute to the viscosity in the binary solvent without the electrolyte. On the other hand, negative terms are observed in five out of six cross correlations in the presence of the electrolyte, implying that these correlations negatively contribute to the shear stress and entropy production, both of which are net positive.

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