Exploring structural and dynamical properties of polymer-ionic liquid ternary electrolytes for sodium ion batteries

This work investigates the ion transport mechanisms in binary and ternary electrolyte systems based on polymers and ionic liquids for Na-ion batteries. Molecular dynamics (MD) simulations were performed on poly(ethylene oxide) (PEO) and ionic liquids (IL) based electrolytes, bis(trifluoromethanesulfonyl)imide (TFSI)/N-methyl-N-propylpyrrolidinium (Pyr13) and bis(fluorosulfonyl)imide (FSI)/Pyr13, varying the composition at 0, 5, 10 and 20 wt% over a range of temperatures from 313 to 400 K. The simulations could satisfactorily reproduce the experimental densities and trends in diffusivities and conductivity data. It was observed that there exists a stronger interaction between sodium ions and the FSI anions as compared to the TFSI counterparts, correlated to a difference in interaction energy between the ionic species. This controls how well the different ILs act as plasticizers for the Na-PEO system, with TFSI actually displaying lower conductivity for low IL loadings while the conductivity increases continuously for the FSI counterparts. Moreover, the simulations show that the sodium ions interact more strongly with the polymer at lower temperatures, leading to a lower polymer free volume which explains the trends in ionic transport. Thereby, these MD simulations unveil an interplay between the coordination chemistry and the dynamic properties in these ternary polymer-ionic liquid-salt electrolytes, and how the coordination strength controls the conductive properties.