Molecular dynamics study on lithium‐ion transport in PEO branched nanopores with PYR14TFSI ionic liquid

Abstract Lithium ion transport in a poly‐(ethylene oxide) (PEO) branched nanopore filled with a solution of [lithium][bis(trifluoromethanesulfonyl)imide]/[1‐butyl‐1‐methylpyrrolidinium][bis(trifluoromethanesulfonyl)imide] (LiTFSI/PYR14TFSI) was investigated by molecular dynamics using many‐body polarizable force field. The structural and dynamic properties of lithium ions in the nanopores with different sizes and ratios of ions to PEO chains were examined. The first coordination shell of the lithium ions had a lower intensity in the longitudinal direction than in the radial direction. Cluster analysis of [Lix(TFSI)n]−(n−x)showed the absence of large lithium clusters (x ≥ 2) as a result of the enhanced suppression of monodentate structures compared with binary electrolytes (i.e., LiTFSI/PYR14TFSI without PEO chains). The emergence of [Li(TFSI)2]−and its relatively small hydrodynamic radiu…