Understanding the Lithium Ion Transport in Concentrated Block-Copolymer Electrolytes on a Microscopic Level

TL;DR

This study uses molecular dynamics simulations to explore how lithium ions move within concentrated block-copolymer electrolytes, revealing a salt-rich layer that enhances ion mobility and transport efficiency.

Contribution

It provides microscopic insights into ion transport mechanisms in highly concentrated block-copolymer electrolytes, highlighting the role of a salt-rich layer in improving conductivity.

Findings

LiTFSI forms a network-like structure in the lamella center.

High salt concentrations lead to ions being coordinated more by TFSI and THF.

The salt-rich layer enables high cation mobility and transport numbers.

Abstract

Block-copolymer electrolytes with lamellar microstructure show promising results regarding the ion transport in experiments. Motivated by these observations we study block-copolymers consisting of a polystyrene (PS) block and a poly(ethylene oxide) (PEO) block which were assembled in a lamellar structure. The lamella was doped with various amounts of lithium-bis(trifluoromethane)sulfonimide (LiTFSI) until very high loadings with ratios of EO monomers to cations up to 1:1 were reached. We present insights into the structure and ion transport from extensive Molecular Dynamics simulations. For high salt concentrations most cations are not coordinated by PEO but rather by TFSI and THF. More specifically, LiTFSI partially separates from the PEO domain and forms a network-like structure in the middle of the lamella. This central salt-rich layer plays a decisive role to enable remarkably good cationic mobilities as well as high transport numbers in agreement with the experimental results.