Structure and Transport Properties of Poly(ethylene oxide)-Based Cross-Linked Polymer Electrolytes─A Molecular Dynamics Simulations Study

We present an extensive molecular dynamics (MD) simulation study of poly(ethylene oxide) (PEO)-based densely cross-linked polymers, focusing on structural properties as well as the systems’ dynamics in the presence of lithium salt. Motivated by experimental findings for networks with short PEO strands, we employ a combination of LiTFSI (lithium bis(trifluoromethanesulfonyl)imide) and LiDFOB (lithium difluoro(oxalato)borate). Recently, it has been shown that such multisalt systems outperform classical single-salt systems [Shaji, I. Energy Storage Mater.2022, 44, 263−277]. To analyze the microscopic scenario, we employ an analytical model, originally developed for non-cross-linked polymer electrolytes or blends [Maitra, A. Phys. Rev. Lett.2007, 98, 227802 and Diddens, D. J. Electrochem. Soc.2017, 164, E3225–E3231]. Excluding very short PEO strands, the local dynamics is only slightly restricted compared to linear PEO and is not significantly dependent on the network structure. The transfer of lithium ions between PEO chains and the motion along the polymer backbone may be controlled through the employed salt.