Role of Molecular Architecture on Ion Transport in Ethylene oxide-Based Polymer Electrolytes

Deng, Chuting; Webb, Michael A.; Bennington, Peter; Sharon, Daniel; Nealey, Paul F.; Patel, Shrayesh N.; de Pablo, Juan J.

doi:10.1021/acs.macromol.0c02424

Role of Molecular Architecture on Ion Transport in Ethylene oxide-Based Polymer Electrolytes

Journal Article · Sun Feb 21 23:00:00 EST 2021 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.0c02424· OSTI ID:1840587

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Univ. of Chicago, IL (United States)
Princeton Univ., NJ (United States)
Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)

This work aims to develop a detailed mechanistic understanding of the role of a graft polymer architecture on lithium ion (Li⁺) transport in poly(ethylene oxide)-based polymer electrolytes. Specifically, we compare Li⁺ transport in poly-(ethylene oxide) (PEO) versus poly(oligo oxyethylene methacrylate) (POEM) polymers doped with lithium bis( trifluoromethanesulfonyl) (LiTFSI) salts, using both experimental electrochemical characterization and molecular dynamics (MD) simulations. Furthermore, our results indicate that POEM exhibits a range of relaxation processes that cannot be interpreted solely in terms of glass-transition temperature (T_g) effects. Due to its side-chain architecture, the segmental relaxation of POEM is nonuniform across ether oxygens (EOs) and shows a more pronounced sensitivity to temperature above T_g compared to PEO. Moreover, POEM also exhibits a nonuniform Li⁺ coordination behavior, in which Li⁺ is primarily solvated by two different chains in POEM, compared to a single chain in PEO. Li⁺ transport in POEM occurs via two events with distinct characteristic times: a fast intrachain hopping along side chains and a slow interchain hopping between side chains. Taken together, the relaxation processes and ion transport mechanisms identified in POEM provide useful insights into design of more effective solid polymer electrolytes.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1840587

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 5 Vol. 54; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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