Entropic Penalty Switches Li+ Solvation Site Formation and Transport Mechanisms in Mixed Polarity Copolymer Electrolytes

Deng, Chuting; Bennington, Peter; Sánchez-Leija, Regina J.; Patel, Shrayesh N.; Nealey, Paul F.; de Pablo, Juan J.

doi:10.1021/acs.macromol.3c00804

Entropic Penalty Switches Li⁺ Solvation Site Formation and Transport Mechanisms in Mixed Polarity Copolymer Electrolytes

Journal Article · Fri Sep 22 00:00:00 EDT 2023 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.3c00804· OSTI ID:2004604

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University of Chicago, IL (United States)
University of Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Emerging solid polymer electrolyte (SPE) designs for efficient Li-ion (Li⁺) conduction have relied on polarity and mobility contrast to improve conductivity. To further develop this concept, we employ simulations to examine Li⁺ solvation and transport in poly(oligo ethylene methacrylate) (POEM) and its copolymers with poly(glycerol carbonate methacrylate) (PGCMA). We find that Li⁺ is solvated by ether oxygens instead of the highly polar PGCMA, due to lower entropic penalties. The presence of PGCMA promotes single-chain solvation, thereby suppressing interchain Li⁺ hopping. The conductivity difference between random copolymer PGCMA-r-POEM and block copolymer PGCMA-b-POEM is explained in terms of a hybrid solvation site mechanism. With diffuse microscopic interfaces between domains, PGCMA near the POEM contributes to Li⁺ transport by forming hybrid solvation sites. The formation of such sites is hindered when PGCMA is locally concentrated. These findings help explain how thermodynamic driving forces govern Li⁺ solvation and transport in mixed SPEs.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); University of Chicago, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; NE0009323

OSTI ID:: 2004604

Alternate ID(s):: OSTI ID: 2202622
OSTI ID: 2587980

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 19 Vol. 56; ISSN 0024-9297; ISSN 1520-5835

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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