Universal Relationship between Conductivity and Solvation-Site Connectivity in Ether-Based Polymer Electrolytes

Pesko, Danielle M.; Webb, Michael A.; Jung, Yukyung; Zheng, Qi; Miller, Thomas F.; Coates, Geoffrey W.; Balsara, Nitash P.

doi:10.1021/acs.macromol.6b00851

Title: Universal Relationship between Conductivity and Solvation-Site Connectivity in Ether-Based Polymer Electrolytes

Journal Article · Fri Jul 15 00:00:00 EDT 2016 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.6b00851· OSTI ID:1474952

Pesko, Danielle M. ^[1]; Webb, Michael A. ^[2]; Jung, Yukyung ^[3]; Zheng, Qi ^[3]; Miller, Thomas F. ^[2]; Coates, Geoffrey W. ^[3]; Balsara, Nitash P. ^[4]

Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering
Cornell Univ., Ithaca, NY (United States). Dept. of Chemistry and Chemical Biology. Baker Lab.
Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division. Environmental Energy Technology Division

In this paper, we perform a joint experimental and computational study of ion transport properties in a systematic set of linear polyethers synthesized via acyclic diene metathesis (ADMET) polymerization. We measure ionic conductivity, σ, and glass transition temperature, T_g, in mixtures of polymer and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. While T_g is known to be an important factor in the ionic conductivity of polymer electrolytes, recent work indicates that the number and proximity of lithium ion solvation sites in the polymer also play an important role, but this effect has yet to be systematically investigated. Here, adding aliphatic linkers to a poly(ethylene oxide) (PEO) backbone lowers T_g and dilutes the polar groups; both factors influence ionic conductivity. To isolate these effects, we introduce a two-step normalization scheme. In the first step, Vogel–Tammann–Fulcher (VTF) fits are used to calculate a temperature-dependent reduced conductivity, σ_r(T), which is defined as the conductivity of the electrolyte at a fixed value of T – T_g. In the second step, we compute a nondimensional parameter f_exp, defined as the ratio of the reduced molar conductivity of the electrolyte of interest to that of a reference polymer (PEO) at a fixed salt concentration. We find that f_exp depends only on oxygen mole fraction, x₀, and is to a good approximation independent of temperature and salt concentration. Molecular dynamics simulations are performed on neat polymers to quantify the occurrences of motifs that are similar to those obtained in the vicinity of isolated lithium ions. Finally, we show that f_exp is a linear function of the simulation-derived metric of connectivity between solvation sites. From the relationship between σ_r and f_exp we derive a universal equation that can be used to predict the conductivity of ether-based polymer electrolytes at any salt concentration and temperature.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC02-05CH11231; CHE-1335486

OSTI ID:: 1474952

Journal Information:: Macromolecules, Vol. 49, Issue 14; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 53 works

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