The Role of Backbone Polarity on Aggregation and Conduction of Ions in Polymer Electrolytes

Schauser, Nicole S.; Grzetic, Douglas J.; Tabassum, Tarnuma; Kliegle, Gabrielle A.; Le, My Linh; Susca, Ethan M.; Antoine, Ségolène; Keller, Timothy J.; Delaney, Kris T.; Han, Songi; Seshadri, Ram; Fredrickson, Glenn H.; Segalman, Rachel A.

doi:10.1021/jacs.0c00587

The Role of Backbone Polarity on Aggregation and Conduction of Ions in Polymer Electrolytes

Journal Article · Fri Apr 03 00:00:00 EDT 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c00587· OSTI ID:1767659

Schauser, Nicole S. ^[1]; ^[2]; Tabassum, Tarnuma ^[2]; Kliegle, Gabrielle A. ^[2]; Le, My Linh ^[2]; Susca, Ethan M. ^[2]; Antoine, Ségolène ^[2]; Keller, Timothy J. ^[2]; ^[2]; ^[2]; ^[2]; ^[2]; ^[2]

Univ. of California, Santa Barbara, CA (United States); OSTI
Univ. of California, Santa Barbara, CA (United States)

The usual understanding in polymer electrolyte design is that an increase in the polymer dielectric constant results in reduced ion aggregation and therefore increased ionic conductivity. We demonstrate here that in a class of polymers with extensive metal–ligand coordination and tunable dielectric properties, the extent of ionic aggregation is delinked from the ionic conductivity. The polymer systems considered here comprise ether, butadiene, and siloxane backbones with grafted imidazole side-chains, with dissolved Li⁺, Cu²⁺, or Zn²⁺ salts. The nature of ion aggregation is probed using a combination of X-ray scattering, electron paramagnetic resonance (in the case where the metal cation is Cu²⁺), and polymer field theory-based simulations. Polymers with less polar backbones (butadiene and siloxane) show stronger ion aggregation in X-ray scattering compared to those with the more polar ether backbone. The T_g-normalized ionic conductivities were however unaffected by the extent of aggregation. The results are explained on the basis of simulations which indicate that polymer backbone polarity does impact the microstructure and the extent of ion aggregation but does not impact percolation, leading to similar ionic conductivity regardless of the extent of ion aggregation. Finally, the results emphasize the ability to design for low polymer T_g through backbone modulation, separately from controlling ion-polymer interaction dynamics through ligand choice.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Materials for Water and Energy Systems (M-WET); Univ. of Texas, Austin, TX (United States)

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

Grant/Contract Number:: SC0019272

OSTI ID:: 1767659

Alternate ID(s):: OSTI ID: 1678696

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 15 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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The Role of Backbone Polarity on Aggregation and Conduction of Ions in Polymer Electrolytes

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