Intrinsic Ion Transport Properties of Block Copolymer Electrolytes

Daniel Sharon, Peter Bennington, Moshe Dolejsi, Michael A. Webb, Ban Xuan Dong, Juan J. De Pablo, Paul F. Nealey, Shrayesh N. Patel

Research output: Contribution to journalArticlepeer-review

26 Scopus citations


Knowledge of intrinsic properties is of central importance for materials design and assessing suitability for specific applications. Self-assembling block copolymer electrolytes (BCEs) are of great interest for applications in solid-state energy storage devices. A fundamental understanding of ion transport properties, however, is hindered by the difficulty in deconvoluting extrinsic factors, such as defects, from intrinsic factors, such as the presence of interfaces between the domains. Here, we quantify the intrinsic ion transport properties of a model BCE system consisting of poly(styrene-block-ethylene oxide) (SEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt using a generalizable strategy of depositing thin films on interdigitated electrodes and self-assembling fully connected parallel lamellar structures throughout the films. Comparison between conductivity in homopolymer poly(ethylene oxide) (PEO)-LiTFSI electrolytes and the analogous conducting material in SEO over a range of salt concentrations (r, molar ratio of lithium ion to ethylene oxide repeat units) and temperatures reveals that between 20% and 50% of the PEO in SEO is inactive. Using mean-field theory calculations of the domain structure and monomer concentration profiles at domain interfaces - both of which vary substantially with salt concentration - the fraction of inactive PEO in the SEO, as derived from conductivity measurements, can be quantitatively reconciled with the fraction of PEO that is mixed with greater than a few volume percent of polystyrene. Despite the detrimental interfacial effects for ion transport in BCEs, the intrinsic conductivity of the SEO studied here (ca. 10-3 S/cm at 90 °C, r = 0.085) is an order of magnitude higher than reported values from bulk samples of similar molecular weight SEO (ca. 10-4 S/cm at 90 °C, r = 0.085). Overall, this work provides motivation and methods for pursuing improved BCE chemical design, interfacial engineering, and processing.

Original languageEnglish
Pages (from-to)8902-8914
Number of pages13
JournalACS Nano
Issue number7
StatePublished - 28 Jul 2020
Externally publishedYes

Bibliographical note

Funding Information:
We gratefully acknowledge support by the U.S. Department of Energy (DOE), Basic Energy Sciences, Materials Sciences and Engineering Division. This work made use of the Pritzker Nanofabrication Facility of the Pritzker School of Molecular Engineering at the University of Chicago, which receives support from Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), a node of the National Science Foundation’s National Nanotechnology Coordinated Infrastructure. We acknowledge the MRSEC Shared User Facilities at the University of Chicago (NSF DMR-1420709).

Publisher Copyright:
Copyright © 2020 American Chemical Society.


  • block copolymer
  • ionic conductivity
  • lithium ion battery
  • nanomaterials
  • polymer electrolyte


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