Intrinsic Ion Transport Properties of Block Copolymer Electrolytes

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

doi:10.1021/acsnano.0c03713

Title: Intrinsic Ion Transport Properties of Block Copolymer Electrolytes

Journal Article · 04 June 2020 · ACS Nano

DOI: https://doi.org/10.1021/acsnano.0c03713 · OSTI ID:1774336

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

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 degrees 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 degrees C, r = 0.085). Finally, this work provides motivation and methods for pursuing improved BCE chemical design, interfacial engineering, and processing.

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Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

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

Grant/Contract Number:: AC02-06CH11357; ECCS-1542205; DMR-1420709

OSTI ID:: 1774336

Journal Information:: ACS Nano, Vol. 14, Issue 7; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
polymer electrolyte
block copolymer
ionic conductivity
lithium ion battery
nanomaterials

Title: Intrinsic Ion Transport Properties of Block Copolymer Electrolytes

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