Effect of Polymer Topology on Microstructure, Segmental Dynamics, and Ionic Conductivity in PEO/PMMA-Based Solid Polymer Electrolytes

Bakar, Recep; Darvishi, Saeid; Li, Tianyu; Han, Mertcan; Aydemir, Umut; Nizamoglu, Sedat; Hong, Kunlun; Senses, Erkan

doi:10.1021/acsapm.1c01178

Title: Effect of Polymer Topology on Microstructure, Segmental Dynamics, and Ionic Conductivity in PEO/PMMA-Based Solid Polymer Electrolytes

Journal Article · Thu Dec 23 00:00:00 EST 2021 · ACS Applied Polymer Materials

DOI:https://doi.org/10.1021/acsapm.1c01178· OSTI ID:1885220

Bakar, Recep ^[1]; Darvishi, Saeid ^[1];

^[2];

^[1];

^[3];

^[1]

Koc University, Istanbul (Turkey)
University of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

We report Poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) have attracted much interest due to their high ionic conductivity resulting from inherently fast segmental dynamics and high salt solubility, yet they lack mechanical stability in their neat form. Blending PEO with another rigid, or high glass transition temperature, polymer is a versatile way to improve the mechanical stability; however, the ionic conductivity is strongly reduced due to slower segmental dynamics of highly interpenetrating linear polymer chains. In this work, we used model PEO/PMMA blend systems prepared with various well-defined PEO architectures (linear, stars, hyperbranched, and bottlebrushes) doped with lithium bis(trifluoromethane-sulfonyl)-imide (LiTFSI) and investigated, for the first time, the role of macromolecular architecture of PEO on crystallization, segmental dynamics, and ionic conductivity in the blends and electrolytes. The results suggest that room-temperature miscibility of these polymers can be dramatically extended by using nonlinear PEO in the blends instead of linear chains, which crystallize above 35 wt %. The broadband dielectric spectroscopy results revealed enhanced decoupling of PMMA and PEO segmental dynamics in compact branched architectures, which helps to achieve faster segmental motion of star PEO in glassy PMMA. This manifests as nearly three-fold higher ionic conductivity in these nonlinear blends compared to the conventional linear PEO/PMMA system. Regardless of the PEO architectures, the temperature dependence of ionic conductivity blends with PMMA and LiTFSI is well defined using the Vogel–Fulcher–Tammann mechanism, suggesting that ion transport is mainly affected by the segmental motion. The activation energy values decrease with the increasing ionic conductivity. Overall, our results show that macromolecular architecture can be a tool to decouple segmental dynamics and ion mobility to rationally design SPEs with improved performance.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC); Koç University SEED

Grant/Contract Number:: AC05-00OR22725; SF.00078

OSTI ID:: 1885220

Journal Information:: ACS Applied Polymer Materials, Vol. 4, Issue 1; ISSN 2637-6105

Publisher:: ACS PublicationsCopyright Statement

Country of Publication:: United States

Language:: English

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