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Ion Transport and Structure in Polymer Electrolytes with Applications in Lithium Batteries


When mixed with lithium salts, polymers that contain more than one chemical group, such as block copolymers and endgroup-functionalized polymers, are promising electrolyte materials for next-generation lithium batteries. One chemical group can provide good ion solvation and transport properties, while the other chemical group can provide secondary properties that improve the performance characteristics of the battery. Secondary properties of interest include non-flammability for safer lithium ion batteries and high mechanical modulus for dendrite resistance in high energy density lithium metal batteries. Block copolymers and other materials with multiple chemical groups tend to exhibit nanoscale heterogeneity and can undergo microphase separation, which impacts the ion transport properties. In block copolymers that microphase separate, ordered self-assembled structures occur on longer length scales. Understanding the interplay between structure at different length scales, salt concentration, and ion transport is important for improving the performance of multifunctional polymer electrolytes.

In this dissertation, two electrolyte materials are characterized: mixtures of endgroup-functionalized, short chain perfluoropolyethers (PFPEs) and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt, and mixtures of polystyrene-block-poly(ethylene oxide) (PS-b-PEO; SEO) and LiTFSI. The PFPE/LiTFSI electrolytes are liquids in which the PFPE backbone provides non-flammability, and the endgroups resemble small molecules that solvate ions. In these electrolytes, the ion transport properties and nanoscale heterogeneity (length scale ~1 nm) are characterized as a function of endgroup using electrochemical techniques, nuclear magnetic resonance spectroscopy, and wide angle X-ray scattering. Endgroups, especially those containing PEO segments, have a large impact on ionic conductivity, in part because the salt distribution is not homogenous; we find that salt partitions preferentially into the endgroup-rich regions. On the other hand, the SEO/LiTFSI electrolytes are fully microphase-separated, solid, lamellar materials in which the PS block provides mechanical rigidity and the PEO block solvates the ions. In these electrolytes longer length scale structure (~10 nm – 1 μm) influences ion transport. We study the relationships between the lamellar grain size, salt concentration, and ionic conductivity using ac impedance spectroscopy, small angle X-ray scattering, electron microscopy, and finite element simulations. In experiments, decreasing grain size is found to correlate with increasing salt concentration and increasing ionic conductivity. Studies on both of these polymer electrolytes illustrate that structure and ion transport are closely linked.

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