![]() We show that β is a sensitive function of end-group chemistry. We introduce a nondimensional parameter, β, that combines microscopic diffusivities and conductivity. The measured ion self-diffusivities did not reflect the measured conductivities in some cases, samples with high diffusivities exhibited low conductivity. The ion self-diffusivities were measured by pulsed field gradient nuclear magnetic resonance spectroscopy (PFG-NMR), and a microscopic cation transference number was calculated from these measurements. The continuum properties, conductivity and cation transference number, were measured by ac impedance spectroscopy and potentiostatic polarization, respectively. We present measurements of continuum and microscopic ion transport properties of nonflammable liquid electrolytes consisting of binary mixtures of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and perfluoropolyethers (PFPE) with different end groups: diol, dimethyl carbonate, ethoxy−diol, and ethoxy−dimethyl carbonate. Better understanding of the relationship between microscopic and continuum scale transport properties would enable the rational design of improved electrolytes for applications such as lithium batteries. Balsara*,‡,§,∥ †ĭepartment of Materials Science and Engineering and ‡Department of Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, California 94720, United States § Materials Sciences Division and ∥Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States ⊥ Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States # Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh, North Carolina 27695, United States S Supporting Information *ĪBSTRACT: Connecting continuum-scale ion transport properties such as conductivity and cation transference number to microscopic transport properties such as ion dissociation and ion self-diffusivities is an unresolved challenge in characterizing polymer electrolytes. Relationship between Conductivity, Ion Diffusion, and Transference Number in Perfluoropolyether Electrolytes Mahati Chintapalli,†,§ Ksenia Timachova,‡,§ Kevin R. ![]()
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