Electrochemical properties of poly(ethylene oxide) electrolytes above the entanglement threshold

Abstract

Ion transport in electrolytes depends on three transport coefficients, conductivity (κ), salt diffusion coefficient (D), and the cation transference number with respect to the solvent velocity (t+0), and the thermodynamic factor (Tf). Current methods for determining these parameters involve four separate experiments, and the coupled nature of the equations used to determine them generally results in large experimental uncertainty. We present data obtained from 64 independent polymer electrolytes comprising poly(ethylene oxide) (PEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. The molecular weights of PEO ranged from 5 to 275 kg mol−1; these samples are all above the entanglement threshold. We minimize the experimental uncertainty in transport and thermodynamic measurements by exploiting the fact that ion transport in entangled polymer electrolytes should be independent of molecular weight. The dependence of κ, D, t+0, and Tf as a function of salt concentration in the range 0.035 ≤ r ≤ 0.30 are presented with a 95% confidence interval, where r is the molar ratio of lithium ions to ethylene oxide monomer units. While κ, D, and Tf are all positive as required by thermodynamic constraints, there is no constraint on the sign of t+0. We find that t+0 is negative in the salt concentration range of 0.093 ≤ r ≤ 0.189.