Negative Stefan-Maxwell Diffusion Coefficients and Complete Electrochemical Transport Characterization of Homopolymer and Block Copolymer Electrolytes

Nanostructured block copolymers are of particular interest as electrolytes in batteries with lithium metal anodes. The performance of electrolytes in batteries can be predicted only if three transport coefficients (ionic conductivity, κ, salt diffusion coefficient, D , and cation transference number, t 0 + ) are known. We present complete electrochemical transport characterization of a microphase-separated SEO block copolymer electrolyte by reporting κ, D, and t 0 + as functions of salt concentration. We compare the properties of the block copolymer electrolyte with those of PEO homopolymer electrolytes. Negative values of t 0 + are observed in many cases. Recasting the transport parameters in terms of Stefan-Maxwell coefficients provides insight into the nature of ion transport in these electrolytes.