Transport properties of solid polymer electrolytes prepared from oligomeric fluorosulfonimide lithium salts dissolved in high molecular weight poly(ethylene oxide).

Transport properties such as ionic conductivity, lithium transference number, and apparent salt diffusion coefficient are reported for solid polymer electrolytes (SPEs) prepared using several oligomeric bis[(perfluoroalkyl)sulfonyl]imide (fluorosulfonimide) lithium salts dissolved in high molecular weight poly(ethylene oxide) (PEO). The salt series consists of polyanions in which two discrete fluorosulfonimide anions are linked together by [(perfluorobutylene)disulfonyl]imide linker chains. The restricted diffusion technique was used to measure the apparent salt diffusion coefficients in SPEs, and cationic transference numbers were determined using both potentiostatic polarization and electrochemical impedance spectroscopy methods. A general trend of diminished salt diffusion coefficient with increasing anion size was observed and is opposite to the trend observed in ionic conductivity. This unexpected finding is rationalized in terms of the cumulative effects of charge carrier concentration, anion mobility, ion pairing, host plasticization by the anions, and salt phase segregation on the conductivity.