Unexpected effect of tetraglyme plasticizer on lithium ion dynamics in PAMPS based ionomers

Li(+) cation conducting ionomers based on poly(2-acrylamido-2-methyl-1-propane sulphonic acid) (PAMPS) incorporating a low molecular weight plasticizer have been characterized. Previously we have observed an apparent decoupling of ionic conductivity and lithium ion dynamics from the Tg of this ionomer along with an increase in ionic conductivity obtained by incorporating a quaternary ammonium co-cation. The incorporation of tetraglyme as a coordinating plasticizer was investigated in order to further improve the ion dissociation and dynamics. Solid-state NMR, thermal analysis, impedance spectroscopy and infrared spectroscopy were used to characterize these systems. As expected, the glass transition temperature Tg decreased upon the addition of the plasticizer. However, in contrast to the previously reported Na-conducting systems, the ionic conductivity was also decreased by several orders of magnitude, indicating that the tetraglyme recouples the conductivity back to the polymer dynamics. Temperature dependent (7)Li NMR line width and T1 measurements were used to probe the Li(+) dynamics, which were found to be dependent on the Li(+) concentration, the nature of the co-cation and the presence or absence of tetraglyme.