Ionic Transport in Polymer Electrolytes:  The Essential Role of Associated Ionic Species

Polymer electrolytes based on poly(bis(methoxyethoxyethoxy)phosphazene) (MEEP) exhibit some of the highest room temperature ionic conductivities reported in a single-phase system. The mechanism of ionic transport in polymer electrolytes, particularly the nature of the charge-carrying species, has been poorly understood at the molecular level. Vibrational spectroscopy is used to determine the nature and relative amounts of ionic species present in MEEP−LiCF3SO3 as a function of salt concentration. The composition corresponding to the conductivity maximum is completely dominated by neutral cation−anion contact ion pairs and the triple anion species, {Li(CF3SO3)2}-. Furthermore, the conductivity changes only slightly at higher salt concentrations where triple cations dominate. These data require a dissociation−reassociation mechanism of ion transport in which dynamic equilibrium is established between the various ionically associated species by exchange of individual Li+ and CF3SO3 - ions. The individual ions migrate between associated ionic species through the liquidlike domains defined by the entangled ethylene oxide side chains.