The mechanism of ionic transport in PAN-based solid polymer electrolytes

The mechanism of ionic transport in PAN based polymer electrolytes with LiBF4 as the Li salt and Al2O3 as ceramic filler is investigated employing a range of advanced solid state NMR methodologies with a special focus on the role of the DMSO employed as a solvent. The residual amount of DMSO present in the samples was found to be virtually independent of the PAN:LiBF4 ratio, but solely dependent on the amount of Li salt ( 1–2 DMSO molecules per equivalent of Li salt). Only a marginal fraction of Li cations seems to be associated with the PAN polymer, identified from a considerable strong 7Li–1H dipolar coupling as exemplified by 7Li–{1H}–CPMAS-REDOR NMR spectroscopy. The majority of Li cations however is involved in a Li(DMSO)1–2 complex and exhibits a rather high mobility which persists down to temperatures of T = 220 K, the same temperature, at which the DMSO and BF4− mobility freezes.

► Mechanism of ion conduction in PAN based electrolytes. ► PAN matrix immobile irrespective of salt and DMSO content. ► Li(DMSO)n as mobile Li species.