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

Abstract

The mechanism of ionic transport in PAN based polymer electrolytes with LiBF 4 as the Li salt and Al 2O 3 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:LiBF 4 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 BF 4 − mobility freezes.