Abstract
Since PMMA-based gel polymer electrolytes could substitute PVDF-HFP based gels currently used in Li-ion batteries at lower financial and environmental costs, we investigate here the solvation and transport properties of the lithium ions in a crosslinked PMMA-based gel polymer electrolyte by a combination of thermal and electrochemical methods, Raman spectroscopy, pulse field gradient (PFG) and electrophoretic NMR (eNMR) techniques, as well as ab initio calculations. The conductivity of the gel containing 10 wt% polymer is only reduced by 14% relative to the liquid electrolyte. In addition, the co-solvation by polymer functional groups, a priori expected to slow lithium transport relatively to the anion, has instead a positive effect on lithium transport. Indeed, the ester groups not only participate in lithium solvation and increase ionic dissociation, but since this interaction is rather weak, rather than lowering the lithium diffusion relatively to other species, it mainly decorrelates lithium transport from anionic mobility. Compared to its liquid fraction, the gels show, at the same time, better dissociation and a higher lithium transference number, which results in a higher cationic conductivity, despite the overall conductivity loss.