Polypropylene carbonate-based electrolytes as model for a different approach towards improved ion transport...

Linear poly(alkylene carbonates) such as polyethylene carbonate (PEC) and polypropylene carbonate (PPC) have gained increasing interest due to their remarkable ion transport properties such as high Li⁺ transference numbers. The cause of these properties is not yet fully understood which makes it challenging to replicate them in other polymer electrolytes. Therefore, it is critical to understand the underlying mechanisms in polycarbonate electrolytes such as PPC. In this work we present insights from impedance spectroscopy, transference number measurements, PFG-NMR, IR and Raman spectroscopy as well as molecular dynamics simulations to address this issue. We find that in addition to plasticization, the lithium ion coordination by the carbonate groups of the polymer is weakened upon gelation, leading to a rapid exhange of the lithium ion solvation shell and consequently a strong increase of the conductivity. Moreover, we study the impact of the anions by employing different conducting salts. Interestingly, while the total conductivity decreases with increasing anion size, the reverse trend can be observed for the lithium ion transference numbers. Via our holistic approach, we demonstrate that this behavior can be attributed to differences in the collective ion dynamics.