ABSTRACT
Poly(ethylene oxide) (PEO)-based polymer electrolytes are a promising class of materials for use in lithium-ion batteries due to their high ionic conductivity and flexibility. In this study, the effects of polymer architecture including linear, star, and hyperbranched and salt (lithiumbis(trifluoromethanesulfonyl)imide (LiTFSI)) concentration on the glass transition (T g), microstructure, phase diagram, free volume, and bulk viscosity, all of which play a significant role in determining the ionic conductivity of the electrolyte, have been systematically studied for PEO-based polymer electrolytes. The branching of PEO widens the liquid phase toward lower salt concentrations, suggesting decreased crystallization and improved ion coordination. At high salt loadings, ion clustering is common for all electrolytes, yet the cluster size and distribution appear to be strongly architecture-dependent. Also, the ionic conductivity is maximized at a salt concentration of [Li/EO ≈ 0.085] for all architectures, and the highly branched polymers displayed as much as three times higher ionic conductivity (with respect to the linear analogue) for the same total molar mass. The architecture-dependent ionic conductivity is attributed to the enhanced free volume measured by positron annihilation lifetime spectroscopy. Interestingly, despite the strong architecture dependence of ionic conductivity, the salt addition in the highly branched architectures results in accelerated yet similar monomeric friction coefficients for these polymers, offering significant potential toward decoupling of conductivity from segmental dynamics of polymer electrolytes, leading to outstanding battery performance.
ABSTRACT
This work reports the effects of free volume on curcumin release in various polymer-based composite films. Curcumin-reinforced biocomposite films were fabricated with natural biopolymers (carrageenan and chitosan) and bioplastics (poly(lactide) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT)) via the solvent casting method. The curcumin release test was performed using an aqueous medium, and it was found that it was released the fastest in the carrageenan film, followed by the chitosan, PLA, and PBAT films, presumably owing to the dissimilarity of the polymer matrix. The free volume of the polymer films was determined using positron annihilation lifetime spectroscopy (PALS) to understand the release phenomena of curcumin. The free volume fraction was varied and reliant on the type of polymer, with the highest in the PBAT-based film followed by the PLA-, chitosan-, and carrageenan-based films. The free volume method helps analyze the release of bioactive compounds in a polymer matrix and may help to achieve a better understanding of the release of bioactive compounds.
