Solid polymer electrolytes with LiClO4 – Theoretical study of polyvinylidene halides

Abstract

The potential of polyvinylidene halides PVDX (X = F, Cl, Br, I), as a materials for energy had been examined by computational chemistry. The reaction of polymer chains with lithium perchlorate was analyzed and we focused on the stability and reactivity of PVDX composites including their different crystalline α- or β-crystal forms. The characterization of cluster models in PVDX-α and PVDX-β, encompassing their geometry, electrostatic potentials, electron density, Gibbs-free energy difference, and HOMO-LUMO gap were examined. Further, an analysis of the crystal structure has unveiled modifications in the HOMO-LUMO gap, geometric distortions, and alterations in the models' reactivity.The results of theoretical study were compared to the results obtained experimentally. Structural information from FTIR spectra showed that PVDF crystalline form affects the ionic conductivity of the polymer composite and thereby its functionality as a solid polymer electrolyte. Significantly, insights into the reactivity and then the functionality of the poly(vinylidene fluoride) have been acquired, serving as a valuable supplement to the existing experimental data.