Polymer-nanocomposite brush-like architectures as an all-solid electrolyte matrix.

Abstract

Herein, we report on polymer-nanocomposites with brush-like architectures and evaluate their feasibility as an all-solid electrolyte matrix supporting Li(+)-ion conduction. Showcased as a first example in the domain of electrolyte research, the study probes several key factors, such as (i) core morphology, (ii) surface modifiers/functionality, (iii) grafting length, and (iv) density of the brushes, and determines their role on the overall electrochemical properties of these nanostructured organic-inorganic hybrids. Nanostructured titania was synthesized via wet-chemical approaches using either controlled hydrolysis or hydrothermal methods. Exercising suitable control on reaction parameters led to well-defined morphologies/phases, such as nanoparticles, nanospindles, nanourchins, nanorods or nanotubes, in either anatase, rutile or mixed forms. Covalent anchoring on titania nanostructures was achieved using dopamine, gallic acid and glycerol as small organic moieties. A one-pot process of priming the available surface functional groups postmodification with isocyanate chemistry was followed by grafting polyethylene glycol monomethyl ethers of desired chain lengths. Finally, complexation with lithium salt yielded electrolyte compositions where the ethylene oxide (EO) fractions aid in ion-solvation with ease. The synthesized materials were characterized in detail employing XRD, TEM, DRS-UV, FTIR, micro-Raman, TG-DTA and DSC at each stage to confirm the products and ascertain the physicochemical properties. Comprehensive evaluation using temperature-step electrochemical impedance spectroscopy (EIS) of these brush-like nanocomposites provided crucial leads toward establishing a plausible physical model for the system and understanding the mechanism of ion transport in these all-solid matrices. The preliminary results on ionic conductivity (σ) obtained for some of the compositions are estimated to be within the range of ∼10(-4) to 10(-5) S cm(-1) in the temperature window of the study that holds excellent promise for further improvement.