Abstract
The correlated ion-transport mechanism and its dependence on microscopic phase separation for a new class of quasi-solid semi-IPN electrolytes is probed in considerable detail using temperature-step electrochemical impedance spectroscopy. The response of electrolyte matrices under alternating current perturbation is comprehensively analyzed using a simulated model fit to extract pertinent information relevant to the phase composition and homogeneity, contribution of each phase, interfacial charge-transfer resistance, phase entanglement zones, bulk relaxation time for ionic hopping mechanisms, coupled segmental motions, rate of site reorganization that dictates successful hopping events, and estimates of ionic transport numbers. The normalized complex plane Nyquist plots (ρ′ versus ρ″) show two well-defined regions for bulk (in mid- and high-frequency regions) and electrode–electrolyte interfacial impedance (in low-frequency regions). Rigorous analysis indicates the presence of three microscopic phases in the matrix bulk (pure poly(ethylene oxide)–polyurethane (PEO-PU), pure poly(ethylene glycol) dimethyl ether (PEGDME), and PEO-PU/PEGDME mixed phase) along with the charge-transfer resistance (Rct) which contribute to the bulk resistance. Spectroscopic plots of complex impedance against frequency (Z″ versus log f) depict Debye peaks, providing an estimate of the bulk relaxation time (τpeak). Profiles depicting the real component of conductivity (σ′(ω)) as a function of frequency (log f) follow a modified universal power law where the simulated fit results reveal vital information on the site relaxation rates, cumulative favorability for successful hopping events, and predominant charge carrier type. The behavior of the dielectric contributions provides insights into the various ion polarization processes dominant in the high-, mid-, and low-frequency windows of the sweep. These trends were further correlated with our prior evaluation of the physico-chemical properties of the semi-IPN matrices to propose a rational physical model for these complex systems.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
