Impedance spectra of soft ionics

Abstract

Impedance spectroscopy is widely adopted for probing the charge and charge mobility of soft ion-conducting media, such as synthetic membranes and biological tissue. The spectra exhibit a variety of distinctive signatures, but the physical basis of these is not well understood, e.g. models have not previously accounted for viscoelasticity, hydrodynamics or microstructural heterogeneity. This study explores a physically grounded continuum model that captures how these factors shape conductivity spectra. Nonlinear thermodynamics and linearised dynamics of a viscous electrolyte and compressible, elastic polymer network are coupled under the forcing of an oscillatory electric field. The model is solved in a one-dimensional spatially periodic unit cell, reporting conductivity and dielectric permittivity spectra, including Nyquist representations. Whereas rigid microstructures exhibit ion-diffusion-controlled relaxation, which manifests as a low-frequency dielectric ‘constant’, hydrodynamic and elastic forces contribute to a strongly diverging dielectric permittivity at low frequencies for heterogeneous anionic microstructures. The model also captures distinctive characteristics of experimentally reported impedance spectra for films bearing alternating layers of cationic and anionic charge, again highlighting the role of coupled hydrodynamic, elastic and electrical forces. Sufficiently thin and highly charged bilayers exhibit a notably low high-frequency conductivity. This is explained by strong low-frequency electrostatic polarisation and counter-ion release. The one-dimensional solutions computed herein provide a foundation for much more challenging computations in two and three dimensions.