Impedance Modeling of Solid-State Electrolytes: Influence of the Contacted Space Charge Layer.

Understanding the interfacial impedance between the solid electrolyte and the electrode is a critical issue for the design of solid-state batteries. We propose a new equivalent circuit model that treats the interface not only as a capacitor but also includes the space charge layer resistance and the resultant polarization resistance. Moreover, the elements of the circuit model are quantified by the physical quantities based on the recently proposed modified Planck-Nernst-Poisson (MPNP) model, which includes the effect of the unoccupied regular lattice sites (vacancies) in the electro-diffusion problem and takes both the ion and electron contributions into the account. We provide a new analytical solution for the space charge layer capacitance. Comparative numerical results demonstrate that our proposed model with additional polarization resistance can explain well the real impedance tail at the low-frequency region, for which the pure capacitor interface model fails. The model is verified against the experimental impedance spectra of LiPON.