Investigation of time domain measurement of electrochemical impedance spectrum in low frequency range for lithium-ion batteries using preset equivalent circuit model

A time domain measurement technique using a preset equivalent circuit model consisting of many series-connected resistor and capacitor parallel elements was examined as a measurement method of the electrochemical impedance spectrum of a lithium-ion battery excluding the apparent impedances from open circuit voltage change in the low frequency range. At first, a comprehensive experimental study was carried out to determine the standard condition of the applied signal suitable for this technique. It was established that an impedance spectrum from several tens of microhertz to several tens of millihertz can be accurately measured by selecting a proper, small rate and long duration constant current charge or discharge as the applied signal. Next, impedance spectra excluding the apparent impedances from open circuit voltage change were measured under various conditions using this technique, and basic characteristics of the impedances of the solid state diffusion processes of lithium that exist in the corresponding low frequency range were investigated. It was revealed that the impedance spectrum excluding the apparent impedances from open circuit voltage change in the low frequency range, from several tens of microhertz to several tens of millihertz, can be reasonably separated into two finite length Warburg impedances that can be clearly characterized by difference in their diffusion time constant values and in the state of charge dependence of their diffusion resistances. An Arrhenius type temperature dependence was confirmed for both of their diffusion resistances.