Dynamic Electrochemical Impedance Spectroscopy for Characterization of the State of Health of Graphite Electrodes

Abstract

Graphitic carbon is the most used material as anode in lithium-ion batteries since the last 30 years. To make batteries cost-effective for mobility or stationary applications the optimization of every aspect is crucial. Advanced techniques can be implied to undercover or demonstrate the main chemical processes at the graphite electrode such as the Electrochemical Impedance Spectroscopy (EIS). EIS is a powerful technique able to reveal and separate resistive and capacitive properties of an interface in a non-destructive way. It has been applied for the characterization of graphite in order to quantify the charge transfer resistance on the intercalation process, to study the mechanism of formation of solid-electrolyte-interface (SEI), and reveal the lithium plating process [1]. There are high requirements for the collection of impedance spectra on a broad range of frequencies (typically from kHz to tens of mHz) at different electrode potentials regarding measurement time and the condition of a system in equilibrium. To overcome these requirements a technique has been developed called Dynamic Electrochemical Impedance Spectroscopy (DEIS). For DEIS a multi-frequency signal, containing all frequencies to probe in a form of summed sine waves, is superimposed to the galvanostatic current. Using this method, it is possible to measure the time-varying impedance while the system is drifting through non-equilibrium states, e.g. during charge/discharge cycling.In this study we propose DEIS measurements performed on a freshly assembled graphite/lithium half-cell cycled at current rates of C/10 and C/5 and 1C (for aging). Figure 1 A shows the working electrode voltage profile of the first 16 cycles. The chosen geometry for the cell is a three-electrode pouch cell with 2x2cm square electrodes and an insulated copper wire with lithium plated at the tip as micro-reference electrode (see Figure 1 B).The novelty of the proposed method is the fully automatized procedure to acquire the dynamic impedance on a wide frequency band (1kHz-10mHz) continuously over an arbitrary number of cycles to investigate the degradation of the electrode. The experimental set-up is shown as a scheme in Figure 1 C [2]. On base of the recorded current and voltage signals, we computed the time-varying impedance using the Dynamic Multi-Frequencies Analysis (DMFA). This method allows to calculate the impedance at the low frequency band by filtering of the sine components in the Fourier domain; the voltage drift is calculate in the same way [3]. An example of the computed time-varying impedance and the respective potential profile for the first cycle is reported in Figure 1 D.