In-Situ EIS to Investigate Effect of C-Rate on Impedance Spectra of Positive Electrodes with Different Ratio of Conductive Additives in Lithium Ion Batteries

Abstract

Active materials, conductive additives and binders are widely used for the fabrication of positive electrodes of lithium ion batteries (LIBs). The electrochemical performance of positive electrodes is affected by the addition rate of conductive additives on the electrode 1). It is important to investigate the effect of the addition rate of conductive additives on the electrode performance of the positive electrode during charge-discharge cycle in order to develop LIBs that can charge and discharge at high C-rate. In the present study, the in-situ EIS 2) was employed to investigate the effect of C-rate on impedance spectra of positive electrode with different additive rates of conductive additives. The positive electrode with different additive rates of acetylene black (AB) was fabricated by screen printing. The mixture of the slurry containing LiCoO2 powder, AB, polyvinylidene fluoride and N-methylpyrrolidone were screen-printed on the aluminum foil. In the present study, the positive electrode with different additive rates of AB was used for the impedance measurement. The spherical natural graphite fabricated on cupper foil was used as the negative electrode and a lithium wire was used as the reference electrode (RE). All measurements were carried out by the three-electrode cell (Toyo system co. ltd.) at room temperature in an argon atmosphere. The 3D impedance of positive electrode, negative electrode and full cell was measured by in-situ EIS during charge and discharge. In the 3D impedance of positive electrode, three loops were observed on the Nyquist plane during charge and discharge. As the diameter of loop in the low frequency range was decreased with the increase of the state of charge (SOC), this loop may be related to the time constant composed of the charge transfer resistance R ct and the electric double layer capacitance 2). In order to examine the effect of C-rate on impedance of positive electrode, the changes of R ct values during charge and discharge were estimated from the instantaneous impedance at arbitrary SOC on 3D impedance of positive electrode. The relationship between C-rate and additive rates of AB on the impedance of positive electrode was discussed. References: 1) F. Y. Su, C. H. You, Y. B. He, W. Lv, W. Cui, F. Jin, B. Li, Q. H. Yang and F. Kang, J. Mater. Chem., 20, 9644-9650 (2010). 2) M. Itagaki, K. Honda, Y. Hoshi, I. Shitanda, J. Electroanal. Chem., 737, 78–84 (2015).