Electrochimica Acta, Vol.109, 355-364, 2013
The kinetics of Li-ion deintercalation in the Li-rich layered Li-1.12[Ni0.5Co0.2Mn0.3](0.89)O-2 studied by electrochemical impedance spectroscopy and galvanostatic intermittent titration technique
The kinetics of Li-ion deintercalation in Li-1.12[Ni0.5Co0.2Mn0.3](0.89)O-2 samples is studied by electrochemical impedance spectroscopy (EIS) and galvanostatic intermittent titration technique (GITT) during the first charge process. The impedance response of Li-1.12[Ni0.5Co0.2MnO3](0.89)O-2 largely depends on the open-circuit voltage (OCV) of the cell, showing that the mechanism of electrode kinetics under different potentials is dominated by different electro-chemical reactions. Meanwhile, the equivalent circuit is proposed to simulate the EIS data, deducing the circuit elements (R-i and C-i) which are normally modeled as a multistep process of electro-chemical reactions. The change trend of R-sf (the resistance of SEI film) and R-ct (the charge-transfer resistance) in the first charge process are exactly similar. The C-dl (double-layer capacitance) as a function of voltage gradually increases, particularly after 4.5 V. The maximum of C-sf (the film capacitor) observed in the first charge process shows that the most intensive ionic fluxes will appear when the Li-1.12[Ni0.5Co0.2Mn0.3](0.89)O-2 electrode reach to the transient equilibrium at different levels of deintercalation. To study the faster capacity fading of Li-1.12[Ni0.5Co0.2Mn0.3](0.89)O-2 during the first charge process, the Li-ion diffusion coefficient (Du) is also calculated based on the results of EIS and GITT. (C) 2013 Elsevier Ltd. All rights reserved.
Keywords:Li-ion battery;Electrochemical kinetics;Lithium-rich layered cathode material;Li-ion diffusion coefficient