Influence of surface modification of LiCoO2 by organic compounds on electrochemical and thermal properties of Li/LiCoO2 rechargeable cells

Abstract

LiCoO2 is the most famous positive electrode (cathode) for lithium ion cells. When LiCoO2 is charged at high charge voltages far from 4.2V, cycleability of LiCoO2 becomes worse. Causes for this deterioration are instability of pure LiCoO2 crystalline structure and an oxidation of electrolyte solutions LiCoO2 at higher charge voltages. This electrolyte oxidation accompanies with the partial reduction of LiCoO2. We think more important factor is the oxidation of electrolyte solutions. In this work, influence of 10 organic compounds on electrochemical and thermal properties of LiCoO2 cells was examined as electrolyte additives. As a base electrolyte solution, 1M (M: molL−1) LiPF6-ethylene carbonate (EC)/ethylmethyl carbonate (EMC) (mixing volume ratio=3:7) was used. These compounds are o-terphenyl (o-TP), Ph-X (CH3)n (n=1 or 2, X=N, O or S) compounds, adamantyl toluene compounds, furans and thiophenes. These additives had the oxidation potentials (Eox) between 3.4 and 4.7V vs. Li/Li+. These Eox values were lower than that (6.30V vs. Li/Li+) of the base electrolyte. These additives are oxidized on LiCoO2 during charge of the LiCoO2 cells. Oxidation products suppress the excess oxidation of electrolyte solutions on LiCoO2. As a typical example of these organic compounds, o-TP (Eox: 4.52V) was used to check the fundamental properties of these organic additives. Charge–discharge cycling tests were carried out for the Li/LiCoO2 cells with and without o-TP. Constant current charge at 4.5V is mainly used as a charge method. Cells with 0.1wt.% o-TP exhibited slightly better cycling performance and lower polarization than those without additives. Lower polarization arises from a decrease in a resistance of interface between electrolyte solutions and LiCoO2 by surface film formation resulted from oxidation of o-TP. Oxidation products were found by mass spectroscopy analysis to be mixture of several polycondensation compounds made from two to four terphenly monomers. Thermal stability of LiCoO2 with electrolyte solutions did not improve by addition of o-TP. Slightly better charge–discharge cycling properties were obtained by using organic modifiers. However, when industrial applications were considered, drastic improvements have not been obtained yet. One of reasons may be too large influence of the deterioration of stability of pure LiCoO2 structure at high voltage charging for industrial use. We hope to realize the tremendous improvements of high energy, long cycle life and safe lithium cells by the combination of both LiCoO2 with more stable structure such as LiCoO2 treated with MgO and new organic additives with molecular structure more carefully designed.