Investigation of the gas evolution in lithium ion batteries: effect of free lithium compounds in cathode materials

Abstract

The evolution of gas in lithium ion batteries (LIBs) was investigated. The large amount of gas emission related to a charged cathode has been a critical issue because it causes deformation and performance degradation of LIBs. This study examined the effect of free lithium compounds such as Li2CO3 or LiOH on gas generation, which revealed several different features comparing with gas generation related to the cathode active materials themselves: CO2 was the main gas generated, chain-structured carbonate solvents such as dimethyl carbonate or ethyl methyl carbonate generated more gas than cyclic-structured ethylene carbonate, and the gas generation did not occur without LiPF6 in the electrolyte solution. These were found to be the main reason for the different gas-generating behaviors between LiCoO2 (LCO) and LiNi0.85Co0.12Al0.03O2 (NCA) cathodes. For LCO, which has a very small amount of free lithium compounds on the surface, the gas was generated mainly by a reaction between delithiated LCO itself and the electrolyte solution, whereas a considerable amount of gas was generated by surface free lithium for NCA. Therefore, the removal of free lithium compounds is essential, particularly for NCA, to prevent the swelling of LIBs.