New insights into the interactions between electrode materials and electrolyte solutions for advanced nonaqueous batteries

In this paper we review some recent work with Li metal and Li–graphite anodes and LixMOy cathodes (M=transition metals such as Ni, Co, Mn). The emphasis was on the study of surface phenomena using in situ and ex situ FTIR spectroscopy, atomic force microscopy (in situ AFM), electrochemical quartz crystal microbalance (EQCM) and impedance spectroscopy (EIS). The performance of Li metal and Li–carbon anodes in secondary batteries depends on the nature of the surface films that cover them. The use of Li metal anodes requires the formation of highly uniform and elastic surface films. Thus, most of the commonly used liquid electrolyte solutions are not suitable for Li metal-based rechargeable batteries. In the case of Li–C-based batteries, the passivating films need not be elastic. Channeling the Li–C electrode surface chemistry towards the formation of Li2CO3 surface films provides adequate passivation for these electrodes. This can be achieved through the use of EC-based solutions of low EC concentration (cosolvents should be less reactive than EC). An interesting finding is that the behavior of many commonly used cathodes also depends on their surface chemistry, and that their overall Li insertion processes include the step of Li ion migration through surface films. Their origin is discussed herein, as well as possible oxidation processes of the relevant solutions.