On the capacity fading of LiCoO₂ intercalation electrodes: The effect of cycling, storage, temperature, and surface film forming additives

The electrochemical behavior and surface chemistry of LiCoO₂ intercalation cathodes as a function of cycling and storage at 25, 45, and 60 °C was studied. The standard solutions for this work comprised ethylene carbonate (EC), ethyl-methyl carbonate (EMC), (1:2) and 1 M LiPF₆. The effect of two surface film-forming additives, vinylene carbonate (VC) and an organo-borate complex (denoted as Merck's AD25) in solutions was also explored. We analyzed temperature-dependent processes of surface film formation on the cathodes, which increase their impedance upon cycling and storage, thus making their electrochemical kinetics sluggish. We also analyzed cobalt dissolution from the cathodes at 25, 45 and 60 °C. The apparent capacity fading of the LiCoO₂ electrodes is attributed mostly to changes on their surface, rather than to bulk degradation. There are signs that the presence of HF in solutions may play a major negative role. Hence, as the electrode's surface/solution volume ratio is higher, the capacity fading of the LiCoO₂ electrodes should be lower. The main tools for this study were cyclic voltammetry, chronopotentiometry, impedance spectroscopy, electrochemical quartz crystal microbalance (EQCM), IR-spectroscopy, XRD, XPS, and SEM.