Electrochimica Acta, Vol.49, No.4, 581-589, 2004
Calorimetric investigation of the reactivity of the passivation film on lithiated graphite at elevated temperatures
Thermal storage of lithiated graphite electrodes has been performed between 40 and 90 degreesC for 8 h to 3 weeks. The results were compared for two separators: Celgard 2402 and a microporous PVdF membrane. The effects of storage on the capacity losses have been discussed with respect to the passivation film on the graphite electrodes in contact with the electrolyte solution EC:DMC:DEC (2:2:1)-1 M LiPF6. The capacity loss shows a thermally activated character, which has been related to transformations of the passivation film at moderate temperatures. At higher temperatures, reaction of the intercalated lithium takes place, controlled by Li+-ion diffusion. DSC measurements were performed on passivated and lithiated graphite electrodes. Two peaks could be distinguished. An effect of the elevated temperature storage on the intensity and onset temperature of the first peak in DSC is evidenced. This peak could be attributed to the transformation of the passivation film. The second peak is due to the diffusion of lithium ions and the subsequent reaction with the liquid electrolyte. The effect of washing the electrode with DMC was thoroughly investigated. Our results allowed to attribute the transformation of the passivation film upon DSC analysis to a reaction taking place in the presence of LiPF6. (C) 2003 Elsevier Ltd. All rights reserved.
Keywords:graphite;differential scanning calorimetry;passivation film;reactivity;rechargeable lithium batteries