ANODE PASSIVATION AND ELECTROLYTE SOLVENT DISPROPORTIONATION - MECHANISM OF ESTER EXCHANGE-REACTION IN LITHIUM-ION BATTERIES

Carbonate-based electrolytes used in Lithium-ion electrochemical cells were found to undergo ester exchange reactions, where the use of dime thyl carbonate and diethyl carbonate resulted in the in situ formation of ethyl methyl carbonate. The reaction was found to be reversible an d occurs during the first charge cycle of the LiCoO2/petroleum coke li thium-ion system. Mechanistic studies were carried out and determined that the ester exchange reaction is reductively initiated at the carbo n anode. A mechanism has been deduced, with an intermediate alkoxide s pecies responsible for the ester exchange reaction. Electrode passivat ion was found to limit the extent of the reaction during subsequent cy cles, with the choice of electrolyte solvent impacting the passivation of the electrode.