Identification of alkylated phosphates by gas chromatography–mass spectrometric investigations with different ionization principles of a thermally aged commercial lithium ion battery electrolyte

• Identification of several new decomposition products with a method in a lithium ion battery electrolyte.
• Structure elucidating with the help of different ionization techniques.
• Proposed reaction cycles for the formation of the decomposition products.

The thermal aging process of a commercial LiPF6 based lithium ion battery electrolyte has been investigated in view of the formation of volatile phosphorus-containing degradation products. Aging products were analyzed by GC–MS. Structure determination of the products was performed by support of chemical ionization MS in positive and negative modes. A fraction of the discovered compounds belongs to the group of fluorophosphates (phosphorofluoridates) which are in suspect of potential toxicity. This is well known for relative derivatives, e.g. diisopropyl fluorophosphate. Another fraction of the identified compounds belongs to the group of trialkyl phosphates. These compounds may provide a positive impact on the thermal and electrochemical performance of Li-based batteries as repeatedly described in the literature.