Date of Award


Degree Type


Degree Name

Doctor of Philosophy in Chemistry



First Advisor

Brett Lucht


The thermal decomposition of LiPF6 in solution with carbonate solvents has been investigated. The thermal dissociation of LiPF6 into LiF and PF5 is known. In solution, PF5 reacts with carbonates to form a variety of decomposition products including: carbon dioxide (CO2), ethers (R2O), alkylfluorides (RF), phosphorus oxyfluoride (OPF3), and fluorophosphates (OPF2OR, OPF(OR)2), assignment of structure is supported by Nuclear Magnetic Resonance (NMR) spectroscopy and Gas Chromatography with Mass Selective Detection (GC-MS). Similar decomposition products are observed during the thermal decomposition of carbonate solutions of LiPF6. Since solutions of LiPF6 are widely used as Li-ion battery electrolytes, there is interest among battery manufacturers and researchers as to the thermal decomposition of this electrolyte. Here we describe the structural and mechanistic investigations of the thermal decomposition of lithium-ion battery electrolytes. The electrolyte undergoes autocatalytic decomposition reactions at moderately elevated temperatures (80-100 °C) to produce a large number of decomposition products. Results indicate that the thermal decomposition reactions are suppressed by the electrode, particularly the cathode, or intended stabilizing additives.



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