The purpose of this paper is to report on the reactivity of PF5 and EC/linear carbonates to understand the thermal and electrochemical decomposition reactions of LiPF6 in carbonate solvents and how these reactions lead to the formation of products that impact the performance of lithium-ion batteries. The behavior of other salts such as LiBF4 and LiTFSI are also examined. Solid LiPF6 is in equilibrium with solid LiF and PF5 gas. In the bulk electrolyte, the equilibrium can move toward products as PF5 reacts with the solvents. The Lewis acid property of the PF5 induces a ring-opening polymerization of the EC that is present in the electrolyte and can lead to PEO-like polymers. The polymerization is endothermic until 170 degreesC and is driven by CO2 evolution. Above this temperature the polymerization becomes exothermic and leads to a violent decomposition. The PEO-like polymers also react with the PF5 to yield further products that may be soluble in the electrolyte or participate in solid electrolyte interphase (SEI) formation in real cells. GPC analysis of the heated electrolytes indicates the presence of material with M-w up to 5000. More details on the polymerization reactions and further reactions with PF5 are reported. Transesterification and polymer products are observed in the electrolytes of cycled and aged Li-ion cells. Formation of polymer materials which are further crosslinked by reaction with acidic species leads to degradation of the transport properties of the electrolyte in the composite electrodes with the accompanying loss of power and energy density. Generation of CO2 in lithium-ion cells leads to saturation of the electrolyte and cessation of the polymerization reaction. However, CO2 is easily reduced at the anode to oxalate, carbonate and CO. The carbonate contributes to the SEI layer while the oxalate is sufficiently soluble to reach the cathode to be re-oxidized to CO2 thus resulting in a shuttle mechanism that explains reversible self-discharge. Irreversible reduction of CO2 to carbonate and CO partially accounts for irreversible self-discharge. (C) 2003 Elsevier Science B.V. All rights reserved.