What Makes Fluoroethylene Carbonate Different

Rechargeable lithium-ion batteries containing silicon-based negative electrodes have the potential to revolutionize electrical energy storage, but the cyclic and acyclic organic carbonate solvents (such as ethylene and propylene carbonates) that are commonly used in graphite Li-ion batteries yield unsatisfactory performance when used with such Li alloying electrodes. It has been found by trial and error that additions of the closely related carbonate additive, fluoroethylene carbonate (FEC), to conventional electrolytes yields a robust solid electrolyte interphase (SEI) on the LixSiy alloy surface. Several mechanisms for this protective action have been considered in the literature and modeled theoretically; however, at present these mechanisms remain hypothetical. In this study, we use radiolysis, laser photoionization, electron paramagnetic resonance, and transient absorption spectroscopy to establish the redox chemistry of FEC. While the oxidation chemistry is similar to that of other organic carbonate...

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