Abstract
The behavior of metallic lithium electrodes with poly (ethylene oxide)‐based polymer electrolytes has been studied as a function of the nature and concentration of the salt, time, temperature, and current density. Impedance spectroscopy and galvanostatic polarization results are reported. Passivating film formation and growth have been observed under open‐circuit conditions. Results have shown that the nature of such films and the kinetics of their formation are related to the electrolyte composition. Data obtained from the literature for one of the systems studied were interpreted according to a proposed film formation mechanism. The reaction occurring at the lithium‐polymer electrolyte interface under polarization is not related to a simple charge‐transfer mechanism. The variation in the interphase resistance under constant current polarization, both anodic and cathodic, is discussed.

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