Electrochemical Corrosion Behavior of Iron in Lithium-ion Battery Electrolyte

The element iron (Fe) is affordable and abundantly available, and thus, it finds use in a wide range of applications. As regards its application in rechargeable lithium-ion batteries (LIBs), the electrochemical reactions of Fe must be clearly understood during battery charging and discharging with the LIB electrolyte. In this study, we conducted systematic electrochemical analyses under various voltage conditions to determine the voltage at which Fe corrosion begins in general lithium salts and organic solvents used in LIBs. During cyclic voltammetry (CV) experiments, we observed a large corrosion current above 4.0 V (vs. Li/Li⁺). When a constant voltage of 3.7 V (vs. Li/Li⁺), was applied, the current did not increase significantly at the beginning, similar to the CV scenario; on the other hand, at a voltage of 3.8 V (vs. Li/Li⁺), the current increased rapidly. The impact of this difference was visually confirmed via scanning electron microscopy and optical microscopy. Our X-ray photoelectron spectroscopy measurements showed that at 3.7 V, a thick organic solid electrolyte interphase (SEI) was formed atop a thin fluoride SEI, which means that at ≥3.8 V, the SEI cannot prevent Fe corrosion. This result confirms that Fe corrosion begins at 3.7 V, beyond which Fe is easily corrodible.