In situ electrochemical surface modification for high-voltage LiCoO2 in lithium ion batteries

Abstract High-voltage LiCoO 2 has been revisited to improve the energy density of lithium ion batteries. LiCoO 2 can deliver the reversible capacity of about 200 mA h g −1 when the upper cut-off voltage increases to 4.55 V (vs. Li/Li + ). However, the high upper cut-off voltage causes the severe failures of LiCoO 2 such as structural degradation, electrolyte decomposition, and Co dissolution. Various surface-modified LiCoO 2 materials have been introduced to suppress electrolyte decomposition and Co dissolution, thereby leading to the improved electrochemical performance. Most of the coated LiCoO 2 materials are obtained through a conventional coating process such as sol-gel synthesis, which is complex and high-cost. In this paper, the in situ electrochemical coating method is introduced as a simple and low-cost coating process, where the electrolyte additive of Mg salts is electrochemically decomposed to form a MgF 2 -based coating layer on the LiCoO 2 surface. LiCoO 2 electrochemically coated with MgF 2 suppresses Co dissolution in electrolytes, resulting in excellent electrochemical performance such as high reversible capacity of 198 mA h g −1 and stable cycle performance over 100 cycles in the voltage range between 3 and 4.55 V (vs. Li/Li + ) at 45 °C. The formation mechanism of MgF 2 is also demonstrated through ex situ XPS and XANES analyses.