LiMn2O4 Surface Chemistry Evolution during Cycling Revealed by in Situ Auger Electron Spectroscopy and X-ray Photoelectron Spectroscopy.
Ching-Yen TangKevin LeungRichard T HaaschShen J DillonPublished in: ACS applied materials & interfaces (2017)
This work utilizes in situ electrochemical and analytical characterization during cycling of LiMn2O4 (LMO) equilibrated at different potentials in an ultrahigh vacuum (UHV) environment. The LMO reacts with organic molecules in the vacuum to form a high surface concentration of Li2CO3 (≈50% C) during initial charging to 4.05 V. Charging to higher potentials reduces the overall Li2CO3 concentration (≈15% C). Discharging to 3.0 V increases the Li2CO3 concentration (≈30% C) and over discharging to 0.1 V again reduces its concentration (≈15% C). This behavior is reproducible over 5 cycles. The model geometry utilized suggests that oxygen from LMO can participate in redox of carbon, where LMO contributes oxygen to form the carbonate in the solid electrolyte interphase (SEI). Similar results were obtained from samples cycled ex situ, suggesting that the model in situ geometry provides reasonably representative information about surface chemistry evolution. Carbon redox at LMO and the inherent voltage instability of the Li2CO3 likely contributes significantly to its capacity fade.