Abstract
Lithium rich, manganese rich composites with general formula xLi2MnO3•(1-x)LiMO2 are promising candidates for high capacity and high voltage cathodes for lithium ion batteries. Lithium rich oxides crystallize as a nanocomposite of layered phases whose structure further evolves with electrochemical cycling. Raman spectroscopy is potentially a powerful tool to monitor the crystal chemistry and correlate phase changes with electrochemical behavior. While several groups have reported Raman spectra of lithium rich oxides, the data show considerable variability in terms of both the vibrational features observed and their interpretation. In this study Raman microscopy is used to investigate lithium-rich manganese-rich cathodes as a function of average charge and electrochemical cycling. LMR-NMC cycled at elevated temperature (60 °C) has a modified crystal structure which may account for some of the observed increase in capacity. Contrary to some reports, no growth of a spinel phase is observed. However, analysis of the Raman spectra does indicate the structure of LMR-NMC deviates significantly from an ideal layered phase. The results also highlight the importance of using low laser power and large sample sizes to obtain consistent data sets.