The structural variation of Li
2MnO
3 during charge–discharge cycling as a lithium-battery cathode was investigated. The Rietveld refinement of neutron diffraction data revealed that the Li
2MnO
3 synthesized at 900°C was assigned to the monoclinic symmetry corresponding to the
C2/
m space group (
z = 4). The transmission electron microscopy (TEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) measurements were carried out using the samples after cycling in the potential ranges of 2.0–4.6, 2.0–4.8, and 2.0–5.0 V. As a result, it was observed that structures based on the cubic (
Fd3m) and rhombohedral (
R3m) symmetries, having the compositions of LiMn
2O
4 and LiMnO
2, respectively, are locally generated on the surface of the particles, depending on the upper voltage for the charge process. It was also found that the voltage at which the
R3m rhombohedral structure is generated tended to be higher than the voltage at which the
Fd3m cubic structure is formed. Such a structural variation of Li
2MnO
3 is anticipated to be related to the extraction of oxygen molecules which is induced during the charge processes. Furthermore, the generation of the
R3m LiMnO
2 could be understood by the introduction of oxygen vacancies into the material.
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