Structural Evolution of Layered $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$ upon Electrochemical Cycling in a Li Rechargeable Battery

Recently $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$ has been consistently examined and investigated by scientists because of its high lithium storage capacity, which exceeds beyond the conventional theoretical capacity based on conventional chemical concepts. Consequently, $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$ is considered as one of the most promising cathode candidates for next generation in Li rechargeable batteries. Yet the mechanism and the origin of the overcapacity have not been clarified. Previously, many authors have demonstrated simultaneous oxygen evolution during the first delithiation. However, it may only explain the high capacity of the first charge process, and not of the subsequent cycles. In this work, we report a clarified interpretation of the structural evolution of $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$, which is the key element in understanding its anomalously high capacity. We identify how the structural evolution of $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$ occurs upon the electrochemical cycling through careful study of electrochemical profiles, ex-situ X-ray diffraction (XRD), HR-TEM, Raman spectroscopy, and first principles calculation. Moreover, we successfully separated the structural change at subsequent cycles (mainly cation rearrangement) from the first charge process (mainly oxygen evolution with Li extraction) by intentionally synthesizing sample with large particle size. Consequently, the intermediate states of structural evolution could be well resolved. All observations made through various tools lead to the result that spinel-like cation arrangement and lithium environment are created and embedded in layered framework during repeated electrochemical cycling.