Structural evolution of layered Li1.2Ni0.2Mn0.6O2 upon electrochemical cycling in a Li rechargeable battery

Recently Li1.2Ni0.2Mn0.6O2, one of the most promising cathode candidates for next generation Li rechargeable batteries, has been consistently investigated especially because of its high lithium storage capacity, which exceeds beyond the theoretical capacity based on conventional chemical concepts. Yet the mechanism and the origin of the overcapacity have not been clearly understood. Previous reports on simultaneous oxygen evolution during the first delithiation 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 Li1.2Ni0.2Mn0.6O2 upon the electrochemical cycling, which is the key element in understanding its anomalously high capacity, through careful study of electrochemical profiles, ex situ X-ray diffraction, HR-TEM, Raman spectroscopy, and first principles calculation. Moreover, we successfully resolved the intermediate states of structural evolution upon electrochemical cycles by intentionally synthesizing sample with large particle size. All observations made through various tools lead to the result that spinel-like cation arrangement and lithium environment are gradually created and locally embedded in layered framework during repeated electrochemical cycling. Moreover, through analyzing the intermediate states of the structural transformation, this gradual structural evolution could explain the mechanism of the continuous development of the electrochemical activity below 3.5 V and over 4.25 V.