First Principles Study on Phase Stability in Li-Rich Layered Li2MnO3-LiMO2 (M=Mn, Ni, Co)
Regarding their structure complexity, there is significant debate in the literature so far on whether these Lithium–rich layered cathode material form homogeneous solid solutions or Li2MnO3 nano-composite within a LiMO2matrix. It is important to get a clear picture of the actual detail structure, to understand and control their electrochemical performance. And without a detailed knowledge of the structure, it will be problematic to further explore failure mechanisms with cycling.
Recently in our research, the atomic order in Li-rich layered composites with composition xLi2MnO3-(1-x)LiMO2 is investigated with first-principles calculations using Generalized Gradient Approximation (GGA) +U method. The random solid solution structure model between Li2MnO3 and LiMO2 are created by Special Quasirandom Structures (SQSs) theory. After calculating the mixing energy, the miscibility gap is achieved and phase separation between Li2MnO3 and LiMO2 are predicted. Further study on the coherency strain energy shows that the strain energy is relatively small compared to mixing energy. Phase separation cannot be inhibited by strain.