First Principles and Experimental Study of Phase Transformation Mechanism of Li-Rich Oxide Cathode Material in Li-Ion Battery
Authors: Lim Jin-Myoung , Kim Duho , Lim Young-Geun , Park Min-Sik , Kim Jeom-Soo , Kim Young-Jun , Cho Kyeongjae , Cho Maenghyo 
Published: February 2020

Li-rich oxide cathode is one of the most promising high capacity cathode materials for the next commercialized Li-ion battery application, and its composition can be described as a mixture of Li2MnO3 and Li(TM)O2(TM: Transition metal). Li-rich cathode material has large capacity based on relatively cheap Mn oxide, and it is easy to synthesize. However, the Li-rich cathode material has critical material challenges such as capacity degradation and voltage drop. It has been reported that the main source of the material challenge is related to phase transformation inside the bulk cathode material during charge/discharge processes.
In this work, detailed phase transformation mechanism of Li2MnO3 is investigated by combining the experimental and computational approaches to develop fundamental understanding on the atomic scale processes. The structure of Li-rich oxide is a composite of Li2MnO3 and layered Li(TM)O2, and the monoclinic layered structure of Li2MnO3 is known to be the source of the degradation problems. We have observed the evidence of phase transformation in Li2MnO3experimentally, and a theoretical analysis based on density functional theory calculations is combined with experimental data for a systematic comparative study.
For experimental study, we have synthesized Li2MnO3 powder by solid state method at low temperature following the literature procedures. Using this powder, we made a coin cell with standard Li reference electrode, and the CV measurement shows the phase transformation during charge/discharge processes. First, basic powder characterization was conducted through XRD, and SEM analyses. Second, coin cell was assembled for cyclic performance test, and charge/discharge profile and cyclic voltammogram were obtained. From the experimental investigation, synthesized Li2MnO3is identified as monoclinic C2/m space group structure and their particle size is around 200~300 nm. The evidences of phase transformation are found from cyclic charge/discharge profile as well as cyclic voltammogram. As reaction cycle is progressed, charge/discharge capacity operated under 4.6 V has a steady increase indicating that, the initial active material is getting transformed to another phase with lower reaction voltage than 4.6 V. As described in Fig. 1, we could observe the changes of charge/discharge profile and reaction voltage fundamentally caused by phase transformation consistent with similar previous experiment studies. As observed before, the first charge voltage is around 4.6 V, but the charge voltage changes to around 3.2 V as cycle goes on. Remarkably, discharge voltage reveals at three different values around 2.8 V, 3.3 V, and 4.0 V, suggesting that there are three different transformed phases inside the active material as the cycle goes on.
To understand this and similar experimental observations of phase transformation, we have examined how and why it could happen in terms of thermodynamics and kinetics based on density functional theory investigation. In case of thermodynamic study, phase stability, intercalation voltage, electronic charge, and electronic structures are studied. From phase stability and intercalation voltage analyses, we would estimate when initial structure could be transformed. The electronic charge and partial density of state for both initial and transformed structure (whose Mn ion is migrated) are investigated for structure stability and physical/chemical characters. We found that thermodynamic stability of structures and the changes in bonding characters between Mn and O ions are to the main cause of phase transformation. For kinetic analysis, we investigated the migration barriers of Li and Mn ions in the Li2MnO3framework with controlled delithiation. Based on the kinetic calculation results, we could show the possibility of Li and Mn ion migrations with different Li contents in active material. As shown in Fig 2, not only the possibility and the delithiation effect of phase transformation, but also the detailed Mn migration mechanism could be predicted providing atomic scale explanation of phase transformation. As a result, detailed phase transformation mechanism could be quantitative understood, and it would be possible to suppress such phase transformation based on theoretical studies on material design such as doping on effect the electronic structure analyses.
By understanding detailed phase transformation mechanism of Li2MnO3, we are developing material modification strategy to solve capacity degradation and voltage drop problems. The developed strategy will be critically validated by experimental implementation of the designed material modification. Such combined material design and experimental validation approaches will accelerated the high capacity cathode material development based on atomic scale understanding.
This work was supported by the Industrial Strategic technology development program(10041589) funded by the Ministry of Knowledge Economy(MKE, Korea)