Combined study of phase transitions in the P2-type NaXNi1/3Mn2/3O2 cathode material: experimental, ab-initio and multiphase-field results

Abstract The research of new electrode materials such as sodium intercalation compounds is key to meet the challenges of future demands of sustainable energy storage. For these batteries, the intercalation behavior on the micro-scale is governed by a complex interplay of chemical, electrical and mechanical forces strongly influencing the overall cell performance. The multiphase-field method is a suitable tool to study these multi-physics and bridge the scale from ab-initio methods to the cell level. In this work, we follow a combined approach of experiments, density functional theory (DFT) calculations and multiphase-field simulations to predict thermodynamic and kinetic properties for the P2-type Na X Ni 1/3 Mn 2/3 O 2 sodium-ion cathode material. Experimentally, we obtain the thermodynamic potential and diffusion coefficients at various sodium contents using electrochemical techniques and discuss limitations of the experimentally applied methods. DFT is used to identify stable phases by calculating an energy hull curve. Then, the influence of long-range dispersion interactions and the exchange-correlation functional on the voltage curve is investigated by comparison with experimental results. Finally, multiphase-field simulations are performed based on inputs from experiments and DFT. The fitting of phase-specific chemical free energies from DFT calculations and experimental data is discussed. Our results highlight the thermodynamic consistency of all three approaches close to thermodynamic equilibrium. Furthermore, the phase-field method accurately describes the kinetics of the system including multiple phase transitions, by which we unravel the mechanism of the P2-O2 phase transition in a single crystal under the influence of intercalation reaction, bulk diffusion and elastic deformation. The model is able to predict the kinetic capacity loss depending on charging rate in agreement with C-rate experiments.