Unraveling the contribution of nucleation to the intercalation energy barrier for phase-transforming Li-ion battery materials

Phase-transforming intercalation compounds, such as LiFePO4 (LFP) and Li4Ti5O12 (LTO), are widely utilized in Li-ion batteries, particularly for applications requiring high power and operation at low temperatures. However, the impact of phase transformation kinetics on energy density losses under extreme conditions has been largely unexplored. Specifically, the role of nucleation, the initial stage of phase transformation, in contributing to battery performance losses has not been previously investigated. In this study, we not only quantified the significance of material-level factors, such as interfacial charge transfer, in the low-temperature and high-rate performance of LFP and LTO materials, but also provided the first estimates of the apparent activation energies of nucleation. Our findings revealed that nucleation, particularly in the case of LFP, contributes significantly to overpotential, highlighting its pivotal role among material-level factors. Furthermore, our analysis allowed us to differentiate between material-level and particle-level limitations for the LTO/LFP cell, emphasizing the paramount importance of controlling the porosity of secondary particles to ensure high tolerance towards high-rate/low-temperature discharge.