Improving Thermodynamic Stability of nano-LiMn₂O₄ for Li-Ion Battery Cathode

Nanomaterials can exhibit improved electrochemical performance in cathode applications, but their inherently high surface areas cause unconventional instability, leading to capacity fading after a limited number of battery cycles. This is because of their high surface reactivity, which makes them more susceptible to phenomena such as grain growth, sintering, solubilization, and phase transformations. Thermodynamically, these can be attributed to an increased contribution of interfacial enthalpies to the total free energy of the system. The lack of experimental data on the interfacial thermodynamics of lithium-based materials has hindered strategies to mitigate such degradation mechanisms. In this study, interfacial energies of LiMn2O4 nanoparticles were directly measured for the first time using calorimetry, and the possibility of thermodynamically manipulating both surface and grain boundary energies using a dopant (scandium) was explored. We show that undoped LiMn2O4 nanoparticles have a surface energy of 0.85 J/m2, which is significantly lower than that of LiCoO2. Moreover, introducing scandium further lowered the LiMn2O4 surface energy, leading to a demonstrated improved stability against coarsening and reactivity to water, which can potentially result in more stable cathode materials for battery applications.