Abstract: Understanding the mechanism of the interfacial reaction between the cathode material and the electrolyte is a significant work because the interfacial reaction is an important factor affecting the stability, capacity, and cycling performance of Li-ion batteries. In this work, spin-polarized density functional theory calculations with on-site Coulomb energy have been employed to study the adsorption of electrolyte components propylene carbonate (PC) on the LiMn₂O₄ (100) surface. The findings show that the PC molecule prefers to interact with the Mn atom on the LiMn₂O₄ (100) surface via the carbonyl oxygen (O _c), with the adsorption energy of -1.16 eV, which is an exothermic reaction. As the adsorption of organic molecule PC increases the Mn atoms coordination with O atoms on the (100) surface, the Mn^{3 +} ions on the surface lose charge and the reactivity is substantially decreased, which improves the stability of the surface and benefits the cycling performance.

Key words: Li-ions batteries, electrolyte, density functional theory, surface, propylene carbonate