Electronic structures and Li diffusion in cathode material Li<sub>2</sub>FeO<sub>2</sub> of Li-ion batteries

Abstract

The electronic structures and lithium diffusion in the cathode material <i>Immm</i>-Li<sub>2</sub>FeO<sub>2</sub> of lithium-ion batteries are calculated by the first-principles method based on the density functional theory. The calculated results show that <i>Immm</i>-Li<sub>2</sub>FeO<sub>2</sub> is ferromagnetic, and the band structure indicates a semi-metal character. The d-electrons of Fe ions are in the low spin state, with a spin polarization of 8.01%. The spin-up and spin-down band structure are also analyzed by using the <i>l</i>-decomposed electronic density of states. Furthermore, the energy barriers for the lithium ion diffusion in different directions are calculated by the nudged elastic band method. For comparison, the potential barriers for the Li<sub>2</sub><i>M</i>O<sub>2</sub> (<i>M</i> = Co, Ni, Cu) are also calculated. The results suggest that it is easier for Li ion to diffuse in the <i>c</i>-axis directionof Li<sub>2</sub>FeO<sub>2</sub>, with an energy barrier of only 0.1 eV. The energy barrier is 0.21 eV for Li to diffuse in the <i>ab</i>-axis direction, while the diffusion barrier is 0.39 eV along the <i>a</i>-axis direction of Li<sub>2</sub>FeO<sub>2</sub>. All these values of energy barriers are lower than those in other Fe-based cathodes mentioned, indicating that the Li diffusion coefficient in <i>Immm</i>-Li<sub>2</sub>FeO<sub>2</sub> should be larger than those of other materials, which also indicates that the Li<sub>2</sub>FeO<sub>2</sub> is of great importance as cathode material.