Lithium transport investigation in LixFeSiO4: A promising cathode material

• Theoretical study of the diffusion mechanisms in Li2FeSiO4.
• Two-dimensional lithium diffusion was predicted by using density functional theory together with nudged elastic band method.
• We calculate the lithium coefficient diffusion in Li2FeSiO4 for different temperatures.

In this paper we investigate lithium mobility in both Li2FeSiO4 and its half-lithiated state LiFeSiO4 considering an orthorhombic crystal structure. We find that the calculated activation energy of Li+ ions hopping between adjacent equilibrium sites predicts two least hindered diffusion pathways in both materials. One of them is along the [100] direction characterizing an ionic diffusion in a straight line and the other follows a zig-zag way between the Fe–Si–O layers. We also show that diffusion of Li+ ions in the half-lithiated structure follows the same behavior as in the lithiated structure. As a whole, the activation energies for the investigated compounds present a greater value compared with the activation energies in currently used materials such as LiFePO4. The results were calculated in the framework of density functional theory in conjunction with the climbing image nudged elastic band method. The Hubbard term was added to the Kohn–Sham Hamiltonian to overcome the delocalization problem of d electrons. Furthermore, the diffusion coefficients were calculated for both structures considering temperatures ranging from 300 to 700 K.