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First Principles Study of Two-Phase Boundary in LiFePO_{4}

First Principles Study of Two-Phase Boundary in LiFePO

_{4}Wednesday, 8 October 2014

Expo Center, 1st Floor, Center and Right Foyers (Moon Palace Resort)

It is well known that a flat plateau at 3.4 V appears in charging/discharging curve of olivine-type LiFePO

However, the lithium distribution in the interface is not clearly understood. The first-principles density functional theory (DFT) is a powerful tool to study such a small region from an atomic scale. In the present work, we theoretically investigated the interface region in LiFePO

The mixing energy of the partially delithiated structure LixFePO

_{4}cathode. The constant voltage indicates that the extraction/insertion proceeds under two-phase reaction in which the electrochemical potential of lithium ions keeps a constant value independent of the state of charge. Thus, in the two-phase reaction, it is considered that the lithium ions can be extracted from the interface between the endmembers, namely, LiFePO_{4}and FePO_{4}. The two-phase interface has been clearly observed on the surface of platelet nanoparticle by using transmission electron microscopy by several groups. The typical interface has a finite thickness about 10 to 20 nm and locates parallel to bc-plane. Delmas et al. explained the mechanism of electrochemical charging by means of “domino cascade model” in which the lithium ions are continuously extracted from the cascade of the interface region.However, the lithium distribution in the interface is not clearly understood. The first-principles density functional theory (DFT) is a powerful tool to study such a small region from an atomic scale. In the present work, we theoretically investigated the interface region in LiFePO

_{4}compounds by using DFT. The crystal and the electronic structures are determined by using spin-polarized generalized gradient approximation with short-range Coulomb interactions (GGA+U). In this work, we employed selfconsistently obtained value of U = 4.3 eV which is sufficient to reproduce localized electronic structure. The wavefunction is expanded by planewaves with a kinetic-energy cutoff of 500 eV. The interface model is composed of three regions: fully lithiated (LiFePO_{4}), fully delithiated (FePO_{4}), and interface region. The interface region is assumed to be parallel to bc-plane, and is sandwiched between the endmembers. It is considered that the lattice parameters in the interface gradually changes along a-axis. The total energy of the structure in the interface can be determined by giving the intermediate value of the lattice parameters to the unit cell at a microscopic area in the interface. We calculated mixing energies of the endmembers to form partially delithiated structures at the microscopic area by considering possible configurations of lithium ions and localized electrons. The mixing energy of the partially delithiated structure, F, is defined as F = E(x) − [(1−x) E(x=1) + x E(x=0)], where E(x) is the total energy of LixFePO4, and x is concentration of lithium ions. The positive value of F means that the two-phase separation is favored, and the negative value of F means that the solid-solution structure of LixFePO_{4}is likely to appear.The mixing energy of the partially delithiated structure LixFePO

_{4}, (x=0, 0.25, 0.50, 0.75, and 1) is calculated. From the calculated mixing energy, it is found that the curves of the mixing energy are different among the three regions. In the interface, the mixing energy shows negative value with lithium concentration of 0.5 and 0.75. It means that the solid-solution phase is spontaneously formed in the interface region parallel to bc-plane.