Article ID Journal Published Year Pages File Type
7740174 Journal of Power Sources 2013 5 Pages PDF
Abstract
LiNi0.5Mn1.5O4, which has a spinel framework structure, is a promising candidate for the cathode material of next-generation lithium-ion batteries with high energy density. We investigate the structural transition in LixNi0.5Mn1.5O4 (0 ≤ x ≤ 1) through first-principles calculations using the projector augmented wave method with the generalized gradient approximation. We calculate all the unique Li-site occupation configurations in a unit cell to obtain the total energies and the most stable structures for various compositions. Thermodynamic analysis shows that Li0.5Ni0.5Mn1.5O4 with x = 0.5 is the only stable phase for 0 < x < 1. The decomposition energy is lower than 0.1 eV for 0 < x < 0.5, but is distinctly higher for 0.5 < x < 1. The decomposition energy reaches 0.39 eV at x = 0.75. The ratios of the structures at room temperature are calculated from Boltzmann factors by using the energy differences between structures. The crystal structure of the unit cell changes gradually from x = 0 to 0.5, but changes markedly from x = 0.5 to 1. This first-principles study provides a general evaluation of the variation in the crystal structure with the composition of the bulk material, which affects the cyclability of the electrode.
Related Topics
Physical Sciences and Engineering Chemistry Electrochemistry
Authors
, , , ,