a Nishi Battery Laboratories, Sony Corporation, 2-1-1 Shin-Sakuragaoka, Hodogaya-ku, Yokohama 240-0036, Japan
Abstract:
Chemical synthesis routes to LixMn2O4 (0.15≤x≤1) in non-equilibrium reduction processes were developed to carry out detailed structural analysis. Non-equilibrium LixMn2O4 (0.15≤x≤1) samples were prepared by chemical lithiation of λ-MnO2 with LiI for 24 h; longer than 1 week was needed to reach true equilibrium at room temperature. The samples were characterized by X-ray diffraction analysis. The phase diagram was different from that in the equilibrium state; three cubic phases (phases A, B and C) were observed for LixMn2O4 (0.15≤x≤1). There were two regions of two-phase coexistence: the region of 0.25<x<0.55 (phase B+phase C) and 0.6<x<1.0 (phase A+phase B). In the compositional range of 0.6<x<1.0, the lattice constants of phases A and B change with the lithium composition, this indicates that it is a structural anomaly with a metastable two-phase character in non-equilibrium reduction processes.