Shigeki Komine

Low-temperature growth of spinel-type Li1+xMn2−xO4 crystals using a LiCl–KCl flux and their performance as a positive active material in lithium-ion rechargeable batteries

Low-temperature growth of idiomorphic spinel-type Li1+xMn2−xO4 (x = 0.09, 0.14) crystals was achieved by using a LiCl–KCl flux. The flux growth driven by rapid cooling resulted in truncated octahedral Li1+xMn2−xO4 crystals surrounded by both dominating {111} and minor {100} faces. The chemical compositions, sizes, and shapes of the Li1+xMn2−xO4 crystals could be tuned by simply changing the growth conditions. Among the various products, the crystals grown at a low temperature of 600 °C showed a small average size of 0.2 μm. The small Li1+xMn2−xO4 crystals grown at 600 °C showed better rate properties than the large crystals grown at 900 °C, when used as a positive active material in lithium-ion rechargeable batteries.

Orbital-Specific observation of O2p and Ni3d electrons in LiNi0.5Mn0.5O2, a cathode material for lithium-ion batteries

Cathode materials for lithium-ion batteries containing Ni2+ have attracted much interest because of their high theoretical capacity. However, the precise electronic structures of these cathode materials have not yet been clearly observed, especially the energy positions of the O2p and Ni3d orbitals and the shape of the density of states. The aim of this study was to investigate the relative energy positions and shape of the density of states of O2p and Ni3d for LiNi0.5Mn0.5O2 experimentally. We cleaved a LiNi0.5Mn0.5O2 pellet in an Ar-filled glove box and performed synchrotron ultraviolet photoelectron spectroscopy for different photon energies, which enabled us to investigate the relative cross-section intensity of O2p and Ni3d. As a result, the valence-band structure was determined. We found that O2p electrons are itinerant and exist in the vicinity of the Fermi energy more than Ni3d electrons. Ni3d electrons are more localized and spread mainly from 1.2–1.5 eV below the Fermi energy. To validate the el...