Chemical Synthesis and Properties of Layered Co1-yNiyO2-d (0  y  1)

A. MANTHIRAM; R.V. CHEBIAM; F. PRADO

Boston

Encuentro; Materials Research Society Fall Meeting: Symposium Solid State Chemistry of Inorganic Materials III; 2000

Material Research Society

Layered Co1-yNiyO2-δ oxides with 0 ≤ y ≤ 1 have been synthesized by chemically extracting lithium from LiNi1-yCoyO2 with NO2PF6 at ambient temperature. The samples have been characterized by X-ray diffraction, wet-chemical analyses, infrared spectroscopy, and magnetic susceptibility measurements. While NiO2-δ retains the initial O3 (CdCl2 structure) layer structure of LiNiO2, CoO2-δ consists of a mixture of P3 and O1 (CdI2 structure) phases that are formed by a sliding of the oxide ions in the initial O3 structure. CoO2-δ and NiO2-δ have oxygen contents of,respectively, 1.67 and 1.95 and the oxygen content increases with increasing Ni content, y, in Co1-yNiyO2-δ. While CoO2-δ exhibits metallic conductivity as revealed by the absence of absorption bands in the infrared spectrum, NiO2-δ exhibits semiconducting behavior due to a completely filled t2g band. Magnetic data reveal a transition from antiferromagnetic to ferromagnetic correlations as the Ni content in Co1-yNiyO2-δ increases.