Evolution of structure, transport properties and magnetism in ternary lithium nitridometalates Li3-x-yMxN, M = Co, Ni, Cu

摘要

The structures, magnetism and ion transport properties of the ternary nitrides Li3-x-yMxN (M = Co, Ni, Cu; y = lithium vacancy) were examined by powder X-ray diffraction, solid-state NMR and SQUID magnetometry. Doping levels are achieved up to x approximate to 0.4 for M = Cu and Co, but much higher substitution levels (x approximate to 1) are obtained in the Li-Ni-N system. Transition metals substitute for Li at the Li(1) interplanar site and the ensuing lithium vacancies are disordered within the [Li2N] planes. High substitution levels in the Li-Ni-N system lead to the formation of ordered phases. Diffusion parameters, including activation energies, correlation times and diffusion coefficients, were obtained from variable-temperature solid-state NMR measurements in several ternary compounds. SQUID magnetometry shows significant variations of the electronic properties with dopant and x. The properties of the ternary nitrides can be rationalised in terms of the identity of the dopant and the structural modifications arising from the substitution process.