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Pure Appl. Chem., 2002, Vol. 74, No. 10, pp. 1885-1894

Cation order/disorder in lithium transition-metal oxides as insertion electrodes for lithium-ion batteries

E. Zhecheva1, R. Stoyanova1, R. Alcántara2, P. Lavela2 and J.-L. Tirado2

1 Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria
2 Laboratorio de Química Inorgánica, Edificio C3, Primera Planta, Campus de Rabanales, Facultad de Ciencias, Universidad de Córdoba, 14071 Córdoba, Spain

Abstract: Results on the local cation ordering in layered lithium-nickel/cobalt oxides and metal-substituted lithium-manganese spinels are presented. It is shown that electron spin resonance of Ni3+ and Mn4+ and magnetic susceptibility measurements are powerful tools to monitor the short-range cation ordering in these compounds, which is not accessible by diffraction techniques. Thus, owing to the different strength of the 90° and 180° Ni3+–O–Ni3+/2+ exchange interactions, the distribution of Ni3+/Ni2+ between the lithium and nickel layers in Li1–xNi1+xO2 with 0 < x < 0.4 can be determined. For layered LiNi1–yCoyO2 and spinel LiMn2–xCoxO4 solid solutions, analysis of the temperature-independent EPR line width in terms of dipole–dipole and exchange interactions has been used to examine the local Ni3+/Co3+ and Mn4+/Co3+ ordering. The results obtained are correlated with the electrochemical intercalation of lithium in these compounds.