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Pure Appl. Chem. 74(10), 1885-1894, 2002

Pure and Applied Chemistry

Vol. 74, Issue 10

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

E. Zhecheva 1, R. Stoyanova 1 ,R. Alc�ntara 2, P. Lavela 2, and J.-L. Tirado 2

1 Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria; 2 Laboratorio de Qu�mica Inorg�nica, Edificio C3, Primera Planta, Campus de Rabanales, Facultad de Ciencias, Universidad de C�rdoba, 14071 C�rdoba, 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.

* Lectures presented at the 10th International Symposium on Solubility Phenomena, Varna, Bulgaria, 22 -26 July 2002. Other lectures are published in this issue, pp. 1785-1920.


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