Cation order/disorder in lithium transition-metal
oxides as insertion electrodes for lithium-ion
batteries*
E. Zhecheva 1, R. Stoyanova 1 ,R. Alcántara 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 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.
* 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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