Lithium-ion rechargeable batteries find wide application in modern portable electronic devices. LiMn₂O₄ spinel is the most attractive cathode material for lithium-ion batteries due to its low cost, low toxicity and high energy density. An important problem prohibiting it from wider use as a cathode material is capacity fading during cycling. Jahn-Teller distortion and spinel solution are two main causes for the capacity loss. The charge ordering of Mn⁴⁺ and Mn³⁺ ions and Jahn-Teller distortion induces a phase transformation near the room temperature. The partial substitution of Li⁺ ions for manganese reduces the concentration of Mn³⁺ ions, suppresses the Jahn-Teller effect, and the cubic spinel phase can be retained at low temperature.
Small deviations in the preparation process can cause distinct structural changes. A slight lithium ions deficiency causes the tetragonal phase formation provided that the samples obtained at high temperature are rapidly quenched structure in the solid CO₂. On the contrary, very small amount of excess lithium can influence the cubic to orthorhombic phase transition observed for stoichiometric LiMn₂O₄. Structure refinement by the Rietveld profile analysis, based on the laboratory and synchrotron radiation X-ray diffraction data, has been performed on the stoichiometric, Li-excess and Li-deficient lithium-manganese spinel oxide samples.

This work was supported by The Committee for Scientific Research (KBN) under the grant No 4T09A 164 23 (2002-2004).

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