Abstract
Abstract Nanocrystalline LiMn 2 O 4 spinel oxides have been synthesized successfully by using a modified citrate route with ethanol dehydration of a Li–Mn–citrate complex solution. The effects of sintering temperature and atmosphere on the physicochemical properties of the LiMn 2 O 4 powders have been carefully examined by means of X-ray diffraction, electron microscopy, BET measurement, and X-ray absorption spectroscopy. It becomes clear that an oxidative atmosphere induces a partial agglomeration of particles at high temperature, but gives rise to an effective decomposition of the citrate precursors at low temperature. It is also found that a lowering of the sintering temperature enhances the average oxidation state of manganese with an increase in surface defects. The electrochemical property of the present LiMn 2 O 4 nanocrystals has also been measured to compare with that of lithium manganate prepared by a solid-state reaction, which confirms the effectiveness of the present modified citrate route. The evolution of geometrical and electronic structures during the charging process has also been investigated with X-ray absorption spectroscopy, and reveals shortening of the (Mn–O) bond distances induced by lithium de-intercalation.
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