Nano-domain structure of Li4Mn5O12 spinel
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XRD-pure Li4Mn5O12 spinels are obtained below 600 °C from oxalate and acetate precursors. The morphology consists of nanometric particles (about 25 nm) with a narrow particle size distribution. HRTEM and electron paramagnetic resonance (EPR) spectroscopy of Mn4+ are employed for local structure analysis. The HRTEM images recorded on nano-domains in Li4Mn5O12 reveal its complex structure. HRTEM shows one-dimensional structure images, which are compatible with the (111) plane of the cubic spinel structure and the (001) plane of monoclinic Li2MnO3. For Li4Mn5O12 compositions annealed between 400 and 800 °C, EPR spectroscopy shows the appearance of two types of Mn4+ ions having different metal environments: (i) Mn4+ ions surrounded by Li+ and Mn4+ and (ii) Mn4+ ions in Mn4+-rich environment. The composition of the Li+, Mn4+-shell around Mn4+ mimics the local environment of Mn4+ in monoclinic Li2MnO3, while the Mn4+-rich environment is related with that of the spinel phase. The structure of XRD-pure Li4Mn5O12 comprises nano-domains with a Li2MnO3-like and a Li4/3−xMn5/3+xO4 composition rather than a single spinel phase with Li in tetrahedral and Li1/3Mn5/3 in octahedral spinel sites. The annealing of Li4Mn5O12 at temperature higher than 600 °C leads to its decomposition into monoclinic Li2MnO3 and spinel Li4/3−xMn5/3+xO4.
KeywordsElectron Paramagnetic Resonance Electron Paramagnetic Resonance Spectrum Electron Paramagnetic Resonance Signal Spinel Phase Electron Paramagnetic Resonance Spectroscopy
Authors are grateful to the financial support from the National Science Fund of Bulgaria (Ch1701/2007). Partial financial support by the National Centre for New Materials UNION (Contract No DCVP-02/2/2009) is also acknowledged.
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