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Spinel-rock salt transformation in LiCoMnO4-?.


ABSTRACT: The transformation on heating LiCoMnO4, with a spinel structure, to LiCoMnO3, with a cation-disordered rock salt structure, accompanied by loss of 25% of the oxygen, has been followed using a combination of diffraction, microscopy and spectroscopy techniques. The transformation does not proceed by a topotactic mechanism, even though the spinel and rock salt phases have a similar, cubic close-packed oxygen sublattice. Instead, the transformation passes through two stages involving, first, precipitation of Li2MnO3, leaving behind a Li-deficient, Co-rich non-stoichiometric spinel and, second, rehomogenization of the two-phase assemblage, accompanied by additional oxygen loss, to give the homogeneous rock salt final product; a combination of electron energy loss spectroscopy and X-ray absorption near edge structure analyses showed oxidation states of Co2+ and Mn3+ in LiCoMnO3. Subsolidus phase diagram determination of the Li2O-CoO x -MnO y system has established the compositional extent of spinel solid solutions at approximately 500°C.

SUBMITTER: Reeves-McLaren N 

PROVIDER: S-EPMC4786028 | biostudies-literature | 2016 Jan

REPOSITORIES: biostudies-literature

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Spinel-rock salt transformation in LiCoMnO<sub>4-<i>δ</i></sub>.

Reeves-McLaren Nik N   Sharp Joanne J   Beltrán-Mir Héctor H   Rainforth W Mark WM   West Anthony R AR  

Proceedings. Mathematical, physical, and engineering sciences 20160101 2185


The transformation on heating LiCoMnO<sub>4</sub>, with a spinel structure, to LiCoMnO<sub>3</sub>, with a cation-disordered rock salt structure, accompanied by loss of 25% of the oxygen, has been followed using a combination of diffraction, microscopy and spectroscopy techniques. The transformation does not proceed by a topotactic mechanism, even though the spinel and rock salt phases have a similar, cubic close-packed oxygen sublattice. Instead, the transformation passes through two stages inv  ...[more]

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