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Spinel–rock salt transformation in LiCoMnO

DOI: 10.1098/rspa.2014.0991 DOI Help

Authors: Nik Reeves-mclaren (University of Sheffield) , Joanne Sharp (University of Sheffield) , Héctor Beltrán-mir (Universidad Jaume I) , W. Mark Rainforth (University of Sheffield) , Anthony R. West (University of Sheffield)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Proceedings Of The Royal Society A: Mathematical, Physical And Engineering Science , VOL 472

State: Published (Approved)
Published: January 2016
Diamond Proposal Number(s): 4591

Open Access Open Access

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-CoOx-MnOy system has established the compositional extent of spinel solid solutions at approximately 500°C.

Journal Keywords: LiCoMnO4 Rietveld electron energy loss spectroscopy X-ray absorption near edge structure Raman oxygen loss

Subject Areas: Chemistry, Energy, Materials

Instruments: I18-Microfocus Spectroscopy

Added On: 19/01/2016 15:21

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