Spinel–rock salt transformation in LiCoMnO4−δ
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Other documents of the author: Reeves-McLaren, Nik; Sharp, Joanne; Beltrán Mir, Héctor; Rainforth, William; West, Anthony R.
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comunitat-uji-handle2:10234/7053
comunitat-uji-handle3:10234/8639
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Title
Spinel–rock salt transformation in LiCoMnO4−δAuthor (s)
Date
2016Publisher
The Royal SocietyISSN
1364-5021; 1471-2946Bibliographic citation
Reeves-McLaren N, Sharp J, Beltrán-Mir H, Rainforth WM, West AR. 2016 Spinel–rock salt transformation in LiCoMnO4−δ.Proc. R. Soc. A 472: 20140991. http://dx.doi.org/10.1098/rspa.2014.0991Type
info:eu-repo/semantics/articlePublisher version
http://rspa.royalsocietypublishing.org/content/472/2185/20140991#pageSubject
Abstract
The transformation on heating LiCoMnO4, with
a spinel structure, to LiCoMnO3, with a cationdisordered
rock salt structure, accompanied by
loss of 25% of the oxygen, has been followed
using a combination of diffr ... [+]
The transformation on heating LiCoMnO4, with
a spinel structure, to LiCoMnO3, with a cationdisordered
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. [-]
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