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@ARTICLE{McCalla:189319,
author = {McCalla, Eric and Abakumov, Artem and Rousse, Gwenaelle and
Reynaud, Marine and Sougrati, Moulay Tahar and Budic, Bojan
and Mahmoud, Abdelfattah and Dominko, Robert and Van
Tendeloo, Gustaaf and Tarascon, Jean-Marie and Hermann,
Raphael},
title = {{N}ovel {C}omplex {S}tacking of {F}ully-{O}rdered
{T}ransition {M}etal {L}ayers in {L}i $_{4}$ {F}e{S}b{O}
$_{6}$ {M}aterials},
journal = {Chemistry of materials},
volume = {27},
number = {5},
issn = {1520-5002},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {FZJ-2015-02497},
pages = {1699 - 1708},
year = {2015},
abstract = {As part of a broad project to explore Li4MM′O6 materials
(with M and M′ being selected from a wide variety of
metals) as positive electrode materials for Li-ion
batteries, the structures of Li4FeSbO6 materials with both
stoichiometric and slightly deficient lithium contents are
studied here. For lithium content varying from 3.8 to 4.0,
the color changes from yellow to black and extra
superstructure peaks are seen in the XRD patterns. These
extra peaks appear as satellites around the four
superstructure peaks affected by the stacking of the
transition metal atoms. Refinements of both XRD and neutron
scattering patterns show a nearly perfect ordering of Li,
Fe, and Sb in the transition metal layers of all samples,
although these refinements must take the stacking faults
into account in order to extract information about the
structure of the TM layers. The structure of the most
lithium rich sample, where the satellite superstructure
peaks are seen, was determined with the help of HRTEM, XRD,
and neutron scattering. The satellites arise due to a new
stacking sequence where not all transition metal layers are
identical but instead two slightly different compositions
stack in an AABB sequence giving a unit cell that is four
times larger than normal for such monoclinic layered
materials. The more lithium deficient samples are found to
contain metal site vacancies based on elemental analysis and
Mössbauer spectroscopy results. The significant changes in
physical properties are attributed to the presence of these
vacancies. This study illustrates the great importance of
carefully determining the final compositions in these
materials, as very small differences in compositions may
have large impacts on structures and properties.},
cin = {JCNS-2 / PGI-4 / JARA-FIT},
ddc = {540},
cid = {I:(DE-Juel1)JCNS-2-20110106 / I:(DE-Juel1)PGI-4-20110106 /
$I:(DE-82)080009_20140620$},
pnm = {144 - Controlling Collective States (POF3-144) / 524 -
Controlling Collective States (POF3-524) / 6213 - Materials
and Processes for Energy and Transport Technologies
(POF3-621) / 6G4 - Jülich Centre for Neutron Research
(JCNS) (POF3-623)},
pid = {G:(DE-HGF)POF3-144 / G:(DE-HGF)POF3-524 /
G:(DE-HGF)POF3-6213 / G:(DE-HGF)POF3-6G4},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000350919000032},
doi = {10.1021/cm504500a},
url = {https://juser.fz-juelich.de/record/189319},
}