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@ARTICLE{Sharma:867204,
author = {Sharma, Monika and Gupta, Mukul and Kaghazchi, Payam and
Murugavel, Sevi},
title = {{S}ize induced structural changes in maricite-{N}a{F}e{PO}
4 : an in-depth study by experiment and simulations},
journal = {Physical chemistry, chemical physics},
volume = {21},
number = {45},
issn = {1463-9084},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {FZJ-2019-06021},
pages = {25206 - 25214},
year = {2019},
abstract = {Rechargeable batteries based on the most abundant elements,
such as sodium and iron, have a great potential in the
development of cost effective sodium ion batteries for large
scale energy storage devices. We report, for the first time,
crystallite size dependent structural investigations on
maricite-NaFePO4 through X-ray diffraction, X-ray absorption
spectroscopy and theoretical simulations. Rietveld
refinement analysis on the X-ray diffraction data reveals
that a decrease in the unit cell parameters leads to volume
contraction upon reduction in the crystallite size. Further,
the atomic multiplet simulations on X-ray absorption spectra
provide unequivocally a change in the site symmetry of
transition metal ions. The high resolution oxygen K-edge
spectra reveal a substantial change in the bonding character
with the reduction of crystallite size, which is the
fundamental cause for the change in the unit cell parameters
of maricite-NaFePO4. In parallel, we performed
first-principles density functional theory (DFT)
calculations on maricite-NaFePO4 with different sodium ion
vacancy concentrations. The obtained structural parameters
are in excellent agreement with the experimental
observations on the mesostructured maricite-NaFePO4. The
volumetric changes with respect to crystallite size are
related to the compressive strain, resulting in the
improvement in the electronic diffusivity. The
nano-crystalline maricite-NaFePO4 with improved kinetics
will open a new avenue for its usage as a cathode material
in sodium ion batteries.},
cin = {IEK-1},
ddc = {540},
cid = {I:(DE-Juel1)IEK-1-20101013},
pnm = {131 - Electrochemical Storage (POF3-131)},
pid = {G:(DE-HGF)POF3-131},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:31696889},
UT = {WOS:000506841300033},
doi = {10.1039/C9CP03838H},
url = {https://juser.fz-juelich.de/record/867204},
}