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@ARTICLE{Ghosh:474147,
author = {Ghosh, Subham and Barman, Nabadyuti and Gonzalez-Correa,
Eliovardo and Mazumder, Madhulika and Zaveri, Aryan and
Giovine, Raynald and Manche, Alexis and Pati, Swapan K. and
Clément, Raphaële J. and Senguttuvan, Premkumar},
title = {{E}lucidating the {I}mpact of {M}g {S}ubstitution on the
{P}roperties of {NASICON}‐{N}a$_{3+y}${V}$_{
2−y}${M}g$_y$({PO}$_4$)$_ 3$ {C}athodes},
journal = {Advanced functional materials},
volume = {31},
number = {48},
issn = {1057-9257},
address = {Weinheim},
publisher = {Wiley-VCH},
reportid = {PUBDB-2022-00537},
pages = {2105463},
year = {2021},
note = {The authors acknowledge DESY (Hamburg, Germany), a member
of the Helmholtz Association HGF, for the provision of
experimental facilities. Parts of this research were carried
out at PETRA III and the authors thank Dr. Edmund Welter for
his assistance in using Beamline P65, and DST for financial
assistance for the measurement at DESY.},
abstract = {Vanadium multiredox-based NASICON-NazV2−yMy(PO$_4$)$_3$
(3 ≤ z ≤ 4; M = Al$^{3+}$, Cr$^{3+}$, and Mn$^{2+}$)
cathodes are particularly attractive for Na-ion battery
applications due to their high Na insertion voltage (>3.5 V
vs Na$^+$/Na$^0$), reversible storage capacity (≈150 mA h
g$^{-1}$), and rate performance. However, their practical
application is hindered by rapid capacity fade due to bulk
structural rearrangements at high potentials involving
complex redox and local structural changes. To decouple
these factors, a series of Mg$^{2+}$-substituted
Na$_{3+y}$V$_{ 2−y}$Mg$_y$(PO$_4$)$_ 3$ (0 ≤ y ≤ 1)
cathodes is studied for which the only redox-active species
is vanadium. While X-ray diffraction (XRD) confirms the
formation of solid solutions between the y = 0 and 1 end
members, X-ray absorption spectroscopy and solid-state
nuclear magnetic resonance reveal a complex evolution of the
local structure upon progressive Mg$^{2+}$ substitution for
V$^{3+}$. Concurrently, the intercalation voltage rises from
3.35 to 3.45 V, due to increasingly more ionic VO bonds, and
the sodium (de)intercalation mechanism transitions from a
two-phase for y ≤ 0.5 to a solid solution process for y
≥ 0.5, as confirmed by in operando XRD, while Na-ion
diffusion kinetics follow a nonlinear trend across the
compositional series.},
cin = {DOOR ; HAS-User},
ddc = {530},
cid = {I:(DE-H253)HAS-User-20120731},
pnm = {6G3 - PETRA III (DESY) (POF4-6G3) / INDIA-DESY - INDIA-DESY
Collaboration $(2020_Join2-INDIA-DESY)$},
pid = {G:(DE-HGF)POF4-6G3 / $G:(DE-HGF)2020_Join2-INDIA-DESY$},
experiment = {EXP:(DE-H253)P-P65-20150101},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000690660700001},
doi = {10.1002/adfm.202105463},
url = {https://bib-pubdb1.desy.de/record/474147},
}