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@ARTICLE{Voronina:894489,
author = {Voronina, Natalia and Kim, Hee Jae and Konarov, Aishuak and
Yaqoob, Najma and Lee, Kug-Seung and Kaghazchi, Payam and
Guillon, Olivier and Myung, Seung-Taek},
title = {{E}lectronic {S}tructure {E}ngineering of {H}oneycomb
{L}ayered {C}athode {M}aterial for {S}odium‐{I}on
{B}atteries},
journal = {Advanced energy materials},
volume = {11},
number = {14},
issn = {1614-6840},
address = {Weinheim},
publisher = {Wiley-VCH},
reportid = {FZJ-2021-03252},
pages = {2003399 -},
year = {2021},
abstract = {In this work, the rational design of O′3-type
Na[Ni2/3−xCoxSb1/3]O2, a solid solution of
Na[Ni2/3Sb1/3]O2–Na[Co2/3Sb1/3]O2, is introduced. Because
of the difficulty of the Co3+/2+ redox reaction, the
electronic structures of Na[Ni2/3−xCoxSb1/3]O2 compounds
are engineered to build electroconducting networks in the
oxide matrix through electrochemical oxidation of Co2+ to
Co3+, after which the formed Co3+ does not participate in
the electrochemical reaction but improves the electrical
conductivity in the structure. Density functional theory
calculations reveal a reduced bandgap energy after the
formation of Co3+ during desodiation of
Na1−y[Ni2/3−xCoxSb1/3]O2. Using the oxidized Co3+
species while improving the electrical conductivity, the
Na[Ni2/3−xCoxSb1/3]O2 (x = 1/6) electrode exhibits
excellent cyclability for 1000 cycles with $≈72.5\%$
capacity retention at 2C (400 mA g−1) and activity even at
50C (10 A g−1) in Na cells. Operando X-ray diffraction and
ex situ X-ray absorption near-edge structure investigations
reveal suppressed lattice variations upon charge and
discharge compared with those of Na[Ni2/3Sb1/3]O2 achieved
by the presence of the electrochemical-driven Co3+ in the
structure. These findings offer a new strategy for the
development of cathode materials for sodium-ion batteries,
providing important insight into their structural
transformations and the electronic nature of advanced
cathode materials.},
cin = {IEK-1 / JARA-ENERGY},
ddc = {050},
cid = {I:(DE-Juel1)IEK-1-20101013 / $I:(DE-82)080011_20140620$},
pnm = {1221 - Fundamentals and Materials (POF4-122)},
pid = {G:(DE-HGF)POF4-1221},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000620225300001},
doi = {10.1002/aenm.202003399},
url = {https://juser.fz-juelich.de/record/894489},
}