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@ARTICLE{Li:599477,
author = {Li, Yongchun and Mazzio, Katherine and Yaqoob, Najma and
Sun, Yanan and Freytag, Annica and Wong, Deniz and Schulz,
Christian and Baran, Volodymyr and San Jose Mendez, Alba and
Schuck, Götz and Zając, Marcin and Kaghazchi, Payam and
Adelhelm, Philipp},
title = {{C}ompeting mechanisms determine oxygen redox in doped
{N}i-{M}n based layered oxides for {N}a-ion batteries},
reportid = {PUBDB-2023-07449},
year = {2023},
abstract = {Cation doping is an effective strategy for improving the
cyclability of layered oxide cathode materials through
suppression of phase transitions in the high voltage region
(>~4.0V). In this study we choose Mg and Sc as
representative dopants in P2-
Na$_{0.67}$Ni$_{0.33}$Mn$_{0.67}$O$_2$. While both dopants
have a positive effect on the cycling stability, they are
found to influence the properties in the high voltage regime
in different ways. Through a combination of RIXS, XRD, XAS,
PDF analysis, and DFT, we show that it is more than just
suppression of the P2 to O$_2$ phase transition that is
critical for promoting the favorable properties, and that
the interplay between Ni and O activity are also critical
aspects that dictate the performance. With Mg doping, we
could enhance the Ni activity while simultaneously
suppressing the O activity. This is surprising because it is
in contrast to what has been reported in other Mn-based
layered oxides where Mg is known to trigger oxygen redox. We
address this contradiction by proposing a competing
mechanism between Ni and Mg that impacts differences in O
activity in Na$_{0.67}$Mg$_x$Ni$_{0.33-x}$Mn$_{0.67}$O$_2$
(x<0<0.33). These findings provide a new direction in
understanding the effects of cation doping on the
electrochemical behavior of layered oxides.},
cin = {DOOR ; HAS-User / FS-PETRA-D},
cid = {I:(DE-H253)HAS-User-20120731 /
I:(DE-H253)FS-PETRA-D-20210408},
pnm = {632 - Materials – Quantum, Complex and Functional
Materials (POF4-632) / 6G3 - PETRA III (DESY) (POF4-6G3)},
pid = {G:(DE-HGF)POF4-632 / G:(DE-HGF)POF4-6G3},
experiment = {EXP:(DE-H253)P-P02.1-20150101},
typ = {PUB:(DE-HGF)25},
doi = {10.26434/chemrxiv-2023-jfnmr},
url = {https://bib-pubdb1.desy.de/record/599477},
}