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@ARTICLE{Arifiadi:1025084,
author = {Arifiadi, Anindityo and Schmuch, Richard and Kasnatscheew,
Johannes and Winter, Martin},
title = {{E}stablishing an {A}ppropriate {V}oltage {W}indow for
{S}table {C}ycling of {L}i/{M}n-{R}ich {L}ayered {O}xide ||
{G}raphite {F}ull {C}ells},
journal = {Meeting abstracts},
volume = {MA2023-01},
number = {2},
issn = {1091-8213},
address = {Pennington, NJ},
publisher = {Soc.},
reportid = {FZJ-2024-02672},
pages = {665 - 665},
year = {2023},
note = {Hierbei handelt es sich lediglich um einen Abstract.},
abstract = {Li/Mn-rich layered oxide cathode active materials (LMR)
have gained attention due to their exceptionally high
practical specific discharge capacity (>250 mAh g-1)
originating from both conventional cationic as well as
anionic oxygen redox contributions. To achieve this high
capacity, the Li2MnO3-like regions of the material, which
give rise to oxygen redox need to be electrochemically
activated at high voltage (above 4.6 V versus Li+/Li0). This
high voltage activation, however, results in the
destabilization of lattice oxygen that creates subsequent
adverse phenomena such as first-cycle hysteresis and the
evolution of redox couples. The latter happens continuously
during cycling and results in the activation of Mn3+/Mn4+
redox couple. This redox couple involving Mn3+ is
problematic because, at this oxidation state, Mn
disproportionation reaction can occur, resulting in the
formation of highly soluble Mn2+ species. In a half-cell
setup, the impact of Mn dissolution may be subtle, however,
in LMR||Graphite full cells, the impact is
consequential.This work focuses on investigating the
degradation mechanism of LMR||Graphite full cells at
different voltage windows applied during the activation
cycles and the long-term cycling. These different voltage
windows alter the redox contributions and thus affect the
long-term performance of the cells. We observe that lowering
the upper cut-off voltage (UCV) from 4.7 V to 4.5 V during
the entire cycling process can increase capacity retention,
although rapid degradation can still be observed. Only when
the UCV during the long-term cycling is lowered to 4.3 V,
can we obtain incremental degradation of the cells. We also
show that lowering the activation cycles UCV to 4.5 V is
beneficial for long-term cycling due to the lower
contribution of Mn3+/Mn4+ redox couple after the activation
cycles. Finally, we observe that increasing the lower
cut-off voltage from 1.9 V to 2.4 V results in higher
discharge voltage. Nevertheless it is followed by a
reduction in discharge capacity, resulting in a lower
specific energy. This study offers insights into the
high-voltage cycling performance of practical LMR||Gr full
cells that can be used for the foundation of material design
to alleviate the adverse effect of oxygen redox in LMR.},
cin = {IEK-12},
ddc = {540},
cid = {I:(DE-Juel1)IEK-12-20141217},
pnm = {1221 - Fundamentals and Materials (POF4-122)},
pid = {G:(DE-HGF)POF4-1221},
typ = {PUB:(DE-HGF)16},
doi = {10.1149/MA2023-012665mtgabs},
url = {https://juser.fz-juelich.de/record/1025084},
}