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@ARTICLE{Daniel:1008999,
author = {Daniel, Davis Thomas and Oevermann, Steffen and Mitra,
Souvik and Rudolf, Katharina and Heuer, Andreas and Eichel,
Rüdiger-A. and Winter, Martin and Diddens, Diddo and
Brunklaus, Gunther and Granwehr, Josef},
title = {{M}ultimodal investigation of electronic transport in
{PTMA} and its impact on organic radical battery
performance},
journal = {Scientific reports},
volume = {13},
number = {1},
issn = {2045-2322},
address = {[London]},
publisher = {Macmillan Publishers Limited, part of Springer Nature},
reportid = {FZJ-2023-02568},
pages = {10934},
year = {2023},
abstract = {Organic radical batteries (ORBs) represent a viable pathway
to a more sustainable energy storage technology compared
toconventional Li-ion batteries. For further materials and
cell development towards competitive energy and power
densities, adeeper understanding of electron transport and
conductivity in organic radical polymer cathodes is
required. Such electrontransport is characterised by
electron hopping processes, which depend on the presence of
closely spaced hopping sites.Using a combination of
electrochemical, electron paramagnetic resonance (EPR)
spectroscopic, and theoretical moleculardynamics (MD) as
well as density functional theory (DFT) modelling
techniques, we explored how compositional characteristicsof
cross-linked poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl
methacrylate) (PTMA) polymers govern electron hopping
andrationalise their impact on ORB performance.
Electrochemistry and EPR spectroscopy not only show a
correlation betweencapacity and the total number of radicals
in an ORB using a PTMA cathode, but also indicates that the
state-of-health degradesabout twice as fast if the amount of
radical is reduced by $15\%.$ The presence of up to $3\%$
free monomer radicals did not improvefast charging
capabilities. Pulsed EPR indicated that these radicals
readily dissolve into the electrolyte but a direct effect
onbattery degradation could not be shown. However, a
qualitative impact cannot be excluded either. The work
further illustratesthat nitroxide units have a high affinity
to the carbon black conductive additive, indicating the
possibility of its participation inelectron hopping. At the
same time, the polymers attempt to adopt a compact
conformation to increase radical–radical contact.Hence, a
kinetic competition exists, which might gradually be altered
towards a thermodynamically more stable configuration
byrepeated cycling, yet further investigations are required
for its characterisation.},
cin = {IEK-12 / IEK-9},
ddc = {600},
cid = {I:(DE-Juel1)IEK-12-20141217 / I:(DE-Juel1)IEK-9-20110218},
pnm = {1222 - Components and Cells (POF4-122) / 1223 - Batteries
in Application (POF4-122) / DFG project 422726248 - SPP
2248: Polymer-basierte Batterien (422726248) / HITEC -
Helmholtz Interdisciplinary Doctoral Training in Energy and
Climate Research (HITEC) (HITEC-20170406)},
pid = {G:(DE-HGF)POF4-1222 / G:(DE-HGF)POF4-1223 /
G:(GEPRIS)422726248 / G:(DE-Juel1)HITEC-20170406},
typ = {PUB:(DE-HGF)16},
pubmed = {37414786},
UT = {WOS:001026209100048},
doi = {10.1038/s41598-023-37308-5},
url = {https://juser.fz-juelich.de/record/1008999},
}