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@ARTICLE{Maiti:1019405,
author = {Maiti, Moumita and Krishnamoorthy, Anand Narayanan and
Mabrouk, Youssef and Mozhzhukhina, Nataliia and Matic,
Aleksandar and Diddens, Diddo and Heuer, Andreas},
title = {{M}echanistic understanding of the correlation between
structure and dynamics of liquid carbonate electrolytes:
impact of polarization},
journal = {Physical chemistry, chemical physics},
volume = {25},
number = {30},
issn = {1463-9076},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {FZJ-2023-05365},
pages = {20350 - 20364},
year = {2023},
abstract = {Liquid electrolyte design and modelling is an essential
part of the development of improved lithium ion batteries.
For mixed organic carbonates (ethylene carbonate (EC) and
ethyl–methyl carbonate (EMC) mixtures)-based electrolytes
with LiPF6 as salt, we have compared a polarizable force
field with the standard non-polarizable force field with and
without charge rescaling to model the structural and dynamic
properties. The result of our molecular dynamics simulations
shows that both polarizable and non-polarizable force fields
have similar structural factors, which are also in agreement
with X-ray diffraction experimental results. In contrast,
structural differences are observed for the lithium
neighborhood, while the lithium–anion neighbourhood is
much more pronounced for the polarizable force field.
Comparison of EC/EMC coordination statistics with Fourier
transformed infrared spectroscopy (FTIR) shows the best
agreement for the polarizable force field. Also for
transport quantities such as ionic conductivities,
transference numbers, and viscosities, the agreement with
the polarizable force field is by far better for a large
range of salt concentrations and EC[thin space
(1/6-em)]:[thin space (1/6-em)]EMC ratios. In contrast, for
the non-polarizable variants, the dynamics are largely
underestimated. The excellent performance of the polarizable
force field is explored in different ways to pave the way to
a realistic description of the structure–dynamics
relationships for a wide range of salt and solvent
compositions for this standard electrolyte. In particular,
we can characterize the distinct correlation terms between
like and unlike ions, relate them to structural properties,
and explore to which degree the transport in this
electrolyte is mass or charge limited.},
cin = {IEK-12},
ddc = {540},
cid = {I:(DE-Juel1)IEK-12-20141217},
pnm = {1221 - Fundamentals and Materials (POF4-122) / BIG-MAP -
Battery Interface Genome - Materials Acceleration Platform
(957189)},
pid = {G:(DE-HGF)POF4-1221 / G:(EU-Grant)957189},
typ = {PUB:(DE-HGF)16},
pubmed = {37465859},
UT = {WOS:001031236300001},
doi = {10.1039/D3CP01236K},
url = {https://juser.fz-juelich.de/record/1019405},
}