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@ARTICLE{Gallus:840033,
author = {Gallus, Dennis Roman and Wagner, Ralf and Wiemers-Meyer,
Simon and Winter, Martin and Cekic-Laskovic, Isidora},
title = {{N}ew insights into the structure-property relationship of
high-voltage electrolyte components for lithium-ion
batteries using the p{K}a value},
journal = {Electrochimica acta},
volume = {184},
issn = {0013-4686},
address = {New York, NY [u.a.]},
publisher = {Elsevier},
reportid = {FZJ-2017-07599},
pages = {410 - 416},
year = {2015},
abstract = {In pursuit of higher energy density in lithium-ion
batteries (LIBs), a most promising approach focuses on
cathode materials that operate at higher potentials and
exhibit even higher specific charges than present LIB
cathodes charged up to only 3.8 to 4.3 V vs. Li/Li+. To
enable a high-voltage (HV) application of the cathode, the
“by-materials”, in particular the electrolyte components
have to be either thermodynamically or kinetically stable.
For this reason, the stability of the electrolyte components
towards oxidation, in particular, depending on their HOMO
energy levels, is crucial. The theoretical calculation of
molecular orbital energies is a helpful and commonly used
tool to predict electrochemical stability. Earlier studies
demonstrated strong correlation between the HOMO energy and
the pKa value, as both depend on electron affinity. Here we
report on the first study referring to a pKa value based
selection procedure on development of new electrolyte
components for the application in lithium-ion batteries. The
identified trimethylsilyl(TMS)-based additives, which are
known to scavenge HF and show sufficient oxidation
stability, enable the application of LiNi1/3Co1/3Mn1/3O2
(NCM) at an increased upper cut-off potential of 4.6 V vs.
Li/Li+ without severe degradation, leading to a $50\%$
higher energy density. The use of pKa values is a simple,
but highly effective methodology to select appropriate
electrolyte components and thus helps to identify functional
electrolytes beyond the typical trial and error approach or
time-consuming theoretical calculations.},
cin = {IEK-12},
ddc = {540},
cid = {I:(DE-Juel1)IEK-12-20141217},
pnm = {131 - Electrochemical Storage (POF3-131)},
pid = {G:(DE-HGF)POF3-131},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000366016900052},
doi = {10.1016/j.electacta.2015.10.002},
url = {https://juser.fz-juelich.de/record/840033},
}