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@ARTICLE{Lechtenfeld:1025070,
author = {Lechtenfeld, Christian and Peschel, Christoph and Van
Wickeren, Stefan and Bloch, Aleksandra and Winter, Martin
and Nowak, Sascha},
title = {{A}nalysis of the {D}ecomposition of {S}ulfur-{B}ased
{E}lectrolyte {A}dditives in {S}pent {L}i{N}i 0.6 {C}o 0.2
{M}n 0.2 {O} 2 ||{AG} {C}ells},
journal = {Meeting abstracts},
volume = {MA2023-01},
number = {2},
issn = {1091-8213},
address = {Pennington, NJ},
publisher = {Soc.},
reportid = {FZJ-2024-02658},
pages = {649 - 649},
year = {2023},
note = {Hierbei handelt es sich lediglich um einen Abstract.},
abstract = {The development and optimization processes of the last
decades in the context of lithium ion batteries (LIBs) have
led to a variety of electrode chemistries, which enable
application-specific targets such as high energy, high
power, high safety or long lifetime. Most of these LIB
systems rely on a liquid carbonate-based electrolyte, whose
basic composition has changed scarcely during this period.1
In this respect, the usage of electrolyte additives is one
of the most economical and effective ways to further improve
the overall performance, while also impact the
application-tailored characteristics of the battery cells at
the elctrolyte level without changing the bulk properties.2
These improvements can range from overcharge protection to
lowered flammability or interphase formation, among others.
In particular, film-forming additives signifcantly influence
the performance and life time of LIBs by preventing
excessive decomposition of the electrolyte, which is in
contact with the positive and negative electrodes, by the
formation of a passivation layer. Investigating the
electrochemical decomposition of the electrolyte components,
especially electrolyte additives, is key to enable a better
understanding of the composition from the
electrode||electrolyte interface layer and the effects on
LIB cell performance.3 Thus, aging mechanisms and parasitic
reactions can be elucidated to improve and design new
electrolyte additives.Herein, the irreversible decomposition
of sulfur-containing electrolyte additives will be
addressed. Sulfur-containing additives represent an
attractive option for film-forming additives as these
compounds endow lower energies in the lowest unoccupied
molecular orbital (LUMO) compared to the organic carbonate
analogs and therefore are more susceptible to
electrochemical reduction.4 However, these class of
electrolyte additives find only a limited use in
state-of-the-art electrolyte mixtures due to the often
reported or suspected carcinogenicity and toxicity towards
the human body. Nevertheless, since sulfur-containing
additives still play an important role in spent LIBs of
recent decades, identification of these hazardous compounds
and formed aging products, which should be also classified
as potential dangers, is of great interest.1This
contribution focused on the identification of aging products
emerging in electrolytes from LIB cells using sulfur-based
electrolyte additives of different chemical classes such as
sulfates, sulfites, sultones and sulfonates. Ion
chromatography and gas chromatography hyphenated to
high-resolution acurrate mass spectrometry (HRAM-MS) were
used to obtain information on the formation of ionic and
volatile compounds after electrochemical operation and to
elucidate the corresponding structures. Thus, specific ionic
and volatile aging marker molecules could be defined for
target-analysis of the original electrolyte additive in LIB
material, despite a potentially complete consumption during
cycling. This allows improved reverse-engineering of LIB
post-mortem analysis and risk assessment. Furthermore,
mechanistic conclusions on the decomposition of the
investigated electrolyte additives could be drawn, extending
literature reports based on X-Ray methods with respect to
species information and ultimately contribute to a better
understanding of the interphase constitutions.[1] C.
Peschel, S. van Wickeren, A. Bloch, C. Lechtenfeld, M.
Winter, S. Nowak, Energy Technol.2022, xxx.[2] S. S. Zhang,
J. Power Sources2006, 162, 1379–1394.[3] J. Henschel, J.
M. Dressler, M. Winter, S. Nowak, Chem. Mater. 2019 31 (24),
9970-9976.[4] B. Tong, Z. Song, H. Wan, W. Feng, M. Armand,
J. Liu, H. Zhang, Z. Zhou, InfoMat2021, 3, 1364–1392.},
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/MA2023-012649mtgabs},
url = {https://juser.fz-juelich.de/record/1025070},
}