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@ARTICLE{Evertz:851129,
author = {Evertz, Marco and Schwieters, Timo and Börner, Markus and
Winter, Martin and Nowak, Sascha},
title = {{M}atrix-matched standards for the quantification of
elemental lithium ion battery degradation products deposited
on carbonaceous negative electrodes using pulsed-glow
discharge-sector field-mass spectrometry},
journal = {Journal of analytical atomic spectrometry},
volume = {32},
number = {10},
issn = {1364-5544},
address = {Cambridge},
publisher = {ChemSoc},
reportid = {FZJ-2018-04831},
pages = {1862 - 1867},
year = {2017},
abstract = {In this work an external calibration approach for glow
discharge-sector field-mass spectrometry (GD-SF-MS) using
matrix-matched self-prepared carbonaceous standards for
elemental battery degradation products of
LiNi1/3Co1/3Mn1/3O2 (NCM111) positive electrodes like
lithium, manganese, cobalt and nickel is adapted. Firstly,
the standards were prepared using graphite mixed with
increasing contents of NCM111 which was coated on a thin
copper foil as a current collector. The homogeneous
distribution of NCM111 in the standards was proven via
SEM/EDX images and the bulk homogeneity of the electrode
sheets was validated via ICP-OES. Afterwards, sufficient
linearity could be obtained in a calibration range of 1 mg
g−1 to 28 mg g−1 for 7Li with respect to the active
material mass. Additionally, the matrix-matched relative
sensitivity factors (RSFs) of each element could be
calculated. Limits of detection (LODs) ranging from 80 μg
g−1 (7Li) up to 393 μg g−1 (58Ni) could be achieved at
low (R > 300) and medium (R > 4000) resolutions for the
Element GD, respectively. Secondly, we adapted the
matrix-matched RSF values in order to investigate cycled
electrodes by monitoring the 7Li signal as well as common
isotopes from lithium ion batteries – such as 31P and 19F,
originating from the conducting salt – and transition
metals to conduct depth-resolved analysis. The concentration
of transition metals in all of the cycled electrodes was
below the LOD of the GD-SF-MS method which was investigated
in a previous study, showing a maximum bulk deposition of
transition metals of 4.5 mg g−1. As expected, an
accumulation of 7Li in the first few minutes (=surface
layers) of sputtering was observed in the cycled
carbonaceous negative electrodes followed by a decreasing
7Li signal with ongoing sputtering indicating the presence
of a solid electrolyte interphase (SEI) passivation layer.},
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:000414347800003},
doi = {10.1039/C7JA00129K},
url = {https://juser.fz-juelich.de/record/851129},
}