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@PHDTHESIS{Dellen:829751,
author = {Dellen, Christian},
title = {{Q}uantitative {A}nalyse der {L}ithiumverteilung in
{K}athoden und {E}lektrolyt-{D}ünnschichten für
{F}estkörperbatterien},
volume = {363},
school = {Universität Bochum},
type = {Dr.},
address = {Jülich},
publisher = {Forschungszentrum Jülich GmbH Zentralbibliothek, Verlag},
reportid = {FZJ-2017-03385},
isbn = {978-3-95806-214-6},
series = {Schriften des Forschungszentrums Jülich Reihe Energie $\&$
Umwelt / Energy $\&$ Environment},
pages = {vi, 161 S.},
year = {2017},
note = {Universität Bochum, Diss., 2016},
abstract = {When searching for new powerful energy storage systems for
mobile consumer electronics and a sustainable energy supply,
the development in the field of lithium ion batteries was
highly pushed in last years. As part of this development the
so called solid state batteries have recently attracted a
lot of attention as a promising energy storage system for
future applications. In a solid state battery the
combustible liquid electrolyte, which is used in
conventional lithium ion batteries, is replaced by a solid
state li ion conductor. Hereby the safety and the
performance of the battery system can be increased
tremendously. Within this work the quantitative analysis of
the lithium distribution in cathode and electrolyte thin
films for solid state batteries is addressed as one major
issue of the current battery research. The lithium
distribution can be regarded as a crucial parameter within
the processing of battery materials as well as in the
operation of the whole battery system. Unfortunately lithium
cannot be quantified by the commonly used characterization
techniques. Therefore secondary ion mass spectrometry (SIMS)
was used in this work to derive depth resolved concentration
profiles of lithium containing thin films. As model systems
for the quantitative analysis of lithium, thin films of the
cathode material LiCoO$_{2}$ and the solid state electrolyte
Li$_{6.6}$La$_{3}$Zr$_{1.6}$Ta$_{0.4}$O$_{12}$ were
selected. These were prepared by magnetron sputtering and
characterized with a variety of analytical techniques. In
addition to the SIMS as the primary analytical method,
further techniques like nuclear reaction analysis (NRA),
Rutherford backscattering (RBS) and glow discharge optical
emission spectroscopy (GDOES) were employed. In case of the
LiCoO$_{2}$ thin films, the lithium distribution was
investigated as a function of the cathode’s state of
charge. Therefore the thin films were first cycled in the
voltage range from 3.0 V to 4.1 V vs. Li/Li$^{+}$ and
afterwards the elemental composition was analyzed. These
measurements revealed a stepwise lithium profile in the
charged LiCoO$_{2}$ thin films, showing a delithiated area
close to the electrolyte facing surface and a fully
lithiated area in the proximity of the substrate. In
addition, quantitative SIMS concentration profiles were
calculated with relative sensitivity factors (RSF), derived
from NRA reference measurements. These profiles showed that
the surface area of the charged thin film cathodes is
delithiated below the reversible limit of
Li$_{0.5}$CoO$_{2}$, which is well known for bulk
LiCoO$_{2}$ cathodes. The elemental distribution within the
Li$_{6.6}$La$_{3}$Zr$_{1.6}$Ta$_{0.4}$O$_{12}$ thin films
was analysed as a function of the deposition temperature.
The combined SIMS and NRA analysis of thin films deposited
in the temperature range between 150 $^{\circ}$C and 800
$^{\circ}$C revealed an increasing lithium concentration
with temperature. At elevated temperatures, the formation of
an Al$_{2}$O$_{3}$ interlayer on top of the used FeCrAlY
substrates was observed as well as the reaction of this
interlayer with lithium from the
Li$_{6.6}$La$_{3}$Zr$_{1.6}$Ta$_{0.4}$O$_{12}$. The measured
elemental distribution was also affected by a surface
reaction of the lithium rich
Li$_{6.6}$La$_{3}$Zr$_{1.6}$Ta$_{0.4}$O$_{12}$ thin films.
In principle, the quantitative SIMS analyses were able to
visualize the depth resolved changes in the lithium
concentration. But in comparison to the NRA results, the
SIMS analyses systematically overestimated the absolute
lithium content.},
cin = {IEK-1},
cid = {I:(DE-Juel1)IEK-1-20101013},
pnm = {131 - Electrochemical Storage (POF3-131)},
pid = {G:(DE-HGF)POF3-131},
typ = {PUB:(DE-HGF)3 / PUB:(DE-HGF)11},
url = {https://juser.fz-juelich.de/record/829751},
}