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@ARTICLE{Moy:1025219,
author = {Moy, Alexandra C. and Häuschen, Grit and
Fattakhova-Rohlfing, Dina and Wolfenstine, Jeffrey B. and
Finsterbusch, Martin and Sakamoto, Jeff},
title = {{T}he effects of aluminum concentration on the
microstructural and electrochemical properties of lithium
lanthanum zirconium oxide},
journal = {Journal of materials chemistry / A},
volume = {10},
number = {41},
issn = {2050-7488},
address = {London [u.a.]},
publisher = {RSC},
reportid = {FZJ-2024-02787},
pages = {21955 - 21972},
year = {2022},
abstract = {Cubic lithium lanthanum zirconium oxide
(Li7−xAlxLa3Zr2O12, LLZO) garnet has gained attention as a
promising next-generation electrolyte for lithium batteries
due to its high ionic conductivity and chemical stability
with lithium metal. The high conductivity can be achieved
through doping over a range of aluminum concentrations. In
this study, we hot-pressed samples to achieve $<2\%$ nominal
porosity with aluminum concentrations from x = 0.25–0.55
mol to understand the effect of aluminum on microstructure
and electrochemistry. It was observed that beyond the
aluminum solubility limit (x = ∼0.40), resistive secondary
phases formed at the grain boundaries. As a result, the
percent grain boundary resistance increased from 17.6 to
$41.2\%$ for x = 0.25 and x = 0.55, respectively. Both the
grain boundary and bulk activation energies remained
relatively constant as the aluminum concentrations increased
(∼0.44 eV and ∼0.39 eV, respectively). It was,
therefore, surmised that the mobility term of the
Nernst–Einstein equation was roughly independent of
aluminum concentration and the major variable controlling
bulk conductivity was the number of lithium charge carriers.
As a result, as the aluminum concentration increased from x
= 0.25 to x = 0.55 the bulk conductivity decreased from 0.56
to 0.15 mS cm−1. Following these trends of increasing
grain boundary resistance and decreasing bulk conductivity
with increasing aluminum concentration, x = 0.25 had the
highest total conductivity (0.46 mS cm−1). We demonstrated
that aluminum concentration has a significant effect on the
microstructure and electrochemical properties of LLZO. We
believe this work could help understand how to link
processing, microstructure, and electrochemical properties
to guide the manufacturing of LLZO for use in solid-state
batteries.},
cin = {IEK-1},
ddc = {530},
cid = {I:(DE-Juel1)IEK-1-20101013},
pnm = {1221 - Fundamentals and Materials (POF4-122) / 1222 -
Components and Cells (POF4-122)},
pid = {G:(DE-HGF)POF4-1221 / G:(DE-HGF)POF4-1222},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000861716200001},
doi = {10.1039/D2TA03676B},
url = {https://juser.fz-juelich.de/record/1025219},
}