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@ARTICLE{Faka:1042707,
author = {Faka, Vasiliki and Samanta, Bibek and Lange, Martin A. and
Helm, Bianca and Martinez de Irujo-Labalde, Xabier and
Kierdorf, Niklas and Ketter, Lukas and Suard, Emmanuelle and
Kraft, Marvin A. and Francisco, Brian E. and Hansen, Michael
Ryan and Zeier, Wolfgang},
title = {{E}nhancing ionic conductivity in ${L}i_{6+ x} {G}e_x
{P}_{1−x}{S}_5{B}r$: impact of ${L}i^+$ substructure on
ionic transport and solid-state battery performance},
journal = {Journal of materials chemistry / A},
volume = {7},
issn = {2050-7488},
address = {London [u.a.]},
publisher = {RSC},
reportid = {FZJ-2025-02653},
pages = {17452-17466},
year = {2025},
abstract = {Solid-state batteries have been investigated as efficient
energy storage systems due to the increased power and energy
densities that they can offer compared to liquid-based
batteries. The search for solid electrolytes with high ionic
conductivities, sufficient electrochemical and mechanical
stability is indispensable. In this work, the $Li_{6+ x}
Ge_x P_{1−x}S_5Br$ substitution series is investigated via
X-ray and neutron powder diffraction, as well as impedance
and solid-state nuclear magnetic resonance spectroscopy.
Structural analyses reveal the expansion of the cage-like
$Li^+$ substructure with increasing degree of substitution
of Ge(IV) for P(V) in $Li_{6+ x} Ge_x P_{1−x}S_5Br$.
Solid-state nuclear magnetic resonance spectroscopy
measurements reveal the gradual changes in cation
environments ($^6Li$ and $^{31}P$) and the effect of Ge(IV)
substitution on local $Li^+$ transport. Impedance
spectroscopy shows an improvement of ionic conductivity at
room temperature up to fivefold for
$Li_{6.31}Ge_{0.31}P_{0.69}S_5Br$ and decreasing activation
energies. Employing $Li_{6.31}Ge_{0.31}P_{0.69}S_5Br$ as a
catholyte in $LiNi_xMn_yCo_zO_2$ based solid-state batteries
results in reproducibly higher active material utilization
and rate stability in comparison to $Li_6PS_5Br$. This work
emphasizes the importance of understanding the $Li^+$
substructure of argyrodites in correlation with the $Li^+$
transport properties to systematically develop highly
conductive $Li^+$ solid electrolytes for improved
solid-state batteries.},
cin = {IMD-4},
ddc = {530},
cid = {I:(DE-Juel1)IMD-4-20141217},
pnm = {1221 - Fundamentals and Materials (POF4-122)},
pid = {G:(DE-HGF)POF4-1221},
typ = {PUB:(DE-HGF)16},
UT = {WOS:001489149300001},
doi = {10.1039/D5TA01651G},
url = {https://juser.fz-juelich.de/record/1042707},
}