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@INPROCEEDINGS{Gross:1019927,
author = {Gross, Jürgen and Dashjav, Enkhtsetseg and Tietz, Frank
and Malzbender, Jürgen and Ziegner, Mirko and Grüner,
Daniel and Peter, Nicolas and Schwaiger, Ruth},
title = {{M}icrostructural properties of tape-cast {LATP} ceramic
sheets for application in solid state batteries},
reportid = {FZJ-2023-05748},
year = {2023},
abstract = {Solid-state batteries (SSB) are promising candidates for
the next generation of energy storage devices, since this
technology promises vastly improved safety and storage
capacity compared to conventional Li-ion batteries [1]. In
order to enable this technology further improvements of the
solid electrolyte (SE) in regards to manufacturing, ionic
conductivity, microstructural and mechanical properties have
to be made [2-4]. The solid electrolyte Li1+xAlxTi2-x(PO4)3
(LATP) is a promising material for the application as SE, in
particular due to its high ionic conductivity and good
compatibility towards certain active materials such as
LiFePO4 [5-7]. Furthermore, in contrast to hygroscopic SEs,
such as Li7La3Zr2O12, LATP exhibits a high stability against
H2O and CO2 [8, 9], thus enabling production and handling in
ambient air, leading to reduced production costs. Advanced
components require industrial relevant production processes,
of which in particular tape casting is of considerable
interest. Processing-relevant sintering behavior needs to be
optimized using sintering additives. Thus, 14 variations of
tape-cast LATP with different chemical compositions and
varying amounts of LiF and SiO2 additions have been
investigated with respect to their microstructure and
especially their phase compositions. A comparison of their
chemical and phase composition revealed an increase in the
amount of the orthorhombic LATP phase with increasing
lithium content, indicating that orthorhombic LATP is a
lithium-rich modification. The orthorhombic LATP phase
exhibit a much lower ionic conductivity compared to its
rhombohedral modification, thus has a negative effect on the
battery performance. Based on high-temperature X-ray
diffraction, a rhombohedral – orthorhombic LATP phase
equilibrium was identified, shifting towards the
rhombohedral phase at temperatures > 800 °C. Above 1000 °C
no orthorhombic LATP could be detected, therefore an
additional heat treatment dissolves this phase, potentially
improving the materials property, however it is known at
higher sintering temperatures the severity of microcracks
within LATP increases. SEM micrograph analysis revealed that
both LiF and SiO2 are beneficial for the densification of
the material. Although increased SiO2 addition led to
decreased densifications, the SiO2 addition successfully
inhibited the LATP grain growth, leading to smaller average
grain sizes, thus reducing the severity of micro-cracks.
Based on Ball-on-3 balls bending results an increase of the
material strength with decreasing porosity can be observed,
however below $18\%$ porosity, a sharp drop of the material
strength from ~150 MPa to ~50 MPa is detected. Fracture
surface analysis revealed a shift of the fracture origin,
where at higher porosities $(>18\%)$ pores and at lower
porosities $(<18\%)$ micro-cracks are causing material
failure under applied stress. This might be expected since
dense tape cast LATP requires higher sintering temperatures,
although the use of SiO2 as a sintering additive appears to
be a promising approach to reduce the micro-crack severity.
However based on these result the application of dense LATP
in solid state batteries is not straight forward. Porous
tape cast LATP on the other hand, might be used as a
skeleton-structure for polymer infiltrated cathode
composites, since it can be obtained at lower sintering
temperatures. However, a high amount of o-LATP might be
expected, which requires clarification of its effects also
on the performance of cathode composites, which will be the
aim of future studies.[1] F. Zheng, M. Kotobuki, S. Song, M.
O. Lai, and L. Lu, "Review on solid electrolytes for
all-solid-state lithium-ion batteries," Journal of Power
Sources, vol. 389, pp. 198-213, 2018.[2] R. Chen, W. Qu, X.
Guo, L. Li, and F. Wu, "The pursuit of solid-state
electrolytes for lithium batteries: from comprehensive
insight to emerging horizons," Materials Horizons, vol. 3,
no. 6, pp. 487-516, 2016.[3] A. Manthiram, X. Yu, and S.
Wang, "Lithium battery chemistries enabled by solid-state
electrolytes," Nature Reviews Materials, vol. 2, no. 4, pp.
1-16, 2017.[4] T. Shi, Y.-Q. Zhang, Q. Tu, Y. Wang, M.
Scott, and G. Ceder, "Characterization of mechanical
degradation in an all-solid-state battery cathode," Journal
of Materials Chemistry A, vol. 8, no. 34, pp. 17399-17404,
2020.[5] E. Dashjav et al., "Microstructure, ionic
conductivity and mechanical properties of tape-cast Li1.
5Al0. 5Ti1. 5P3O12 electrolyte sheets," Journal of the
European Ceramic Society, 2020.[6] E. Dashjav et al., "The
influence of water on the electrical conductivity of
aluminum-substituted lithium titanium phosphates," Solid
State Ionics, vol. 321, pp. 83-90, 2018.[7] M. Gellert, E.
Dashjav, D. Grüner, Q. Ma, and F. Tietz, "Compatibility
study of oxide and olivine cathode materials with lithium
aluminum titanium phosphate," Ionics, vol. 24, no. 4, pp.
1001-1006, 2018.[8] G. y. Adachi, N. Imanaka, and H. Aono,
"Fast Li⊕ conducting ceramic electrolytes," Advanced
Materials, vol. 8, no. 2, pp. 127-135, 1996.[9] E.
Bucharsky, K. Schell, A. Hintennach, and M. Hoffmann,
"Preparation and characterization of sol–gel derived high
lithium ion conductive NZP-type ceramics Li1+ x AlxTi2− x
(PO4) 3," Solid State Ionics, vol. 274, pp. 77-82, 2015.},
month = {Jun},
date = {2023-06-12},
organization = {Helmholtz Energy Conference 2023,
Koblenz (Germany), 12 Jun 2023 - 13 Jun
2023},
subtyp = {After Call},
cin = {IEK-2 / IEK-1},
cid = {I:(DE-Juel1)IEK-2-20101013 / I:(DE-Juel1)IEK-1-20101013},
pnm = {1221 - Fundamentals and Materials (POF4-122) / ProFeLi -
Produktionstechnik für Festkörperbatterien mit
Lithium-Metall-Anode (13XP0184B)},
pid = {G:(DE-HGF)POF4-1221 / G:(BMBF)13XP0184B},
typ = {PUB:(DE-HGF)6},
url = {https://juser.fz-juelich.de/record/1019927},
}