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@INPROCEEDINGS{Roitzheim:905787,
author = {Roitzheim, Christoph and Finsterbusch, Martin and
Kaghazchi, Payam and Fattakhova-Rohlfing, Dina},
title = {{M}odified {C}athode {M}aterials for {G}arnet {B}ased
{A}ll-{S}olid-{S}tate {L}ithium {B}atteries},
reportid = {FZJ-2022-01010},
year = {2020},
abstract = {All solid-state batteries (ASB) are an emerging energy
storage technology, which is expected to improve the safety
on the cell level and to increase the battery energy
density. One of important issues in the development of
bulk-type ASBs with a high energy density is a possibility
of processing thick composites cathodes with percolating
pathways for ion and electron transport. For the ceramic
electrolytes such as garnet-type Ta-substituted LLZ
(Li6.6La3Zr1.6Ta0.4O12; LLZ:Ta) the practical realization of
composite cathodes is however challenging due to the
necessity of high temperature processing, raising the issues
of material compatibility and the formation of reaction
interphases influencing the total cell resistance. So far,
the thick garnet-based composite cathodes could be made only
with LiCoO2 (LCO) as an active material. For this kind of
ASB, high areal capacities of up to 1.63 mAh/cm² were
obtained. However, the utilization of high capacity cathode
materials like LiNixCoyMn1–x–yO2 (NCM) was so far not
possible due to the lower thermal stability of NCM as
compared to LCO and the resulting enhanced reactivity
between LLZ:Ta and NCM.Usually NCM materials were only
optimized for liquid electrolyte based batteries. Therefore,
an optimization of these active materials with respect to
their integration into ASBs is intended in this work.
Possible strategies for this optimization are doping or
substitution, surface coatings or core-shell structures.We
present the synthesis of optimized cathode materials for
bulk-type, fully inorganic ASBs based on ceramic materials.
A detailed material screening of NCM materials with
different compositions and modifications is performed by
evaluating the compatibility with cubic LLZ:Ta during
co-sintering at elevated temperatures. The compatibility is
tested by in situ high temperature X-ray diffraction
(HT-XRD), differential thermal analysis/thermogravimetry
(DTA/TG), Raman spectroscopy and X-ray photoelectron
spectroscopy (XPS). The experimental work is supported by
simulation studies using ab-initio-based approaches such as
density functional theory (DFT), ab initio molecular
dynamics (AIMD) as well as ab initio atomistic
thermodynamics and kinetics approaches. These simulation
based methods enable the prediction of lattice parameter of
NCM at different stages of charge. Additionally, the
calculation of interchange energies needed for the cation
interchange between NCM and cubic LLZ:Ta during co-sintering
is possible.Boron doping of NCM was investigated as a
possible strategy to improve its compatibility with LLZ:Ta,
as this strategy was demonstrated to be very efficient for
liquid electrolytes. The theoretical and experimental
results on B-doped NCM with different compositions are
already available. However, the formation of secondary
phases after co-sintering that was predicted by us
theoretically and confirmed experimentally using Rietveld
refinement discard boron doping as a way to enhance thermal
stability of NCM during the co-sintering with cubic LLZ:Ta.
Introduction of other dopants and surface coatings is
currently investigated to improve the compatibility of NCM
with cubic LLZ:Ta during co-sintering. The combined
experimental and theoretical approach is expected to result
in an optimized cathode material for ASBs with enhanced
performance.},
month = {Oct},
date = {2020-10-04},
organization = {ECS PRiME 2020, online (USA), 4 Oct
2020 - 9 Oct 2020},
subtyp = {Other},
cin = {IEK-1},
cid = {I:(DE-Juel1)IEK-1-20101013},
pnm = {1221 - Fundamentals and Materials (POF4-122) /
Verbundvorhaben SimCaMat: Modellierung und Synthese
verbesserter Kathodenmaterialien (03EK3054A)},
pid = {G:(DE-HGF)POF4-1221 / G:(BMBF)03EK3054A},
typ = {PUB:(DE-HGF)6},
doi = {10.1149/MA2020-025987mtgabs},
url = {https://juser.fz-juelich.de/record/905787},
}