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@ARTICLE{Abramchuk:892381,
author = {Abramchuk, Mykola and Voskanyan, Albert A. and Arinicheva,
Yulia and Lilova, Kristina and Subramani, Tamilarasan and
Ma, Qianli and Dashjav, Enkhtsetseg and Finsterbusch, Martin
and Navrotsky, Alexandra},
title = {{E}nergetic {S}tability and {I}ts {R}ole in the {M}echanism
of {I}onic {T}ransport in {NASICON}-{T}ype {S}olid-{S}tate
{E}lectrolyte {L}i 1+ x {A}l x {T}i 2– x ({PO} 4 ) 3},
journal = {The journal of physical chemistry letters},
volume = {12},
number = {XXX},
issn = {1948-7185},
address = {Washington, DC},
publisher = {ACS},
reportid = {FZJ-2021-02042},
pages = {4400 - 4406},
year = {2021},
abstract = {We apply high-temperature oxide melt solution calorimetry
to assess the thermodynamic properties of the material
Li1+xAlxTi2–x(PO4)3, which has been broadly recognized as
one of the best Li-ion-conducting solid electrolytes of the
NASICON family. The experimental results reveal large
exothermic enthalpies of formation from binary oxides
(ΔHf,ox°) and elements (ΔHf,el°) for all compositions in
the range 0 ≤ x ≤ 0.5. This indicates substantial
stability of Li1+xAlxTi2–x(PO4)3, driven by thermodynamics
and not just kinetics, during long-term battery operation.
The stability increases with increasing Al3+ content.
Furthermore, the dependence of the formation enthalpy on the
Al3+ content shows a change in behavior at x = 0.3, a
composition near which the Li+ conductivity reaches the
highest values. The strong correlation among thermodynamic
stability, ionic transport, and clustering is a general
phenomenon in ionic conductors that is independent of the
crystal structure as well as the type of charge carrier.
Therefore, the thermodynamic results can serve as guidelines
for the selection of compositions with potentially the
highest Li+ conductivity among different NASICON-type series
with variable dopant contents.},
cin = {IEK-1},
ddc = {530},
cid = {I:(DE-Juel1)IEK-1-20101013},
pnm = {1221 - Fundamentals and Materials (POF4-122)},
pid = {G:(DE-HGF)POF4-1221},
typ = {PUB:(DE-HGF)16},
pubmed = {33944567},
UT = {WOS:000651787900010},
doi = {10.1021/acs.jpclett.1c00925},
url = {https://juser.fz-juelich.de/record/892381},
}