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@ARTICLE{Case:878099,
author = {Case, David and McSloy, Adam J. and Sharpe, Ryan and
Yeandel, Stephen R. and Bartlett, Thomas and Cookson, James
and Dashjav, Enkhtsetseg and Tietz, Frank and Naveen Kumar,
C. M. and Goddard, Pooja},
title = {{S}tructure and ion transport of lithium-rich {L}i1+{A}l
{T}i2−({PO}4)3 with $0.3\<x\<0.5:$ {A} combined
computational and experimental study},
journal = {Solid state ionics},
volume = {346},
issn = {0167-2738},
address = {Amsterdam [u.a.]},
publisher = {Elsevier Science},
reportid = {FZJ-2020-02630},
pages = {115192},
year = {2020},
abstract = {New solid state electrolytes are becoming increasingly
sought after in the drive to replace flammable liquid
electrolytes. To this end, several Li conducting solids have
been identified as promising candidates including Li stuffed
garnets and more recently Li-rich materials such as
Li1+xAlxTi2−x(PO4)3 with 0.3< x <0.5. However, the
structure/property relationships of LATP are incredibly
sensitive to synthesis conditions and therefore challenging
to optimise. In this joint computational and experimental
investigation, we examine the structural sensitivities by
modelling the site occupancies at varying temperature, which
clarifies previously reported discrepancies of the crystal
structures. Furthermore, we investigate the Li ion transport
properties which have not reported computationally before.
We confirm from our simulations that the migration pathway
only involves the M1(6b) and M2(18e) site, in excellent
agreement with the neutron diffraction data, clarifying all
past controversies regarding the Li ion occupancies in LATP.
Interestingly, we calculate low migration barriers (0.3 eV)
in line with experimental findings but also show evidence of
Li ion trapping on Al doping in LATP (where x = 0.4),
possibly explaining the experimental observation that the Li
ion conductivity does not improve above x = 0.3, due to a
stronger repulsion between Li+–>Ti4+ compared to
Li+–>Al3+. Furthermore, our calculated ionic
conductivities are in excellent agreement with experimental
values, highlighting the robustness of our computational
models.},
cin = {IEK-1 / IEK-12},
ddc = {530},
cid = {I:(DE-Juel1)IEK-1-20101013 / I:(DE-Juel1)IEK-12-20141217},
pnm = {131 - Electrochemical Storage (POF3-131)},
pid = {G:(DE-HGF)POF3-131},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000517851600016},
doi = {10.1016/j.ssi.2019.115192},
url = {https://juser.fz-juelich.de/record/878099},
}