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@ARTICLE{Koettgen:867884,
author = {Koettgen, Julius and Grieshammer, Steffen and Hein, Philipp
and Grope, Benjamin O. H. and Nakayama, Masanobu and Martin,
Manfred},
title = {{U}nderstanding the ionic conductivity maximum in doped
ceria: trapping and blocking},
journal = {Physical chemistry, chemical physics},
volume = {20},
number = {21},
issn = {1463-9084},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {FZJ-2019-06486},
pages = {14291 - 14321},
year = {2018},
abstract = {Materials with high oxygen ion conductivity and low
electronic conductivity are required for electrolytes in
solid oxide fuel cells (SOFC) and high-temperature
electrolysis (SOEC). A potential candidate for the
electrolytes, which separate oxidation and reduction
processes, is rare-earth doped ceria. The prediction of the
ionic conductivity of the electrolytes and a better
understanding of the underlying atomistic mechanisms provide
an important contribution to the future of sustainable and
efficient energy conversion and storage. The central aim of
this paper is the detailed investigation of the relationship
between defect interactions at the microscopic level and the
macroscopic oxygen ion conductivity in the bulk of doped
ceria. By combining ab initio density functional theory
(DFT) with Kinetic Monte Carlo (KMC) simulations, the oxygen
ion conductivity is predicted as a function of the doping
concentration. Migration barriers are analyzed for energy
contributions, which are caused by the interactions of
dopants and vacancies with the migrating oxygen vacancy. We
clearly distinguish between energy contributions that are
either uniform for forward and backward jumps or favor one
migration direction over the reverse direction. If the
presence of a dopant changes the migration energy
identically for forward and backward jumps, the resulting
energy contribution is referred to as blocking. If the
change in migration energy due to doping is different for
forward and backward jumps of a specific ionic
configuration, the resulting energy contributions are
referred to as trapping. The influence of both effects on
the ionic conductivity is analyzed: blocking determines the
dopant fraction where the ionic conductivity exhibits the
maximum. Trapping limits the maximum ionic conductivity
value. In this way, a deeper understanding of the underlying
mechanisms determining the influence of dopants on the ionic
conductivity is obtained and the ionic conductivity is
predicted more accurately. The detailed results and insights
obtained here for doped ceria can be generalized and applied
to other ion conductors that are important for SOFCs and
SOECs as well as solid state batteries.},
cin = {IEK-12 / JARA-HPC},
ddc = {540},
cid = {I:(DE-Juel1)IEK-12-20141217 / $I:(DE-82)080012_20140620$},
pnm = {131 - Electrochemical Storage (POF3-131) / Attempt
frequency of oxygen ion jumps in doped ceria
$(jhpc27_20151101)$},
pid = {G:(DE-HGF)POF3-131 / $G:(DE-Juel1)jhpc27_20151101$},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:29479588},
UT = {WOS:000434246300002},
doi = {10.1039/C7CP08535D},
url = {https://juser.fz-juelich.de/record/867884},
}