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@TECHREPORT{Erning:863796,
author = {Erning, J. W.},
title = {{U}ntersuchungen zur {S}auerstoffreduktion an {K}athoden
für {H}ochtemperatur-{B}rennstoffzellen},
volume = {3561},
number = {Juel-3561},
address = {Jülich},
publisher = {Forschungszentrum Jülich, Zentralbibliothek, Verlag},
reportid = {FZJ-2019-03783, Juel-3561},
series = {Berichte des Forschungszentrums Jülich},
pages = {145 p.},
year = {1998},
abstract = {Lanthan-Strontium-Manganite perowskites are the most
widespread materials in use for Solid Oxide Fuel Cell
cathodes. The electrode reaction taking place, i.e. the
reduction of oxygen supplied by air, was investigated by
electrochemical means to obtain further knowledge about the
electrode processes. The high activation energy of this
reaction (200 kJ/mol), preventing lower operation
temperatures of the SOFC, was the starting point for the
investigation. Quasi steady state current voltage
measurements and impedance spectroscopy were perfouned in a
three electrode configuration. The electrodes were of
circular shape with a diameter of 10 mm. The preparation was
made by screen printing as well as Wet Powder Spraying onto
plates made of Yttria-stabilized Zirconia. Perowskite
powders of varying chemical and stoichiometric composition
were used. To obtain higher power densities and, more
important, lower apparent activation energies, catalytic
layers were added at the interface electrode/electrolyte.
Additionally, a less complex system, a model
electrode/electrolyte setup made from single-crystal YSZ as
electrolyte and gold in liquid and solid state as electrode
was developed to create a better defined system. This setup
was used to investigate the behaviour of the
electrode/electrolyte interface. Reliable, reproducible
results could be obtained using either setup. The
experimental conditions i.e. oxygen partial pressure,
temperature and overpotential were varied in order to
determine the kinetic properties of the electrodes. Apparent
activation energies, pre-exponential factors, apparent
charge-transfer coefficients and electrochemical orders of
reaction were calculated from the current-voltage data in
order to propose possible reaction steps. The catalytic
layer made of palladium lowered the apparent activation
energy to about 138 kJ/mol, but lowered the apparent
pre-exponential factor as well, thus resulting in current
densities one order of magnitude higher than without
catalyst. By using a mixture of platinum and palladium, the
current densities obtained were even higher, caused by a
higher pre-exponential factor. Several electrodes showed a
charge-transfer reaction determined behaviour for small
cathodic overpotentials (<100 mV). For these potentials the
behaviour of the electrodes with additional catalytic layers
was dominated by the influence of the catalyst. The apparent
electrochemical reaction orders for intermediate
temperatures were calculated in the region between 0.4 and
0.8 giving evidence for dissociative adsorption of oxygen.
The analysis of the charge-transfer coefficient a and its
temperature dependence showed negative values for the
entropic part $\alpha^{s}_{c}$. Impedance data gave further
evidence for the proposed reaction steps but it was not
possible to correlate the time constants with singular
reaction steps. All results indicate a complex reaction
mechanism involving several rate-determining steps. The use
of the model electrode/electrolyte setup made it possible to
isolate several reaction steps which are depending on the
geometry of the electrode. The combination of all results
gave evidence for the formulation of possible reaction
mechanisms which were verified by using a complex simulation
program which simultaneously fits current-voltage and
impedance measurements using a model based on the kinetic
analysis of an assumed reaction mechanism. The activation
energies computed by the simulation program for single
reaction steps are similar to those calculated from specific
potential regions for the current potential measurements.
Thus the assumption of potential regimes in which specific,
different reactions are rate-determining is affirmed.},
cin = {PRE-2000},
cid = {I:(DE-Juel1)PRE2000-20140101},
pnm = {899 - ohne Topic (POF3-899)},
pid = {G:(DE-HGF)POF3-899},
typ = {PUB:(DE-HGF)3 / PUB:(DE-HGF)29},
url = {https://juser.fz-juelich.de/record/863796},
}