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@ARTICLE{Schalenbach:1020444,
author = {Schalenbach, Maximilian and Raijmakers, Luc and Selmert,
Victor and Kretzschmar, Ansgar and Durmus, Yasin Emre and
Tempel, Hermann and Eichel, Rüdiger-A.},
title = {{H}ow {M}icrostructures, {O}xide {L}ayers, and {C}harge
{T}ransfer {R}eactions influence {D}ouble {L}ayer
{C}apacitances},
journal = {Physical chemistry, chemical physics},
volume = {26},
number = {19},
issn = {1463-9076},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {FZJ-2024-00164},
pages = {14288-14304},
year = {2024},
abstract = {Varying the electrode potential rearranges the charges in
the double layer (DL) of an electrochemical interface by a
resistive-capacitive current response. The capacitances of
such charge relocations are frequently used in the research
community to estimate electrochemical active surface areas
(ECSAs), yet the reliability of this methodology is
insufficiently examined. Here, the relation of capacitances
and ECSAs is critically assessed with electrochemical
impedance spectroscopy (EIS) and cyclic voltammetry (CV)
data on polished (Au, Ti, Ru, Pt, Ni, glassy carbon,
graphite plate) and porous (carbon fleeces) electrodes. By
investigating this variety of electrodes, the
frequency-dependencies observed in the measured capacitances
are shown to arise from the inherent resistive-capacitive DL
response, charge transfer reactions, and resistively damped
capacitive currents in microstructures (such as pores,
pinholes, or cracks). These frequency-dependencies are
typically overlooked when capacitances are related to ECSAs.
The capacitance at the specimen-characteristic relaxation
frequency of the resistive-capacitive DL response is
proposed as a standardized capacitance-metric to estimate
ECSAs. In 1 M perchloric acid, the polished gold electrode
and the high-surface area carbon fleeces show ratios of
capacitance-metric over surface-area of around 3.7 µF/cm².
Resistively damped currents in microstructures and
low-conducting oxide layers are shown to complicate
trustworthy capacitance-based estimations of ECSAs. In the
second part of this study, advanced equivalent circuits
models to describe the measured EIS and CV responses are
presented.},
cin = {IEK-9},
ddc = {540},
cid = {I:(DE-Juel1)IEK-9-20110218},
pnm = {1232 - Power-based Fuels and Chemicals (POF4-123)},
pid = {G:(DE-HGF)POF4-1232},
typ = {PUB:(DE-HGF)16},
pubmed = {38693897},
UT = {WOS:001216696500001},
doi = {10.1039/D3CP04743A},
url = {https://juser.fz-juelich.de/record/1020444},
}