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@BOOK{Suo:1021557,
author = {Suo, Yanpeng and Korte, Carsten},
title = {{I}nvestigation of the influence of cation acidity in
proton-conducting ionic liquids for the application as
electrolyte in a future intermediate-temperature fuel cell},
address = {online},
publisher = {RWTHpublications},
reportid = {FZJ-2024-00831},
pages = {pages 1 Online-Ressource : Illustrationen, Diagramme},
year = {2023},
abstract = {The operation of a Polymer electrolyte membrane fuel cells
in an intermediate temperature range between 100–140 °C
(IT-PEMFCs) would allow a significant simplified setup for
system (no water management, more efficient cooling), and
thus a cost cut. The use of proton-conducting ionic liquids
(PILs) as electrolytes for future IT-PEMFCs is a promising
approach, because of their unique properties. As water is
produced during fuel cell operation, the bulk properties of
PILs and the properties of the catalyst/PIL interface,
including the ORR kinetics, are significantly affected. It
is therefore crucial to investigate thoroughly the interface
structure and properties of binary PIL/H2O systems. In this
thesis, three PILs with different cation acidities were
selected to investigate the influence of the cation
acidities on the physicochemical and electrochemical
properties of PILs: 2-sulfoethylmethylammonium triflate
[2-Sema][TfO] ([2-Sema]+: pKa = 0.94), 1-Ethylimidazolium
triflate [EIm][TfO] ([EIm]+: pKa = 7.70) and
Diethylmethylammonium triflate [Dema][TfO] ([Dema]+: pKa =
10.55). PILs with higher pKa exhibit better thermal
stability due to a complete proton transfer to the cation.
All three PILs are thermally stable at 120 °C. The
conductivity of PILs depends strongly on their cation
acidities and the interaction between cations and anions.
All three PILs have 3–40 times higher values of the
product of oxygen diffusivity and solubility (DO2 ∙ cO2)
compared to the common electrolyte H3PO4 for high
temperature (HT-)PEMFCs, which is beneficial especially for
the mass transport in the ORR. The analysis of polarization
curves and cyclic voltammograms show that the ORR on
platinum electrodes takes place via an associative mechanism
with molecular adsorbed oxygen, where the first electron and
proton transfer to the oxygen molecules is rate determining.
It turned out, that only [2-Sema][TfO] with the highly
acidic [2-Sema]+ cation provides sufficient current
densities in the potential range relevant for fuel cell
application. Hence, a high acidity of the PIL cation is
crucial. Moreover, only the [2-Sema]+ cation participates in
the proton transfer to the oxygen molecules. On the other
hand, the significantly higher DO2 ∙ cO2 value and ORR
limiting current of the low acidic PILs suggests combining
favorable kinetic and bulk properties by mixing PILs with
highly and low acidic cations. For a future improvement of
the ORR, a detailed knowledge of the structure and
properties of the catalyst/PIL interface, such as the double
layer capacitance, is mandatory. The impedance analysis
revealed high and low frequency capacitances, C1 and C2,
assigned to (fast) ion transport and (slow)
pseudo-capacitive processes. The PILs exhibit significant
differences in the capacitance C1, which are attributed to a
higher compacity of the ions in the double layer in case of
[2-Sema][TfO] compared to the low acidic PILs. The increase
of peaks of C1 and C2 in the HUPD (hydrogen underpotential
deposition) and Pt oxidation region correlate well with the
corresponding effects in cyclic voltammograms. By addition
of water, C1 tends to increase. This is explained by a
change in the dielectric properties and the structure of the
double layer, including a lower stiffness of the ion layers,
a higher permittivity and a lower thickness.},
keywords = {Hochschulschrift (Other) / fuel cells ; protic ionic
liquids ; oxygen reduction reaction (ORR) ; electrode
kinetics ; double layer capacitance ; Brennstoffzellen ;
protische ionische Flüssigkeiten ;
Sauerstoffreduktionsreaktion ; Elektrodenkinetik ;
Doppelschichtskapazität (Other)},
cin = {IEK-14},
cid = {I:(DE-Juel1)IEK-14-20191129},
pnm = {1231 - Electrochemistry for Hydrogen (POF4-123)},
pid = {G:(DE-HGF)POF4-1231},
typ = {PUB:(DE-HGF)3},
doi = {10.18154/RWTH-2023-08372},
url = {https://juser.fz-juelich.de/record/1021557},
}