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@INPROCEEDINGS{Jovanovic:1047385,
author = {Jovanovic, Sven and Rameker, Robert and Poc, Jean-Pierre
and Jodat, Eva and Karl, André and Eichel, Rüdiger-A. and
Granwehr, Josef},
title = {{A} novel perspective on accelerated degradation studies of
proton exchange membranes},
publisher = {Zenodo},
reportid = {FZJ-2025-04271},
pages = {9},
year = {2025},
abstract = {Accelerated degradation studies are widely applied in
research on proton exchange membranes (PEMs) for the
investigation of the origins and mechanisms of performance
loss for electrolysis or fuel cell applications. In a
nutshell, it is reported in literature that degradation in
PEMs commonly occurs following Fenton-like reactions, where
in situ formed H2O2 reacts with transition metal cations to
produce radicals. These radicals then alter the ionomer on a
chemical level by attacking particularly its polar side
chains, causing a loss of functional moieties for proton
transport [1]. Fast degradation studies mimic and promote
these conditions by subjecting PEMs to high concentrations
of H2O2 and Fe2+ cations at elevated temperatures. However,
these studies often exhibit discrepancies when compared to
degradation occurring during long-term operation [2].The
presented work attempts to elucidate these discrepancies by
i) addressing inconsistencies in accelerated degradation and
testing procedures, ii) studying the dependence of
degradation on PEM chemistry and structure and iii)
utilizing both NMR spectroscopy and SEM microscopy among
other techniques for a comprehensive picture. Hereby,
solid-state magic angle spinning (MAS) NMR spectroscopy
provides information on both chemical and local structural
transformations of the PEM, while SEM offers concrete
insights into structural changes on a microscopic scale. The
Fenton-like accelerated degradation experiments were
optimized for homogeneity and effectiveness by introducing
the catalytic iron centers into the PEMs. Additionally,
interferences in the analytical techniques were minimized by
careful removal of excess reactants after accelerated
degradation. The combined analytical techniques reveal that
chemical degradation in PEMs is significantly less
pronounced than suggested in literature, although
differences were observed depending on the type of PEM
material. Moreover, organic radicals that form during
Fenton-like reactions could not be detected by EPR
spectroscopy. However, all samples experienced significant
changes in the local structure, as indicated by NMR
relaxometry, and microscopic structure, as illustrated by
SEM techniques. Thus, instead of chemical degradation, the
PEM may be affected on a structural level by mechanical
stress due to microscopic gas pockets and macroscopic
bubbles forming inside the gas impermeable material.[1] L.
Ghassemzadeh et al., J. Am. Chem. Soc. 135, 8181–8184
(2013).[2] J. Mališ et al., Int. J. Hydrogen Energy 41,
2177–2188 (2016).},
month = {Jul},
date = {2025-07-01},
organization = {European Electrolyser $\&$ Fuel Cell
Forum (EFCF), Lucerne (Switzerland), 1
Jul 2025 - 4 Jul 2025},
keywords = {EFCF2025 (Other) / H2 (Other) / LowTemp. Fuel Cells $\&$
Electrolysers (Other) / PEMs (Other) / degradation (Other) /
Fenton (Other) / analytics (Other)},
cin = {IET-1},
cid = {I:(DE-Juel1)IET-1-20110218},
pnm = {1231 - Electrochemistry for Hydrogen (POF4-123) / HITEC -
Helmholtz Interdisciplinary Doctoral Training in Energy and
Climate Research (HITEC) (HITEC-20170406)},
pid = {G:(DE-HGF)POF4-1231 / G:(DE-Juel1)HITEC-20170406},
typ = {PUB:(DE-HGF)8},
doi = {10.5281/zenodo.17244134},
url = {https://juser.fz-juelich.de/record/1047385},
}