Octahedrally shaped Pt–Ni alloy nanoparticles on carbon supports have demonstrated unprecedented electrocatalytic activity for the oxygen reduction reaction (ORR), sparking interest as catalysts for low-temperature fuel cell cathodes. However, deterioration of the octahedral shape that gives the catalyst its superior activity currently prohibits the use of shaped catalysts in fuel cell devices, while the structural dynamics of the overall catalyst degradation are largely unknown. We investigate the time-resolved degradation pathways of such a Pt–Ni alloy catalyst supported on carbon during cycling and startup/shutdown conditions using an in situ STEM electrochemical liquid cell, which allows us to track changes happening over seconds. Thereby we can precisely correlate the applied electrochemical potential with the microstructural response of the catalyst. We observe changes of the nanocatalysts’ structure, monitor particle motion and coalescence at potentials that corrode carbon, and investigate the dissolution and redeposition processes of the nanocatalyst under working conditions. Carbon support motion, particle motion, and particle coalescence were observed as the main microstructural responses to potential cycling and holds in regimes where carbon corrosion happens. Catalyst motion happened more severely during high potential holds and sudden potential changes than during cyclic potential sweeps, despite carbon corrosion happening during both, as suggested by ex situ DEMS results. During an extremely high potential excursion, the shaped nanoparticles became mobile on the carbon support and agglomerated facet-to-facet within 10 seconds. These experiments suggest that startup/shutdown potential treatments may cause catalyst coarsening on a much shorter time scale than full collapse of the carbon support. Additionally, the varying degrees of attachment of particles on the carbon support indicates that there is a distribution of interaction strengths, which in the future should be optimized for shaped particles. We further track the dissolution of Ni nanoparticles and determine the dissolution rate as a function of time for an individual nanoparticle – which occurs over the course of a few potential cycles for each particle. This study provides new visual understanding of the fundamental structural dynamics of nanocatalysts during fuel cell operation and highlights the need for better catalyst-support anchoring and morphology for allowing these highly active shaped catalysts to become useful in PEM fuel cell applications.
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Mechanistic interactions in polymer electrolyte fuel cell catalyst layer degradation
Polymer Electrolyte Fuel Cells (PEFCs) exhibit considerable performance decay with cycling owing to the degradation of platinum (Pt) catalysts, resulting in the loss of the valuable electrochemically active surface area. Catalyst inventory retention is thus a necessity for a sustained cathodic oxygen reduction reaction (ORR) and to ameliorate the life expectancy of PEFCs. We demonstrate a thermo-kinetic model cognizant of processes like platinum particle dissolution–reprecipitation and oxide formation coupled with an electrochemical reactive transport model to derive mechanistic insights into the deleterious phenomena at the interfacial scale. The heterogeneous nature of particle aging in a catalyst layer environment is delineated through coarsening–shrinking zones and further comprehension of instability signatures is developed from the dissolution affinity of diameter bins through a metric, onset time. The severe degradation at high temperature and under fully humidified conditions is intertwined with the local transport resistance and the critical transient, where the catalyst nanoparticles reach a limiting diameter stage. We further reveal the degradation-performance characteristics through variation in the ionomer volume fraction and the mean size of the particle distribution in the electrode. It has been found that the kinetic and transport characteristics are crucially dependent on the interplay of two modes – one leading to the depletion of the catalyst nanoparticles and the other that emanates from catalyst coarsening.
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- Award ID(s):
- 1805215
- NSF-PAR ID:
- 10386877
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 10
- Issue:
- 28
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 15101 to 15115
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D2TA02177C
