No abstract

FeNC catalysts are promising substitutes of platinum-type catalysts for the oxygen reduction reaction (ORR). While previous research disclosed that high pyrolysis temperatures are required to achieve good stability, it was identified that a trade-off needs to be made regarding the active site density. The central question is, if a good stability can also be reached at milder pyrolysis conditions but longer duration retaining more active sites, while enabling the defect-rich carbon to heal during a long residence time? To address this, a variation of pyrolysis temperatures and durations is used in FeNC fabrication. Carbon morphology and iron species are characterized by Raman spectroscopy and Mössbauer spectroscopy, respectively. Fuel cell (FC) activity and stability data are acquired. The results are compared to ORR activity and selectivity data from rotating ring disc electrode experiments and resulting durability in accelerated stress tests mimicking the load cycle and start-up and shut-down cycle conditions. It is discussed how pyrolysis temperature and duration affect FC activity and stability. But, more important, the results connect the pyrolysis conditions to the required accelerated stress test protocol combination to enable a prediction of the catalyst stability in fuel cells.

Today's energy problems, caused by the irrational consumption of fossil fuels and, as a result, terrible environmental consequences, require the global population to quickly introduce clean energy sources. Electrochemical power sources, which include the fuel cell, provide the technological basis for electrical energy production. While proton exchange membrane fuel cells (PEMFC) rely on platinum based catalysts, obtaining stable and earth abundant catalytic materials for the oxygen reduction reaction (ORR) is an important step towards large scale integration. Our work focusses on FeNC noble-metal free catalysts in PEMFC conditions. The reaction conditions are much more complex in comparison to half cells, as transport processes and e.g. carbon oxidation affect the performance data. Thus, it turns out to be extremely difficult to determine the most important factors affecting the catalytic activity and stability of the material and to optimize the structure of the membrane-electrode assembly as several factors are overlaying each other: For example, the pyrolysis temperature affects the surface area, degree of graphitization and iron-related composition as well as extent of surface functional groups [1]. The metal loading, pyrolysis temperature and a use of possible precursor templates effects the structure, surface area as well as ORR activity and selectivity of catalysts [2], [3]. In our recent work, it was shown that in contrast to the electrochemical characteristics observed in rotating disc electrode (RDE) measurements, the best performing catalyst was prepared at the highest investigated temperature for both FC activity and stability [1]. In contrast, the dwell time had only a limited impact at low pyrolysis temperature, whereas a variation from 30 min to 90 min gave significant destruction of molecular FeNx moieties for the high temperature pyrolysis. [1] To gain further insights on the effect of preparation parameters on FC performance and in specific stability, we coupled a quadrupole mas-spectrometer to the cathode exhaust to follow possible release of CO2 depending on the applied conditions. The data are interpreted together with the structural characterization of the materials. We will discuss how the dwell time and pyrolysis temperature effected on morphology changes of the catalyst and to what extent this impacts the FC activity and short-term stability. Acknowledgements A.O. would like to thank you the TU Darmstadt for the Future talent scholarship, UIK gratefully acknowledges financial support by the BMBF young research group StRedO (03XP0092), and we thank Y. Ostroverkh, and Z. L. Müller, for the consultation and assistance with the fuel cell setup. [1] J. Scharf, M. Kübler, V. Gridin, W.D.Z. Wallace, L. Ni, S.D. Paul, U.I. Kramm, Relation between half-cell and fuel cell activity and stability of FeNC catalysts for the oxygen reduction reaction, (2022) SusMat, accepted (doi: 10.1002/sus2.84). [2] P.Theis, W.D. Z. Wallace, L. Ni, M. Kübler, A. Schlander, R. W. Stark, N. Weidler, M, Gallei, U. I. Kramm. Systematic study of precursor effects on structure and oxygen reaction activity of FeNC catalysts, (2021) Philos. Trans. Royal Soc. A PHILOS T R SOC A, (doi: 10.6084/m9.figshare.c.5506708). [3] P. Boldrin, D. Malko, A. Mehmood, U. I. Kramm, S. Wagner, S. Paul, N. Weidler, A. Kucernak. Deactivation, reactivation and super-activation of Fe-N/C oxygen reduction electrocatalysts: Gas sorption, physical and electrochemical investigation using NO and O2., (2021) Appl. Catal. B, Vol. 292, 120169, (doi: 10.1016/j.apcatb.2021.120169).

Online electrochemical mass spectrometry (OEMS) is a promising analytical technique to monitor minor side reactions with gaseous species, taking place while charging and discharging a lithium-ion cell. However, besides the manifold examples of these custom-made systems and their application, a clear analytical view on the origin of the evolving gasses and their manifold interactions within the cell environment is missing and therefore given in this work. To get a better understanding of the complexity of gas evolution associated with electrochemical reactions in lithium-ion cells, the use of chronoamperometry as an analytical method was chosen. This led to a precise variation of the applied voltage and voltage-pulse length and enabled therewith a clear starting point of the electrochemically triggered reactions. It was found that chronoamperometry can be used to precisely trigger those reactions with gaseous products. Additionally, it was found that the release of gaseous species depends on many parameters including the cell configuration, the current, and the gas species. The response time determination showed that a custom-made highly porous electrode configuration had an overall better response behavior within minutes with differences for the respective gasses of interest, compared to a standard foil configuration cells. The herein presented methodology shows how an electroanalytical approach can help gain further insight into advanced hyphenated methods, such as OEMS in the context of studies of lithium-ion cells. Graphical abstract