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In polymer electrolyte fuel cells, the oxygen reduction reaction (ORR) rate increases at high temperatures. Therefore, ORR catalysts must be designed for use at high temperatures and require evaluation. To address the problem of decreased dissolved oxygen concentrations in conventional channel flow double electrode (CFDE) systems, this study develops a CFDE system capable of electrochemical measurement at 120 °C that can evaluate the ORR activity of Pt-supported carbon (Pt/C) and carbon-based non-precious metal catalysts (NPMC). The ORR activity increased with an increasing reaction temperature, regardless of the catalyst, and the current density ratios at 120 °C and room temperature were estimated to be 2.4 and 5.4 for Pt/C and NPMC, respectively. This indicates that the NPMC ORR activity increased significantly with the increasing reaction temperature. This increased activation energy, which is approximately 2.3 times greater than that of Pt/C at the overpotential of 0.38 V, contributes to a significant increase in the ORR activity at higher temperatures. [Display omitted] • An improved channel flow double electrode system is developed. • Kinetic analysis of ORR up to 120 °C was performed by using the system. • The activation energy of NPMC is higher than Pt/C catalyst. • ORR activity of NPMC increased significantly with the increasing reaction temperature. [ABSTRACT FROM AUTHOR]

The use of carbon cathode catalysts in polymer electrolyte fuel cells instead of the current platinum catalysts is attracting increasing attention. We claim that two factors are important for enhancing the activity of carbon cathode catalysts in the oxygen reduction reaction (ORR): the formation of a nanoshell structure and co-doping with boron and nitrogen. Herein, we investigate the preparation and characterization of active ORR carbon catalysts that combine the above factors. Boron and nitrogen (BN)-doped nanoshell-containing carbon (BN-NSCC) was prepared by carbonizing a mixture of poly(furfuryl alcohol), cobalt phthalocyanine, melamine, and a trifluoroborane–methanol complex at 1000 °C. Transmission electron microscopy and X-ray photoelectron spectroscopy revealed the formation of nanoshell structures with distorted graphitic layers and the introduction of boron and nitrogen atoms, respectively. The ORR activity was evaluated in oxygen-saturated 0.5 mol dm −3 H 2 SO 4 using Koutecky–Levich analysis. The BN-NSCC showed an eight to ten times higher ORR activity than undoped NSCC, with an increased number of electrons participating in the reaction. Tafel analysis revealed a change in the rate-determining step caused by BN-doping. Thus, the combination of a nanoshell structure and co-doping with boron and nitrogen was found to improve the ORR activity of carbon catalysts. [ABSTRACT FROM AUTHOR]

The activity of non-precious metal catalysts (NPMCs) has now reached a stage at which they can be considered as possible alternatives to Pt for some proton exchange membrane fuel cell (PEMFC) applications. However, despite significant efforts over the past 50 years on catalyst development, only limited studies have been performed on NPMC-based cathode catalyst layer (CCL) designs. In this work, an extensive ionomer study is performed to investigate the impact of ionomer equivalent weight on performance, which has uncovered two crucial findings. Firstly, it is demonstrated that beyond a critical CCL conductance, no further improvement in performance is observed. The procedure used to determine this critical conductance can be used by other researchers in this field to aid in their design of high performing NPMC-based CCLs. Secondly, it is shown that the stability of NPMC-based CCLs can be improved through the use of low equivalent weight ionomers. This represents a completely unexplored pathway for further stability improvements, and also provides new insights into the possible degradation mechanisms occurring in NPMC-based CCLs. These findings have broad implications on all future NPMC-based CCL designs. [ABSTRACT FROM AUTHOR]

A major hurdle to the widespread commercialization of proton exchange membrane fuel cells (PEMFCs) is the high loading of noble metal (Pt/Pt-alloy) catalyst at the cathode, which is necessary to facilitate the inherently sluggish oxygen reduction reaction (ORR). To eliminate the use of Pt/Pt-alloy catalysts at the cathode of PEMFCs and thus significantly reduce the cost, extensive research on non-precious metal catalysts (NPMCs) has been carried out over the past decade. Major advances in improving the ORR activity of NPMCs, particularly Fe- and Co-based NPMCs, have elevated these materials to a level at which they can start to be considered as potential alternatives to Pt/Pt-alloy catalysts. Unfortunately, the stability (performance loss following galvanostatic experiments) of these materials is currently unacceptably low and the durability (performance loss following voltage cycling) remains uncertain. The three primary mechanisms of instability are: (a) Leaching of the metal site, (b) Oxidative attack by H 2 O 2 , and (c) Protonation followed by possible anion adsorption of the active site. While (a) has largely been solved, further work is required to understand and prevent losses from (b) and/or (c). Thus, this review is focused on historical progress in (and possible future strategies for) improving the stability/durability of NPMCs. [ABSTRACT FROM AUTHOR]