Transition-Metal- and Nitrogen-Doped Carbide-Derived Carbon/Carbon Nanotube Composites as Cathode Catalysts for Anion-Exchange Membrane Fuel Cells.

Abstract

Transition-metal- and nitrogen-codoped carbide-derived carbon/carbon nanotube composites (M-N-CDC/CNT) have been prepared, characterized, and used as cathode catalysts in anion-exchange membrane fuel cells (AEMFCs). As transition metals, cobalt, iron, and a combination of both have been investigated. Metal and nitrogen are doped through a simple high-temperature pyrolysis technique with 1,10-phenanthroline as the N precursor. The physicochemical characterization shows the success of metal and nitrogen doping as well as very similar morphologies and textural properties of all three composite materials. The initial assessment of the oxygen reduction reaction (ORR) activity, employing the rotating ring–disk electrode method, indicates that the M-N-CDC/CNT catalysts exhibit a very good electrocatalytic performance in alkaline media. We find that the formation of HO2– species in the ORR catalysts depends on the specific metal composition (Co, Fe, or CoFe). All three materials show excellent stability with a negligible decline in their performance after 10000 consecutive potential cycles. The very good performance of the M-N-CDC/CNT catalyst materials is attributed to the presence of M-Nx and pyridinic-N moieties as well as both micro- and mesoporous structures. Finally, the catalysts exhibit excellent performance in in situ tests in H2/O2 AEMFCs, with the CoFe-N-CDC/CNT reaching a current density close to 500 mA cm–2 at 0.75 V and a peak power density (Pmax) exceeding 1 W cm–2. Additional tests show that Pmax reaches 0.8 W cm–2 in an H2/CO2-free air system and that the CoFe-N-CDC/CNT material exhibits good stability under both AEMFC operating conditions.