Enhancing Anode Reversal Tolerance by Low-Carbon and Carbon-Free Anode Catalyst Layers for Proton Exchange Membrane Fuel Cells

Abstract

Proton exchange membrane fuel cells (PEMFCs), as the main hydrogen utilization device, are considered a powerful tool for accelerating a carbon-neutral society. However, durability and cost are the two main obstacles to the commercialization of PEMFCs. Specifically, the anode reversal has been extensively studied as a severe issue that deteriorates the performance and durability of PEMFCs and leads to cell failure. Commercially, iridium oxide (IrOx) or iridium black is intensively utilized as oxygen evolution reaction catalysts to fabricate reversal tolerant anodes (RTAs) despite the slight performance loss. However, previous studies concentrated on investigating the origin or phenomena during the cell-reversal, the key factors and mechanisms affecting the anti-reversal performance, and the interaction among the anode catalyst layer components are still yet to be explored.Hence, we systematically studied the performance using three typical carbon supports with three metal contents and different metal deposition orders by experiments and model calculations. First, we synthesized Ir outside Ir/Pt/C and Pt outside Pt/It/C with uniform nanoparticle size and distribution and characterized them comprehensively. A new parameter, “relative metal coverage”, is put forward to evaluate and predict the anti-reversal ability, showing that higher relative metal coverage results in a longer reversal time and lower polarization performance degradation rate. In addition, Ir outside Ir/Pt/C shows better reversal tolerance than Pt outside Pt/It/C, which has been rarely mentioned in previous studies. Further, the experimental results show that even though the metal coverage is high, the performance degradation caused by carbon corrosion is still inevitable. On this basis, we synthesized a high specific surface area conductive oxide Ti4O7 as the anode catalyst support to eliminate the adverse effects of carbon corrosion. Previously, the initial performance of Ti4O7-supported catalyst was obstructed by the disadvantaged electrical conductivity of Ti4O7. We obtain a comparable polarization performance after optimizing the Ti4O7-supported anode catalyst layer parameters by shortening the electron transfer pathway and increasing metal coverage. Typically, the Ir@IrOx/Pt/Ti4O7-fabricated RTA with low Ir loading displays approximately ten times longer reversal time (6 hours) and two orders of magnitude lower degradation rate than a conventional carbon-supported counterpart. The degradation origin of the Ti4O7-supported anodes is also studied by postmortem characterizations, pointing to the Pt oxidation caused by the formation of TiOx thin layers on the Pt surface. These two works aim to promote the development of highly durable and reversal tolerance anode and provide a bright perspective for practical high-performance, low-degradation, and cost-friendly RTA fabrication.