Regulating local phosphoric acid environment via HDTMPA-modified catalyst layers for enhanced high-temperature proton exchange membrane fuel cells

Managing phosphoric acid (PA) distribution within the catalyst layers is a critical challenge for the development of high-performance high-temperature proton exchange membrane fuel cells (HT-PEMFCs). This work introduces a novel strategy using hexamethylenediamine tetra(methylenephosphonic acid) (HDTMPA) as a functional additive in the cathode to precisely regulate the local PA environment. HDTMPA performs a dual function: its strong hydrogen-bonding interactions with PA effectively anchor the acid, which prevents the excessive flooding and poisoning of Pt catalyst sites, while its electron-rich nitrogen atoms help establish a robust proton-conduction network. Consequently, a membrane electrode assembly (MEA) with an HDTMPA-modified cathode (0.5 mgPt cm −2 ) achieves a peak power density of 715 mW cm −2 at 150 °C, a 42% enhancement over the unmodified baseline (503 mW cm −2 ). Furthermore, the modified MEA demonstrates exceptional durability, exhibiting only a 5.0% performance decay after an accelerated durability test of 10,000 cycles, compared to a 17.5% decay for the control. In-situ electrochemical analysis confirms the enhanced kinetics, validating this molecular design approach as a new avenue for developing highly stable and efficient HT-PEMFCs.