Recent Progress on Electrocatalyst for High-Temperature Polymer Exchange Membrane Fuel Cells

High-temperature polymer exchange membrane fuel cells (HT-PEMFCs), promising and sustainable energy conversion devices, have received considerable attention ascribed to their high energy conversion efficiency and zero emission. Different from the traditional Nafion PEMFCs, the working temperature ranks from 120 to 250 degrees C for HT-PEMFCs; as a result, HT-PEFMCs show impressive merits, such as theoretically higher kinetics, simple water/heat management and better tolerance toward impurities in hydrogen fuel; especially the elimination of flooding issue in fuel cells. Moreover, the working temperature matches well with the temperature for hydrogen generation from methanol reforming revealing that the generated heat from HT-PEMFCs can be utilized for methanol reforming to generate hydrogen; in this case, hydrogen tank can be replaced by methanol reforming system for HT-PEMFCs leading to a higher safety. Similar to traditional Nafion PEMFCs, polymer electrolyte membrane (PEM) associated with two electrodes representing for anode and cathode compose the membrane electrode assembly (MEA). Electrocatalyst as heart of HT-PEMFCs significantly affects the output of fuel cells, especially the cathodic electrocatalyst since the oxygen reduction reaction (ORR) kinetics is substantially sluggish than hydrogen oxidation reaction (HOR). Phosphoric acid doped polybenzimidazole (PA-PBI) is the state-of-the-art PEM for HT-PEMFCs; while, due to the low interaction between PA and PBI, PA leaching to the catalyst layer is normally observed during the long-term operation resulting in blocking of active sites to reduce three-phase boundary (TPB); besides, oxygen dissolution/diffusion in PA is much lower compared to Nafion, thereby, lower fuel cell performance is customarily recorded than Nafion PEMFCs. Thus, construction of high-performance ORR electrocatalyst with exceptional tolerance toward phosphate and increasing of oxygen concentration at TPB are highly desirable to realize the commercialization of HT-PEMFCs. Additionally, the stability of electrocatalyst should be significantly considered because the coalescence of platinum (Pt) nanoparticles as well as carbon corrosion is accelerated at high working temperature. In this review, we have summarized the recently reported Pt, non-Pt and meta-free electrocatalysts in HT-PEMFCs application. Surficial modification, alloying effect as well as substrate effect have been invited to construct high-performance Pt electrocatalyst in phosphoric acid electrolyte since the adsorption of phosphate on Pt is alleviated by surface coating and modulation of electronic configuration of Pt. Due to the comparably lower interaction with phosphate than Pt and considerable catalytic activity toward ORR, non-Pt and metal-free electrocatalyst have also been systematically investigated as HT-PEMFCs cathodic electrocatalyst. Finally, the perspectives and challenges in HT-PEMFCs have been discussed.