Acta Phys. -Chim. Sin. ›› 2021, Vol. 37 ›› Issue (9): 2010072.

Special Issue: Fuel Cells

• REVIEW •

### Principles, Strategies, and Approaches for Designing Highly Durable Platinum-based Catalysts for Proton Exchange Membrane Fuel Cells

Jiashun Liang, Xuan Liu, Qing Li()

• Received:2020-10-29 Accepted:2020-11-23 Published:2020-11-30
• Contact: Qing Li E-mail:qing_li@hust.edu.cn
• Supported by:
the National Natural Science Foundation of China(21972051);the Graduates' Innovation Fund, Huazhong University of Science and Technology, China(2020yjsCXCY020)

Abstract:

Proton exchange membrane fuel cells (PEMFCs) have attracted significant attention owing to their high conversion efficiency, high power density, and low pollution. Their performance is mainly governed by the oxygen reduction reaction (ORR) occurring at the cathode. Owing to the sluggish kinetics of ORR, a large amount of electrocatalysts, i.e., platinum (Pt), is required to accelerate the reaction rate and improve the performance of PEMFCs for practical applications. The use of Pt electrocatalysts inevitably increases the cost, thereby hindering the commercialization of PEMFCs. In addition, the activity and stability of the commercial Pt/C catalyst are still insufficient. Therefore, advanced electrocatalysts with high activity, good stability, and low cost are urgently needed. To date, some theoretical models, especially d-band center theory, have been proposed and guided the search for next-generation electrocatalysts with higher ORR activity. Based on these theories, several strategies and catalysts, especially Pt-based alloy catalysts, have been developed to accelerate ORR and improve the fuel cell performance. For instance, Pt–Ni octahedral nanoparticles (NPs) electrocatalysts have achieved remarkable ORR activity, with one order of magnitude higher activity than that of commercial Pt/C. However, PEMFCs are usually operated at a high voltage (0.6–0.8 V) and an acidic electrolyte, where the transition metals (M) are easily oxidized and etched away. The electronic effect induced by the introduction of M would be eliminated due to the dissolution of transition metals and the agglomeration of NPs, leading to the decay of ORR activity. Therefore, the long-term stability of oxygen reduction catalysts and fuel cells remains highly challenging. It is crucial to design an efficient and highly stable ORR catalyst to promote the application of PEMFCs. Aiming to the stability issues of fuel cell cathode catalysts, the current review summarizes the principles, strategies, and approaches for improving the stability of Pt-based catalysts. First, we introduce thermodynamic and kinetic principles that affect the stability of catalysts. Thermodynamic (such as cohesive energy, alloy formation energy, and segregation energy) and kinetic parameters (such as vacancy formation and diffusion barrier) regarding the structural stability of catalysts significantly affect the metal dissolution and atomic diffusion processes. In addition, these parameters seem to be associated with chemical bond energy to some extent, which could be employed as a descriptor for the stability of catalysts. Later, we outline some representative strategies and methods for improving catalyst stability, namely elemental doping, atomic arrangement engineering, chemical or physical confinement, and supporting material design. Finally, a brief summary and future research perspectives are provided.

MSC2000:

• O643