To fabricate intermetallic nanoparticles with high oxygen reduction reaction activity, a high-temperature heat treatment of 700 to 1,000 °C is required. This heat treatment provides energy sufficient to induce an atomic rearrangement inside the alloy nanoparticles, increasing the mobility of particles, making them structurally unstable and causing a sintering phenomenon where they agglomerate together naturally. These problems cannot be avoided using a typical heat treatment process that only controls the gas atmosphere and temperature. In this study, as a strategy to overcome the limitations of the existing heat treatment process for the fabrication of intermetallic nanoparticles, we propose an interesting approach, to design a catalyst material structure for heat treatment rather than the process itself. In particular, we introduce a technology that first creates an intermetallic compound structure through a primary high-temperature heat treatment using random alloy particles coated with a carbon shell, and then establishes catalytic active sites by etching the carbon shell using a secondary heat treatment process. By using a carbon shell as a template, nanoparticles with an intermetallic structure can be kept very small while effectively controlling the catalytically active area, thereby creating an optimal alloy catalyst structure for fuel cells.
During a long-term operation of polymer electrolyte membrane fuel cells(PEMFCs), the fuel cell performance may degrade due to severe agglomeration and dissolution of metal nanoparticles in the cathode. To enhance the electrochemical durability of metal catalysts and to prevent the particle agglomeration in PEMFC operation, this paper proposes a hybrid catalyst structure composed of PtCo alloy nanoparticles encapsulated by porous carbon layers. In the hybrid catalyst structure, the dissolution and migration of PtCo nanoparticles can be effectively prevented by protective carbon shells. In addition, O2 can properly penetrate the porous carbon layers and react on the active Pt surface, which ensures high catalytic activity for the oxygen reduction reaction. Although the hybrid catalyst has a much smaller active surface area due to the carbon encapsulation compared to a commercial Pt catalyst without a carbon layer, it has a much higher specific activity and significantly improved durability than the Pt catalyst. Therefore, it is expected that the designed hybrid catalyst concept will provide an interesting strategy for development of high-performance fuel cell catalysts.
In anion exchange membrane fuel cells, Pd nanoparticles are extensively studied as promising non-Pt catalysts due to their electronic structure similar to Pt. In this study, to fabricate Pd nanoparticles well dispersed on carbon support materials, we propose a synthetic strategy using mixed organic ligands with different chemical structures and functions. Simultaneously to control the Pd particle size and dispersion, a ligand mixture composed of oleylamine(OA) and trioctylphosphine(TOP) is utilized during thermal decomposition of Pd precursors. In the ligand mixture, OA serves mainly as a reducing agent rather than a stabilizer since TOP, which has a bulky structure, more strongly interacts with the Pd metal surface as a stabilizer compared to OA. The specific roles of OA and TOP in the Pd nanoparticle synthesis are studied according to the mixture composition, and the oxygen reduction reaction(ORR) activity and durability of highly-dispersed Pd nanocatalysts with different particles sizes are investigated. The results of this study confirm that the Pd nanocatalyst with large particles has high durability compared to the nanocatalyst with small Pd nanoparticles during the accelerated degradation tests although they initially indicated similar ORR performance.
In this study, a membrane electrode assembly(MEA) composed of three electrodes(anode, cathode, and reference electrode) is designed to investigate the effects of methanol concentration on the overpotentials of anode and cathode in direct methanol fuel cells(DMFCs). Using the three-electrode cell, in-situ analyses of the overpotentials are carried out during direct methanol fuel cell operation. It is demonstrated that the three-electrode cell can work effectively in transient state operating condition as well as in steady-state condition, and the anode and cathode exhibit different overpotential curves depending on the concentration of methanol used as fuel. Therefore, from the real-time separation of the anode and cathode overpotentials, it is possible to more clearly prove the methanol crossover effect, and it is expected that in-situ analysis using the three-electrode cell will provide an opportunity to obtain more diverse results in the area of fuel cell research.