Engineering the catalyst layers towards enhanced local oxygen transport of Low-Pt proton exchange membrane fuel cells: Materials,designs, and methods

Proton exchange membrane fuel cells (PEMFCs) help to achieve decarbonized energy demand due to their advantages of no pollution emission and high power efficiency. But the commercialization of fuel cells has encountered difficulties due to the high-cost issue. The key to addressing the cost issue of PEMFCs lies in reducing Pt amount. However, concentration polarization in the high current density region increases as the decrease of Pt loading, of which the local transport loss of oxygen in the cathode catalyst layer (CCL) occupies the most significant part. Therefore, reducing local oxygen transport resistance is necessary to achieve ultra-low Pt loading in practical PEMFC. This paper focuses on summarizing various electrode design methods for the CCL that optimize the local transport resistance of oxygen, including modifications to the ionomer layer, catalyst structure, and overall electrode structure. Each improvement method is explained with the mechanism of the local oxygen transport process, investigating the effect of different ionomer and Pt-based nanoparticle structures, distribution, and surface chemistries on the local transport pathways. The insights proposed in this paper provide recommendations for the fabrication and design of high-efficiency low-platinum fuel cells.     

A hydrophobic blend binder for anti-water flooding of cathode catalyst layers in polymer electrolyte membrane fuel cells

We report polymer electrolyte membrane fuel cells (PEMFCs) in which poly(vinylidene fluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) copolymer was added to the existing sPEEK binder in cathode catalyst layers (CCLs). Compared to a control case with no such copolymer, the cell with the copolymer exhibits improved performance, particularly in the oxygen mass transport. The improved mass transport behavior is attributed to the copolymer that makes CCLs more hydrophobic and thus suppresses water flooding significantly. Contact angle measurements and various electrochemical characterizations consistently support the copolymer effect for the improved oxygen mass transport. In addition, the introduction of P(VdF-co-HFP) lowers the glass transition temperature of the binder, which contributes to enhancing the adhesion properties between the CCLs and membranes.     

Non-precious metal catalysts synthesized from precursors of carbon, nitrogen, and transition metal for oxygen reduction in alkaline fuel cells

Non-precious metal catalysts (NPMCs) synthesized from the precursors of carbon, nitrogen, and transition metals were investigated as an alternate cathode catalyst for alkaline fuel cells (AFCs). The procedures to synthesize the catalyst and the post-treatment were tailored to refine its electrocatalytic properties for oxygen reduction reaction (ORR) in alkaline electrolyte. The results indicated that the performance of NPMCs prepared with carbon-supported ethylenediamine-transition metal composite precursor and subjected to heat-treatment shows comparable activity for oxygen reduction with Pt/C catalyst. The NPMC exhibits an open circuit potential of 0.97 V and a maximum power density of 177 mW cm⁻² at 50 °C when tested in anion exchange membrane (AEM) fuel cells.     

Activity and stability of non-precious metal catalysts for oxygen reduction in acid and alkaline electrolytes

The activity and stability of non-precious metal catalysts (NPMCs) for the oxygen reduction reaction (ORR) in both acid and alkaline electrolytes were studied by the rotating disk electrode technique. The NPMCs were prepared through the pyrolysis of cobalt-iron-nitrogen chelate followed by combination of pyrolysis, acid leaching, and re-pyrolysis. In both environments, the catalysts heat-treated at 800-900 °C exhibited relatively high activity. Particularly, an onset potential of 0.92 V and a well-defined limiting current plateau for the ORR was observed in alkaline medium. The potential cycling stability test revealed the poor stability of NPMCs in acid solution with an exponential increase in the performance degradation as a function of the number of potential cycling. In contrast, the NPMCs demonstrated exceptional stability in alkaline solution. The numbers of electron transferred during the ORR on the NPMCs in acid and alkaline electrolytes were 3.65 and 3.92, respectively, and these numbers did not change before and after the stability test. XPS analysis indicated that the N-containing sites of catalysts are stable before and after the stability test when in alkaline solution but not in acid solution.     

Highly active and durable carbon support Pt-rare earth catalyst for proton exchange membrane fuel cell

Pt-rare earth catalysts are highly efficient novel electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) due to their high stability and activity. In this study, we prepare Pt-YO_x/C catalysts using the traditional wet chemical reduction method. The optimal quantity of Y-oxides loaded onto the Pt/C surface is determined based on electrochemical performance using linear sweep voltammetry (LSV) and cyclic voltammetry (CV) methods. After accelerated durability tests (ADT), the remnant electrochemical surface area (ECSA) and mass active (MA) in Pt-YO_x/C catalyst are relatively higher compared to the commercial Pt/C (JM). In the single-cell test, the maximum mass power densities of the MEAs prepared by self-made Pt-YO_x/C and Pt/C (JM) catalysts in cathodes record at 1895 and 1371 mW mg_Pt⁻¹, respectively, which shows a successful increment in platinum utilization. These results indicate that Pt-YO_x/C catalyst can potentially improve the durability and lower the cost of PEMFCs.     

Carbon corrosion behaviors and the mechanical properties of proton exchange membrane fuel cell cathode catalyst layer

Carbon corrosion-induced catalyst layer destruction is the primary reason to the performance decay of proton exchange membrane fuel cells (PEMFCs). In this study, the accelerated stress test (AST) on carbon corrosion was conducted, and real-time CO₂ evolution was measured in-situ by non-dispersive infrared (NDIR) analysis. The performance degradation was investigated by the reduction of the current density and the loss of electrochemical active surface area (ECSA) of Pt. The loss of catalyst layer porosity and increase of mass transport resistance were investigated by the visible reduction of porosity and thickness in the cathode catalyst layer (CCL). Further mechanical tensile tests showed that the elastic modulus of CCL remained unchanged initially, and then increased probably due to the compaction of CCL. In the final step, it decreased due to the complete failure of the material. Thus, carbon corrosion was proved to alter the mechanical strength of CCL.     

A novel non-platinum group electrocatalyst for PEM fuel cell application

Precious-metal catalysts (predominantly Pt or Pt-based alloys supported on carbon) have traditionally been used to catalyze the electrode reactions in polymer electrolyte membrane (PEM) fuel cells. However as PEM fuel systems begin to approach commercial reality, there is an impending need to replace Pt with a lower cost alternative. The present study investigates the performance of a carbon-supported tantalum oxide material as a potential oxygen reduction reaction (ORR) catalyst for use on the cathode side of the PEM fuel cell membrane electrode assembly. Although bulk tantalum oxide tends to exhibit poor electrochemical performance due to limited electrical conductivity, it displays a high oxygen reduction potential; one that is comparable to Pt. Analysis of the Pourbaix electrochemical equilibrium database also indicates that tantalum oxide (Ta₂O₅) is chemically stable under the pH and applied potential conditions to which the cathode catalyst is typically exposed during stack operation. Nanoscale tantalum oxide catalysts were fabricated using two approaches, by reactive oxidation sputtering and by direct chemical synthesis, each carried out on a carbon support material. Nanoscale tantalum oxide particles measuring approximately 6 nm in size that were sputtered onto carbon paper exhibited a mass-specific current density as high as one-third that of Pt when measured at 0.6 V vs. NHE. However, because of the two-dimensional nature of this particle-on-paper structure, which limits the overall length of the triple-phase boundary junctions where the oxide, carbon paper, and aqueous electrolyte meet, the corresponding area-specific current density was quite low. The second synthesis approach yielded a more extended, three-dimensional structure via chemical deposition of nanoscale tantalum oxide particles on carbon powder. These catalysts exhibited a high ORR onset potential, comparable to that of Pt, and displayed a significant improvement in the area-specific current density. Overall, the highest mass-specific current density of the carbon-powder supported catalyst was ˜9% of that of Pt.     

Carbons as low-platinum catalyst supports and non-noble catalysts for polymer electrolyte fuel cells

Polymer electrolyte fuel cells, including acidic proton exchange membrane fuel cells (PEMFCs) and alkaline anion exchange membrane fuel cells (AEMFCs), are the types of the most promising high-efficiency techniques for conversion hydrogen energy to electricity energy. However, the catalysts’ insufficient activity and stability toward oxygen reduction reaction (ORR) at the cathodes of these devices are still the important constraints to their performance. So far, carbon black supported platinum (Pt/C) and its alloys are still the most practical and best-performing type of catalysts. However, the scarcity of Pt is highly challenging and the high price of commercial catalyst will continue to drive up the cost of both PEMFCs and AEMFCs. Moreover, the traditional carbon black support is susceptible to corrosion especially under electrochemical operation, itself inactive for ORR and weakly binding with Pt-based nanoparticles. In this review, the advanced carbons synthesized by various template methods, including hard-template, soft-template, self-template and combined-template, are systematically evaluated as low-Pt catalyst supports and non-noble catalysts. For the templates-induced carbon-based catalysts, this review presents a comprehensive overview on the carbon supported low-Pt catalysts from aspect of composition, size and shape control as well as the non-noble carbon catalysts such as transition metal-nitrogen-carbons, metal-free carbons and defective carbons. Furthermore, this review also summarizes the applications of low/non-Pt carbon-based catalysts base on the template-induce advanced carbons at the cathodes of PEMFCs and AEMFCs. Overall, the templates-induced carbons can show some perfect attributes including ordered morphology, reasonable pore structure, high conductivity and surface area, good corrosion resistance and mechanical property, as well as strong metal–support interaction. All of these features are of particular importance for the construction of high-performance carbon-based ORR catalysts. However, some drawbacks mainly involve the removal of templates, maintenance of morphological structure, and demetalation. To address these issues, this review also summarizes some effective strategies, such as employing the easily removed hard/soft-templates, developing the advantageous self-templates, enhancing the metal–support interaction by formation of chemical binds, etc. In conclusion, this review provides an effective guide for the construction of template-induced advanced carbons and carbon-based low/non-Pt catalysts with analysis of technical challenges in the development of ORR electrocatalysts for both PEMFCs and AEMFCs, and also proposes several future research directions for overcoming the challenges towards practical applications.     

Numerical analyses on oxygen transport resistances in polymer electrolyte membrane fuel cells using a novel agglomerate model

Characterizing oxygen transport resistances in different components of a polymer electrolyte membrane fuel cell (PEMFC) is essential to achieve better cell performance at high current under low Pt loading. In this work, a macroscopic three-dimensional model, together with a novel agglomerate model was proposed to analyze impacts of operating conditions on these resistances via limiting current strategy. By introducing a focusing factor obtained with lattice Boltzmann method at mesoscopic level, the structure-dependent local transport resistance in ionomer thin-film of the electrode was comprehensively captured and validated by existing experimental studies. Contributions of the cell components to the total transport resistance were dissected. Results show that the present agglomerate model could well reproduce the local transport behaviors of oxygen in catalyst layer by fully considering the detailed nanoscale diffusion and adsorption processes. A small mass fraction of oxygen was favored to minimize the relative deviation of the local transport resistance from its intrinsic one due to the water production and heat generation, which can reach 7% for the mass fraction of oxygen of 1%. Contribution of the in-plane diffusion of oxygen in the inactive electrode is around 1%. The total transport resistance increased with the absolute pressure, mainly due to the dominated molecular diffusion mechanism in gas channel and gas diffusion layer. Gas convection accounted for 26% of the oxygen transport resistance originated from gas channel. The transport resistance of catalyst layer increased significantly with the reduction of Pt loading, and decreased with relative humidity and operating temperature, particularly at high Pt loading.     

PEMFC modeling based on characterization of effective diffusivity in simulated cathode catalyst layer

Oxygen diffusion in the cathode catalyst layer (CCL) is crucial to the high performance of polymer electrolyte membrane fuel cells (PEMFCs), especially in high current density or concentration loss regions. Recently, PEMFC performance has been reported to be enhanced by increasing CCL pore size and pore volume due to the reduction of diffusion resistance by capillary water equilibrium [Yim et al., Electrochimica Acta 56 (2011) 9064–9073]. Herein, we simulate these experimental results utilizing a new one-dimensional PEMFC model considering the effects of accumulated water film in CCL on oxygen diffusion. Two CCL microstructures were numerically generated based on agglomerate models to examine the experimental results obtained for two membrane electrode assembly (MEA) samples with different CCL porosity. The effective diffusivity of oxygen in the CCL was estimated by performing auxiliary simulations of oxygen concentration in CCL microstructures covered by a film of liquid water, with exponential correlation obtained between effective diffusivity and the thickness of the above film. Polarization curves predicted by the present model were in good agreement with experimental results. In agreement with the results of Yim et al., the present model predicts that the MEA featuring a CCL with smaller pores (which are more easily filled by liquid water) should exhibit a larger concentration loss at high current densities.     

Modeling an ordered nanostructured cathode catalyst layer for proton exchange membrane fuel cells

A 3D mathematical model of an ordered nanostructured cathode catalyst layer (CCL) has been developed for proton exchange membrane (PEM) fuel cells. In an ordered nanostructured CCL, carbon nanotubes (CNTs) are used as support material for Pt catalyst, upon which a thin layer of proton-conducting polymer (Nafion) is deposited, which are then aligned along the main transport direction (perpendicular to the membrane) of various species. The model considers all the relevant processes in different phases of an ordered nanostructured CCL. In addition, the effect of Knudsen diffusion is accounted in the model. The model can predict not only the performance of an ordered nanostructured CCL at various operating and design conditions but also can predict the distributions of various fields in different phases of an ordered nanostructured CCL. The predicted nanostructured CCL performance with estimated membrane overpotential is validated with measured data found in the literature, and a good agreement is obtained between the model prediction and measured result. Moreover, a parametric study is conducted to investigate the effect of key design parameters on the performance of an ordered nanostructured CCL. In the absence of liquid water, it is found that oxygen diffusion in the pore phase is not the limiting factor for the performance of an ordered nanostructured CCL, owing to its parallel gas pores and high porosity. However, the transport of dissolved oxygen through the Nafion phase has a significant effect on the performance of an ordered nanostructured CCL. Further, it is found that increasing the spacing between CNTs results in a considerable drop in the performance of an ordered nanostructured CCL at the base case conditions considered in the simulation.     

Iron and cobalt containing electrospun carbon nanofibre-based cathode catalysts for anion exchange membrane fuel cell

The use of Pt-based cathode catalyst materials hinders the widespread application of anion exchange membrane fuel cells (AEMFCs). Herein, we present a non-precious metal catalyst (NPMC) material based on pyrolysed Fe and Co co-doped electrospun carbon nanofibres (CNFs). The prepared materials are studied as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts in alkaline and acidic environments. High activity towards the ORR in alkaline solution indicated the suitability of the prepared NPMCs for the application at the AEMFC cathode. In the AEMFC test, the membrane-electrode assembly bearing a cathode with the nanofibre-based catalyst prepared with the ionic liquid (IL) (Fe/Co/IL–CNF–800b) showed the maximum power density (P_max) of 195 mW cm⁻², which is 78% of the P_max obtained with a commercial Pt/C cathode catalyst. Such high ORR electrocatalytic activity was attributed to the unique CNF structure, high micro-mesoporosity, different nature of nitrogen species and metal-N_x active centres.     

On the possibility of replacement of Pt by Pd in a hydrogen electrode of PEM fuel cells

Nanostructured Pt- and Pd-based electrocatalysts for hydrogen oxidation in proton exchange membrane (PEM) fuel cells have been synthesized and characterized. Electro-active metallic particles were obtained by chemical reduction of precursor salts on Vulcan XC-72 carbon carrier using ethylene glycol with the addition of formaldehyde. Using the synthesized Pd- and Pt-based catalysts membrane–electrode assemblies (MEAs) have been prepared and successfully tested in single fuel cells. Comparison of MEA performances demonstrates the principal possibility of replacement of the Pt by the Pd on the hydrogen electrode of PEM fuel cells.     

Microstructured membranes for improving transport resistances in proton exchange membrane fuel cells

Proton exchange membrane fuel cells (PEMFCs) have been identified as one of the most promising renewable energy system for use in automotive applications. However, due to the wide range of weather conditions around the world, the PEMFCs must be stable for operating under these variable conditions. One of the inefficiencies of PEMFCs in automotive applications is during vehicle warm-up, where the low hydration level within the PEMFC can lead to a low performance of the fuel cell. In this study, a proton exchange membrane (PEM) was prepared with regular, microstructured features tuned over a range of aspect ratios. These microstructured membranes were incorporated into MEAs and analyzed for their membrane, proton, and oxygen transport resistances. These fuel cells were tested under different conditions to simulate vehicle start-up, normal operating conditions, and hot operating conditions. It was determined that microstructured PEMs improved performance over planar PEMs under both the start-up and hot conditions. Despite the improved performance of the microstructured PEMs, a high hydrogen cross-over and short-circuit current were also observed for these samples. Adjusting the preparation techniques and tuning the dimensions of the microstructures may provide avenues for further optimization of PEMFC performance.     

Pore-scale study of effects of different Pt loading reduction schemes on reactive transport processes in catalyst layers of proton exchange membrane fuel cells

Reducing the Platinum (Pt) loading while maintaining the performance is highly desired for promoting the commercial use of proton exchange membrane fuel cells (PEMFCs). Different methods have been adopted to fabricate catalyst layers (CLs) with low Pt loading, including utilizing lower Pt/C catalysts (MA), mixing high Pt/C catalysts with bare carbon black particles (MB), and reducing CL thickness while maintaining high Pt/C ratio (MC). In this study, self-developed pore-scale model is adopted to investigate the performance of the three Pt reduction methods. It is found that MA shows the best performance while MB shows the worst. Then, effects of Pt dispersion are further explored. The results show that denser Pt sites will result in higher local oxygen flux and thus higher local transport resistance. Therefore, MA method, which shows the better Pt dispersion, leads to improved performance. Third, CLs with quasi-realistic structures are investigated. Higher tortuosity resulting from the random pores produces higher bulk resistance along the thickness direction, while MA still exhibits the best performance. Finally, improved CL structures are investigated by designing perforated CL structures. It is found that adding perforations can significantly reduce the bulk transport resistance and can improve the CL performance. It is demonstrated that CL structure plays important roles on performance, and there are still huge potentials to further improve CL performance by increasing Pt dispersion and optimizing CL structures.     

Encapsulated iron-based oxygen reduction electrocatalysts by high pressure pyrolysis

Non-precious metal catalysts (NPMCs) are candidate materials to replace platinum for proton exchange membrane fuel cells (PEMFCs). Herein we reported a type of iron-based NPMCs prepared by high pressure pyrolysis for the oxygen reduction reaction (ORR) in acidic media. The catalysts are in form of carbon microspheres in a sub-microscale consisting of iron-containing nanoparticles encapsulated by graphitic layers. By tailoring temperatures and duration of pyrolysis, the best ORR catalyst was achieved at 700 °C and 75 min, which exhibits an onset potential of 0.85 V at 0.1 mA cm^?2 and a half-wave potential of 0.72 V in acid media. After 10,000 potential cycles, only 25 mV shift of half-wave potential is observed showing excellent stability. An analogue material prepared from nitrogen-free precursors shows significant electrochemical activity though it is much lower than that from the nitrogen containing precursors and can be improved by post treatment in ammonia. These results indicate the contribution to the catalysis from surface nitrogen functionalities and encapsulated metal-containing nanoparticles.     

Performance of carbon-supported PtPd as catalyst for hydrogen oxidation in the anodes of proton exchange membrane fuel cells

In this work, the replacement of platinum by palladium in carbon-supported catalysts as anodes for hydrogen oxidation reaction (HOR), in proton exchange membrane fuel cells (PEMFCs), has been studied. Anodes with carbon-supported Pt, Pd, and equiatomic Pt:Pd, with various Nafion^® contents, were prepared and tested in H₂|O₂ (air) PEMFCs fed with pure or CO-contaminated hydrogen. An electrochemical study of the prepared anodes has been carried out in situ, in membrane electrode assemblies, by cyclic voltammetry and CO electrooxidation voltammetry. The analyses of the corresponding voltammograms indicate that the anode composition influences the cell performance. Single cell experiments have shown that platinum could be replaced, at least partially, saving cost with still good performance, by palladium in the hydrogen diffusion anodes of PEMFCs. The performance of the PtPd catalyst fed with CO-contaminated H₂ used in this work is comparable to Pt, thus justifying further work varying the CO concentration in the H₂ fuel to assert its CO tolerance and to study the effect of the Pt:Pd atomic ratio.     

Ultra-low catalyst loading cathode electrode for anion-exchange membrane fuel cells

A new cathode architecture for anion-exchange membrane fuel cells (AEMFCs) is proposed and fabricated by direct deposition of palladium (Pd) particles onto the surface of the micro-porous layer (MPL) that is interfaced with a backing layer. The MPL is composed of carbon nanotubes while the backing layer is made of a carbon paper. The sputter-deposited electrode with a worm-like shape not only extends the electrochemical active surface area, but also facilitates the oxygen transport. This new cathode, albeit with a Pd loading as low as 0.035 mg cm⁻², enables the peak power density of an AEM direct ethanol fuel cell to be as high as 88 mW cm⁻² (at 60 °C), which is even higher than that using a conventional cathode with a 15-times higher Pd loading. The significance of the present work lies in the fact that the new sputter-deposited electrode is more suitable for fuel-electrolyte-fed fuel cells than the conventional electrode designed for proton-exchange membrane fuel cells (PEMFCs).     

Recent advances in activity and durability enhancement of Pt/C catalytic cathode in PEMFC: Part II: Degradation mechanism and durability enhancement of carbon supported platinum catalyst

Polymer electrolyte membrane fuel cell (PEMFC) technology has advanced rapidly in recent years, with one of active area focused on improving the long-term performance of carbon supported catalysts, which has been recognized as one of the most important issues to be addressed for the commercialization of the PEMFCs. The cathode catalyst layer in PEMFCs typically contains platinum group metal/alloy nanoparticles supported on a high-surface-area carbon. Carbon support corrosion and Pt dissolution/aggregation are considered as the major contributors to the degradation of the Pt/C catalysts. If the platinum particles cannot maintain their structure over the lifetime of the fuel cell, change in the morphology of the catalyst layer from the initial state will result in a loss of electrochemical activity. This paper reviews the recent advances in the stability improvement of the Pt/C cathodic catalysts in PEMFC, especially focusing on the durability enhancement through the improved Pt–C interaction. Future promising strategies towards the extension of catalysts operation life are also prospected.     

Understanding cathode flooding and dry-out for water management in air breathing PEM fuel cells

An analysis of water management in air breathing small polymer electrolyte membrane fuel cells (PEMFCs) is presented. Comprehensive understanding of flooding and dry-out limiting phenomena is presented through a combination of analytical modeling and experimental investigations using a small PEMFC prototype. Configurations of the fuel cell with different heat and mass transfer properties are experimentally evaluated to assess the impact of thermal resistance and mass transport resistance on water balance. Manifestation of dry-out and flooding problems, as limiting phenomena, are explained through a ratio between these two resistances. Main conclusions are that decreasing the ratio between thermal and mass transport resistance under a certain point leads to flooding problems in air breathing PEMFC. Increasing this ratio leads to dry-out of the polymer electrolyte membrane. However, too high thermal resistance or too low mass transport resistance reduces the limiting current by pushing forward the dry-out problem. This work provides a framework to achieve the proper balance between thermal rejection and mass transport to optimize the maximum current density of free convection fuel cells.