Proton Exchange Membrane Fuel Cell Cathode Research Articles

Metal–Single Atom Support Interactions for Enhancing Proton-Exchange Membrane Fuel Cell Cathode Stability: A Review

Metal–Single Atom Support Interactions for Enhancing Proton-Exchange Membrane Fuel Cell Cathode Stability: A Review

Carbon‐Embedded Pt Alloy Cluster Catalysts for Proton Exchange Membrane Fuel Cells

AbstractMinimizing the use of platinum (Pt) in proton exchange membrane fuel cells (PEMFCs) is crucial for expanding the PEMFC market. The most straightforward approach would be to reduce the size of Pt particles. However, small Pt clusters, particularly those <2 nm in size, typically exhibit reduced activity for the oxygen reduction reaction (ORR) due to the overly strong adsorption of oxygen intermediates. Additionally, these small Pt clusters tend to degrade more quickly, resulting in lower durability. In this study, carbon‐embedded Pt alloy cluster catalysts (PtFe, PtCo, PtNi) that demonstrate high activity and durability in the PEMFC cathode are presented. Density functional theory calculations indicate that carbon atoms stably adsorb onto the Fe sites of PtFe clusters, making the neighboring Pt sites active for ORR with an optimal adsorption strength for oxygen intermediates. This research can pave the way for developing durable and efficient ORR catalysts while significantly reducing Pt usage in PEMFCs.

Corrosion Resistance and Conductivity of Ta-Nb-N-Coated 316L Stainless Steel as Bipolar Plates for Proton Exchange Membrane Fuel Cells

The large-scale application of stainless steel (SS) bipolar plates (BPs) in proton exchange membrane fuel cells (PEMFCs) is mainly limited by insufficient corrosion resistance and electrical conductivity. In this work, Ta-Nb-N coatings were prepared on 316L SS substrates by unbalanced magnetron sputtering to improve corrosion resistance and conductivity. The Ta-Nb-N coatings had a dense structure without obvious defects. In simulated PEMFC cathode environments consisting of 0.5 M H2SO4 + 2 ppm HF at 70 ± 0.5 °C, which is harsher than the U.S. Department of Energy specification, the corrosion current density of Ta-Nb-N-coated BPs was reduced to 2.2 × 10−2 μA·cm−2. Ta-Nb-N-coated samples showed better electrical conductivity than 316L SS, which had an excellent interfacial contact resistance of 9.2 mΩ·cm2. In addition, the Ta-Nb-N-coated samples had a water contact angle of 100.7°, showing good hydrophobicity for water management. These results indicate that Ta-Nb-N coatings could be a promising material for BPs.

Evaluation criterion of cathode flow field in air-cooling proton exchange membrane fuel cells

In recent years, air-cooling proton exchange membrane fuel cells (PEMFCs) have become a priority choice for applications due to their lightweight and simple structure. In this work, the mechanism of cathode flow field characteristics on PEMFC performance is revealed, and the evaluation criterion of the cathode flow field is proposed. A 2 kW PEMFC stack of 100 cells is used, and the different uniformity and airflow rate of the cathode flow field are achieved by varying the position and number of cathode fans with a constant total parasitic fan power. The PEMFC power, cathode temperature distribution, and single-cell voltage consistency of different configurations are evaluated. The results show that the maximum difference in output power and maximum temperature of different PEMFC cathode flow field configurations reach 6.5% and 22.3%, respectively. Three key parameters are proposed to evaluate the PEMFC cathode flow field: total uniformity rate can evaluate the overall uniformity of the PEMFC cathode flow field, vertical uniformity rate can be used to predict and evaluate the single-cell voltage consistency of the PEMFC stack, and cathode airflow rate determines the continuous operating power of the PEMFC stack. The evaluation criterion can guide the design and optimization of air-cooling PEMFCs.

Manipulation of Electronic States of Pt Sites via d-Band Center Tuning for Enhanced Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells.

Expediting the torpid kinetics of the oxygen reduction reaction (ORR) at the cathode with minimal amounts of Pt under acidic conditions plays a significant role in the development of proton exchange membrane fuel cells (PEMFCs). Herein, a novel Pt-N-C system consisting of Pt single atoms and nanoparticles anchored onto the defective carbon nanofibers is proposed as a highly active ORR catalyst (denoted as Pt-N-C). Detailed characterizations together with theoretical simulations illustrate that the strong coupling effect between different Pt sites can enrich the electron density of Pt sites, modify the d-band electronic environments, and optimize the oxygen intermediate adsorption energies, ultimately leading to significantly enhanced ORR performance. Specifically, the as-designed Pt-N-C demonstrates exceptional ORR properties with a high half-wave potential of 0.84 V. Moreover, the mass activity of Pt-N-C reaches 193.8 mA gPt-1 at 0.9 V versus RHE, which is 8-fold greater than that of Pt/C, highlighting the enormously improved electrochemical properties. More impressively, when integrated into a membrane electrode assembly as cathode in an air-fed PEMFC, Pt-N-C achieved a higher maximum power density (655.1 mW cm-2) as compared to Pt/C-based batteries (376.25 mW cm-2), hinting at the practical application of Pt-N-C in PEMFCs.

Optimal design of locally improved structure for enhancing mass transfer in PEMFC cathode flow field

At high current density, the mass transfer in proton exchange membrane fuel cells (PEMFC) is significantly influenced by the flow field structure. In this paper, a bilateral track flow field (BTFF) is proposed to improve the transverse and longitudinal mass transfer as well as the water removal capacity of PEMFC. The geometry of the BTFF is optimized by orthogonal tests to obtain the optimal combination of geometric parameters and levels. Then using numerical modeling, the impact of the optimized BTFF (BT6) on the efficiency of the PEMFC was examined. The results show that BT6 significantly improves the utilization of the under-rib region by shortening the reactive gas diffusion path length to obtain a more uniform oxygen distribution, and the average oxygen concentration in the midline of the under-rib of the BT6 is increased by 102.60%, furthermore, the current density is increased by 16.32% compared with that of the parallel flow field (case0). In addition, by reducing the cross-sectional area of the gas flow channel, the BT6 has a higher gas flow velocity, which accelerates the removal of cathode liquid water, and the average liquid water saturation in the midline of the under-rib of the BT6 is reduced by 15.26% compared with case0. Finally, by analyzing the net power density of PEMFC, it can be found that the net power density of BT6 is increased by 15.68% compared with case0, which has good practical application value.

Assessing Pt and Ni dissolution mechanism and kinetics of shape-controlled oxygen reduction nanocatalysts

An electrochemical flow cell combined with inductively coupled plasma mass spectrometry (FC-ICP-MS) is a powerful tool to understand the mechanisms of metal dissolution and to develop mitigation strategies. Herein, we quantified in situ the amount of Pt and Ni atoms dissolved from PtNi/C nanocatalysts employed to electrocatalyze the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cell cathode. The nanocatalysts feature similar crystallite size and Pt:Ni atomic ratio but different morphologies (spheres, octahedra, sponges). The FC-ICP-MS results reveal that the nanocatalyst morphology affects the dissolution rate of Pt and Ni but not the dissolution mechanism. They also provide analytical evidence that dissolution of Pt atoms is consistently accompanied by the dissolution of Ni atoms exceeding the stoichiometric composition. Furthermore, we demonstrate that ex situ acid leaching mitigates, but does not entirely prevent, the electrochemical dissolution of Ni atoms. Stabilized Pt and Ni dissolution rates were achieved after a one hour long accelerated stress test (AST). We provide evidence that the Pt dissolution rate remains constant before and after the AST. In contrast, the dissolution rate of Ni decreases by a factor of 10 following the AST. Among various nanoparticle shapes, spherical PtNi/C nanoparticles offer the best solution regarding the Pt and Ni retention compared to other nanoparticle shapes.

Silver and Silver Alloy on Carbon-supported Catalysts for Cathodes in Proton Exchange Membrane Fuel Cell and Direct Ethanol Fuel Cell

This research was focused on the synthesis of 20 %wt silver, silver platinum alloy, and silver-copper alloy catalysts on carbon Vulcan XC-72 supporter for proton exchange membrane fuel cell (PEMFC) and direct ethanol fuel cell (DEFC) cathode using sodium borohydride method. Herein, the ratio of silver and platinum or copper sources was 1:1 by weight. The obtained catalysts were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and the electro-activity performance was investigated on single-cell testing. XRD and TEM results confirmed the catalytic products of the Ag metal, AgPt alloy, and silver copper oxide (AgxCu2-xO). Therefore, the particle size of the catalytic 20 %wt AgPt/C was observed in the smallest size of about 4.71±1.03 nm. The catalyst was selected for PEMFC and DEFC cathode testing. It showed high power density of 14.68 and 1.26 W/cm2.g(M), respectively.

Elucidation of the Interplay between the Features of the Precursor and the Physicochemical Properties of “Core-Shell” Hierarchical Carbon Nitride Electrocatalysts for the Oxygen Reduction Reaction

The oxygen reduction reaction (ORR) is a major bottleneck in the operation of proton-exchange membrane fuel cells (PEMFCs) since it introduces large overpotentials (no less than 250-300 mV), which degrade significantly the energy conversion efficiency of the device. In addition, the electrocatalysts (ECs) yielding the lowest ORR overpotentials in the acidic environment found at the PEMFC cathode are based on Pt, a very scarce critical raw material (CRM). Pt raises concerns as it might trigger serious supply bottlenecks in the event of a practical widespread implementation of PEMFCs in the framework of today’s energy transition. Hence, the development of high-performing and durable ECs for the ORR is a major stepping stone towards the large-scale rollout of PEMFCs.In our research group a new breakthrough approach has been devised for the synthesis of ORR ECs, that is completely different form the preparation routes that are commonly adopted in the state of the art [1, 2]. Briefly, the approach consists in the pyrolysis and subsequent treatment of a precursor obtained by coupling suitable carbon species/sacrificial supports with a zeolitic inorganic-organic polymer electrolyte (Z-IOPE). The latter comprises anionic complexes including the Pt “catalyst” and other “co-catalysts”, which are bridged by organic binders [1,2].On one hand, the proposed approach has already shown its potential to yield ECs exhibiting a performance and durability improved with respect to Pt/C benchmark ECs. On the other hand, the proposed approach is extremely flexible, especially with respect to the synthesis of the initial EC precursor. In principle, it is possible to modulate a number of crucial features of such EC precursor, with a particular reference to: (i) the chemical composition (e.g., in terms of Pt, other “co-catalysts” and N; the latter plays a crucial role to stabilize the active sites into “coordination nests” on the EC surface, raising durability); and (ii) the morphology, that can be “templated” on suitable species (e.g., carbon species, sacrificial supports). The very flexibility of the proposed synthetic process needs to be leveraged appropriately to maximize the performance of the final ORR ECs, at the same time minimizing the efforts wasted on approaches with a low development potential.Herein it is elucidated how the modulation in the parameters involved in the synthesis of the EC precursor (e.g., the binder and the approaches to couple the Z-IOPE with the support) impact the physicochemical and electrochemical properties of the final ECs, with a particular reference to the chemical composition, morphology and distribution of the ORR active sites. An extensive characterization of the final ECs is carried out. Inductively-coupled plasma atomic emission spectroscopy (ICP-AES) and microanalysis are adopted to determine the bulk chemical composition. Near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) is used to elucidate the surface chemical composition and the chemical states of the surface elements. Ultra-high resolution scanning electron microscopy (UHR-SEM) and transmission electron microscopy (TEM) allow for the elucidation of EC morphology. The porosimetric features are probed by automatic gas adsorption instrumentations. Wide-angle X-ray diffraction (WAXD) is crucial to resolve the crystal structure. Cyclic voltammetry with the rotating ring-disk electrode method (CV-TF-RRDE) is used to clarify the “ex-situ” electrochemical performance and ORR reaction mechanism. Finally, the most promising ECs are used in the fabrication of single PEMFCs, that are tested as a function of the operating conditions.It is revealed that, in comparison with the Pt/C benchamark, some ECs are characterized by a much higher intrinsic kinetic performance due to the electronic and bifunctional effects bestowed by the carbon nitride support and the «co-catalysts». Finally, the binder has a marked effect on the stoichiometry, size, and distribution of the PtMx aggregates bearing the active sites.

Pressure and Impedance Based in Situ Diagnostic Methods for Water Management in Proton Exchange Membrane Fuel Cells Applications

Recent advancements in proton exchange membrane fuel cells (PEMFCs) have led to significant developments in low-carbon transport technology, enabling the generation of clean, efficient electricity with minimal noise and toxic emissions for heavy-duty applications. However, effective water management remains a critical challenge in PEMFCs due to the intricate phase changes and liquid-gas transport processes within key components, which significantly impact cell performance and longevity in industrial applications. Given the rapid dynamics of water activities and material responses within cells, in situ diagnostic techniques for water management in PEMFCs are essential for optimizing cell performance and extending the lifespan of fuel cell stack and system.Water, electrochemically produced on the cathode side, can cause potential flooding in key components including the catalyst layer (CL) and gas diffusion layers (GDLs), impeding air/oxygen supply to the cathode side. To characterize the performance loss induced by water flooding, Electrochemical Impedance Spectroscopy (EIS) is commonly employed as a fuel cell diagnostic tool. EIS records the contributions of different polarization processes to the global impedance with individual time constants during operation. However, the interpretation of complex EIS spectra can be very challenging, as polarization processes may overlap in frequency and be difficult to identify. To address this issue, Distribution of Relaxation Times (DRT) analysis is implemented as a powerful tool that allows for a clear separation and quantification of the polarization processes showing as peaks in a frequency domain [1]. Thus, we utilize EIS-based DRT analysis as an in-situ diagnostic tool to detect cathode flooding during cell operation. To validate this approach, we have conducted tests on a 300 cm2 low temperature PEMFC, varying one operation parameter at a time and evaluating its effects on cathode flooding by studying the frequency and height evolution of DRT peaks.Nevertheless, water flooding is not confined to the cathode side, as water can also permeate through the proton exchange membrane (PEM) and reach the anode side, resulting in potential fuel starvation on the cathode's counterpart and subsequent degradation of carbon-based materials. To address the sensitivity limitation of the EIS-based DRT method in detecting anode flooding, we employ an in-house developed pressure drop indicator (PDI) tool, as a non-invasive and real-time approach for diagnosing water flooding in the anode. The PDI tool assesses the pressure drop across anode channels, which is a function of the liquid water contents in bipolar plates considering the pressure reduction mainly caused by the frictional drag [2]. The effectiveness of the PDI tool is validated through cell testing at different water flooding levels by varying relative humidity and pressure conditions. This technique offers timely and sensitive detection of anode water flooding in PEMFCs, which is crucial for alarming irreversible material degradation in the electrode and facilitating appropriate follow-up actions.To conclude, we have developed and employed in situ PDI and EIS-based DRT methods within our water management framework for diagnosing water flooding in both the anode and cathode of PEMFCs in industrial applications. The combination of these techniques offers real-time and accurate assessments on water management conditions, which is crucial for optimizing overall performance and longevity of PEMFC stacks and systems.[1] Heinzmann, M., Weber, A., Ivers-Tiffée, E. (2018). Advanced impedance study of polymer electrolyte membrane single cells by means of distribution of relaxation times. Journal of Power Sources, 402, 24-33.[2] Barbir, F., Gorgun, H., & Wang, X. (2005). Relationship between pressure drop and cell resistance as a diagnostic tool for PEM fuel cells. Journal of Power Sources, 141(1), 96-101. Figure 1

Excellent anti-corrosion and conductivity of NbN coated on Ti bipolar plate by controlling N2 flow rates

The metal bipolar plates which play a crucial role in proton exchange membrane fuel cells (PEMFCs) are applied extensively due to their excellent property. However, the degraded corrosion resistance by corrosive ion and the increased interfacial contact resistance by passivation layer under acidic operating environment will affect the efficiency of PEMFCs. Metal nitride can solve that problem in some extent, however, the effect of nitrogen flow rates on the metal nitride formation during coating deposition is unclear. To solve these, NbN coatings with different N2 flow rates were applied to the bare Ti substrate via magnetron sputtering and thereafter studied. Compared with bare Ti substrate, outstanding anticorrosion performance is exhibited for the coated sample, whose corrosion current decreased three orders of magnitude (∼10−8 A/cm2) in simulated PEMFC cathode environment and the interfacial contact resistance decreased to tenth of that bare Ti substrate (∼5 mΩ cm2).

Adaptive neural network observer for proton-exchange membrane fuel cell system

Abstract This paper develops an adaptive neural network (NN) observer for proton-exchange membrane fuel cells (PEMFCs). Indeed, information on the oxygen excess ratio (OER) value is crucial to ensure optimal management of the durability and reliability of the PEMFC. The OER indicator is computed from the mass of oxygen and nitrogen inside the PEMFC cathode. Unfortunately, the measurement process of both these masses is difficult and costly. To solve this problem, the design of a PEMFC state observer is attractive. However, the behaviour of the fuel cell system is highly non-linear and its modelling is complex. Due to this constraint, a multilayer perceptron neural network (MLPNN)-based observer is proposed in this paper to estimate the oxygen and nitrogen masses. One notable advantage of the suggested MLPNN observer is that it does not require a database to train the NN. Indeed, the weights of the NN are updated in real time using the output error. In addition, the observer parameters, namely the learning rate and the damping factor, are online adapted using the optimization tools of extremum seeking. Moreover, the proposed observer stability analysis is performed using the Lyapunov theory. The observer performances are validated by simulation under MATLAB®/Simulink®. The supremacy of the proposed adaptive MLPNN observer is highlighted by comparison with a fixed-parameter MLPNN observer and a classical high-gain observer (HGO). The mean relative error value of the excess oxygen rate is considered the performance index, which is equal to 1.01% for an adaptive MLPNN and 3.95% and 9.95% for a fixed MLPNN and HGO, respectively. Finally, a robustness test of the proposed observer with respect to measurement noise is performed.

Multi-Objective sliding mode control of proton exchange membrane fuel cell system based on adaptive algebraic observer

To improve the efficiency and extend the lifespan of the proton exchange membrane fuel cells (PEMFC), it is imperative to control PEMFC’s supply system effectively. A sliding mode controller (SMC) based on adaptive algebraic observer is designed to control the oxygen excess ratio and the pressure difference between the cathode and anode of PEMFC. First, a 9th order physical model of the PEMFC system is established including air supply system, hydrogen supply system and the stack, which is validated against the experimental data with the maximum output voltage error of 2.91%. Then, a SMC is designed based on the control-oriented PEMFC model. An adaptive algebraic observer for the estimation of the gas partial pressure is designed to be used in the SMC. Finally, simulation is conducted and results show that the performance of the designed SMC is superior than that of the PID controller in terms of the oxygen excess ratio settling time (1s less), the pressure difference settling time (50% less) and overshoot (0.5 kPa less).

(Keynote) Interplay between Physicochemical Properties of Precursors and “Core-Shell” Hierarchical Carbon Nitride Electrocatalysts for the Oxygen Reduction Reaction

The oxygen reduction reaction (ORR) is a major bottleneck in the operation of proton-exchange membrane fuel cells (PEMFCs) since it introduces large overpotentials (no less than 250-300 mV), which degrade significantly the energy conversion efficiency of the device. In addition, the electrocatalysts (ECs) yielding the lowest ORR overpotentials in the acidic environment found at the PEMFC cathode are based on Pt, a very scarce critical raw material (CRM). Pt raises concerns as it might trigger serious supply bottlenecks in the event of a practical widespread implementation of PEMFCs in the framework of today’s energy transition. Hence, the development of high-performing and durable ECs for the ORR is a major stepping stone towards the large-scale rollout of PEMFCs.In our research group a new breakthrough approach has been devised for the synthesis of ORR ECs, that is completely different form the preparation routes that are commonly adopted in the state of the art [1, 2]. Briefly, the approach consists in the pyrolysis and subsequent treatment of a precursor obtained by coupling suitable carbon species/sacrificial supports with a zeolitic inorganic-organic polymer electrolyte (Z-IOPE). The latter comprises anionic complexes including the Pt “catalyst” and other “co-catalysts”, which are bridged by organic binders [1,2].On one hand, the proposed approach has already shown its potential to yield ECs exhibiting a performance and durability improved with respect to Pt/C benchmark ECs. On the other hand, the proposed approach is extremely flexible, especially with respect to the synthesis of the initial EC precursor. In principle, it is possible to modulate a number of crucial features of such EC precursor, with a particular reference to: (i) the chemical composition (e.g., in terms of Pt, other “co-catalysts” and N; the latter plays a crucial role to stabilize the active sites into “coordination nests” on the EC surface, raising durability); and (ii) the morphology, that can be “templated” on suitable species (e.g., carbon species, sacrificial supports). The very flexibility of the proposed synthetic process needs to be leveraged appropriately to maximize the performance of the final ORR ECs, at the same time minimizing the efforts wasted on approaches with a low development potential.Herein it is elucidated how the modulation in the parameters involved in the synthesis of the EC precursor (e.g., the binder and the approaches to couple the Z-IOPE with the support) impact the physicochemical and electrochemical properties of the final ECs, with a particular reference to the chemical composition, morphology and distribution of the ORR active sites. An extensive characterization of the final ECs is carried out. Inductively-coupled plasma atomic emission spectroscopy (ICP-AES) and microanalysis are adopted to determine the bulk chemical composition. Near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) is used to elucidate the surface chemical composition and the chemical states of the surface elements. Ultra-high resolution scanning electron microscopy (UHR-SEM) and transmission electron microscopy (TEM) allow for the elucidation of EC morphology. The porosimetric features are probed by automatic gas adsorption instrumentations. Wide-angle X-ray diffraction (WAXD) is crucial to resolve the crystal structure. Cyclic voltammetry with the rotating ring-disk electrode method (CV-TF-RRDE) is used to clarify the “ex-situ” electrochemical performance and ORR reaction mechanism. Finally, the most promising ECs are used in the fabrication of single PEMFCs, that are tested as a function of the operating conditions.It is revealed that, in comparison with the Pt/C benchamark, some ECs are characterized by a much higher intrinsic kinetic performance due to the electronic and bifunctional effects bestowed by the carbon nitride support and the «co-catalysts». Finally, the binder has a marked effect on the stoichiometry, size, and distribution of the PtMx aggregates bearing the active sites.

(Invited) Model-Predictive Design of Low Pt Loaded PEMFC Catalyst Layers

Proton exchange membrane fuel cells (PEMFCs) are a promising means to decarbonize the global vehicle fleet, but commercialization is limited by costly Pt catalysts, among other challenges. PEMFC designs with low Pt loading typically suffer anomalous performance losses. Previous studies have agreed that poor device performance is linked to complex physiochemical processes in the cathode catalyst layer (CL) [1]. More specifically, poor performance with low Pt-loading is attributed to sluggish proton and/or oxygen transport through the nano-thin Nafion ionomer in the CL. Previous studies have also identified that the properties of the Nafion thin films in the CL vary from those previously measured for thicker membranes. However, research has not yet definitively connected CL polymer properties with PEMFC limitations in low Pt-loaded cells, nor found a means to address the limitations for low cost, higher-performance PEMFCs.In this presentation, we will describe efforts to quantify structure-property relationships for thin-film Nafion and incorporate these relationships into PEMFC numerical simulations to identify advantageous PEMFC catalyst layer designs. We model nm-scale transport in thin-film Nafion to develop structure-property relationships for thin-film Nafion, based on in situ neutron reflectometry [2], and conductivity measurements [3] on thin film Nafion. These result in a model that calculates the conductivity as a function of temperature, local water uptake, film thickness, and underlying substrate (Pt or carbon). Incorporating these structure-property models into a continuum-scale PEMFC cathode half-cell model to locally resolve proton conductivity and O2 diffusion improves model fits to PEMFC data with varying Pt loading [4]. The fits provide new insights into the coupling between kinetic, mass transport, and Ohmic losses in low-Pt-loaded PEMFC cathodes and show that Ohmic losses in thin film Nafion play a key limiting role in low-Pt loaded cells. We conclude with a parametric study of PEMFC CL design parameters with low Pt loading. Incorporating multi-scale modelling of Nafion transport processes enhances the predictive model capabilities and unlocks new insights into CL design. We will present a detailed analysis of how best to manage coupled limiting phenomena in PEM fuel cells, and identify functionally graded catalyst layer designs that could significantly improve PEMFC power density with low Pt loading [4]. Weber, A. and Kusoglu, A. Mater. Chem. A. 2014. DOI: 10.1039/c4ta02952fDeCaluwe, S.C. et al. Nano Energy 2018. DOI: 10.1016/j.nanoen.2018.01.008Paul, D.K. et al. Electrochem. Soc. 2014. DOI: 10.1149/2.0571414jesRandall, C.R. and DeCaluwe, S.C., Electrochem. Soc. 2022. DOI: 10.1149/1945-7111/ac8cb4

Platinum–Nickel Electrocatalysts for a Proton-Exchange Membrane Fuel Cell Cathode: Their Synthesis, Acid Treatment, Microstructure and Electrochemical Behavior

Within this research, we studied the structural–morphological and electrochemical characteristics of the PtNi/C catalysts synthesized via the two-stage sequential reduction of precursors. We also carried out a comparative study of the obtained bimetallic catalysts and their commercial Pt/C analog. The use of triethylamine as a surfactant as well as the acid treatment as an additional synthesis stage, were shown to have a positive effect on the functional parameters of the bimetallic electrocatalysts. The resulting PtNi/C electrocatalyst demonstrates a mass activity value of 389 A gPt−1, which is 1.6 times higher than this parameter for a commercial analog.

High-entropy L12-Pt(FeCoNiCuZn)3 intermetallics for ultrastable oxygen reduction reaction

Enhancing the stability of Pt-based electrocatalysts for the sluggish cathodic oxygen reduction reaction (ORR) is critical for proton exchange membrane fuel cells (PEMFCs). Herein, high-entropy intermetallic (HEI) L12-Pt(FeCoNiCuZn)3 is designed for durable ORR catalysis. Benefiting from the unique HEI structure and the enhanced intermetallic phase stability, Pt(FeCoNiCuZn)3/C nanoparticles demonstrate significantly improved stability over Pt/C and PtCu3/C catalysts. The Pt(FeCoNiCuZn)3/C exhibits a negligible decay of the half-wave potential during 30,000 potential cycles from 0.6 to 1.0 V, whereas Pt/C and PtCu3/C are negatively shifted by 46 and 36 mV, respectively. Even after 10,000 cycles at potential up to 1.5 V, the mass activity of Pt(FeCoNiCuZn)3/C still shows ∼70% retention. As evidenced by the structural characterizations, the HEI structure of Pt(FeCoNiCuZn)3/C is well maintained, while PtCu3/C nanoparticles undergo severe Cu leaching and particle growth. In addition, when assembled Pt(FeCoNiCuZn)3/C as the cathode in high-temperature PEMFC of 160 °C, the H2-O2 fuel cell delivers almost no degradation even after operating for 150 h, demonstrating the potential for fuel cell applications. This work provides a facile design strategy for the development of high-performance ultrastable electrocatalysts.

Catalyst Aggregate Size Effect on the Mass Transport Properties of Non-Noble Metal Catalyst Layers for PEMFC Cathodes

Non-noble metal catalysts (NNMCs) are regarded as a promising alternative to the costly Pt-based materials required to catalyze the oxygen reduction reaction (ORR) in proton exchange membrane fuel cell (PEMFC) cathodes. However, the large diversity of NNMC synthesis approaches reported in the literature results in materials featuring a wide variety of particle sizes and morphologies, and the effect of these properties on these catalysts’ PEMFC performance remains poorly understood. To shed light on this matter, in this work we studied the physical and electrochemical properties of NNMC layers prepared from materials featuring broadly different aggregate sizes, whereby this property was tuned by ball milling the precursors used in the NNMCs’ synthesis in the absence vs presence of a solvent. This led to two NNMCs featuring similar Fe-speciations and ORR-activities, but with vastly different aggregate sizes of >5 μm vs ≈100 nm, respectively. Following the extensive characterization of catalyst layers (CLs) prepared with these materials via electron microscopy and X-ray tomography, PEMFC tests at different loadings unveiled that the smaller aggregate size and ≈20% higher porosity of the CL prepared from the wet-milled sample resulted in an improvement of its mass transport properties (as well as a ≈2-fold enhancement of its peak power density under H2/air operation) over the dry-milled material.

Inducing Covalent Atomic Interaction in Intermetallic Pt Alloy Nanocatalysts for High-Performance Fuel Cells.

The harsh working environments of proton exchange membrane fuel cells (PEMFCs) pose huge challenges to the stability of Pt-based alloy catalysts. The widespread presence of metallic bonds with significantly delocalized electron distribution often lead to component segregation and rapid performance decay. Here we report L10 -Pt2 CuGa intermetallic nanoparticles with a unique covalent atomic interaction between Pt-Ga as high-performance PEMFC cathode catalysts. The L10 -Pt2 CuGa/C catalyst shows superb oxygen reduction reaction (ORR) activity and stability in fuel cell cathode (mass activity=0.57 A mgPt -1 at 0.9 V, peak power density=2.60/1.24 W cm-2 in H2 -O2 /air, 28 mV voltage loss at 0.8 A cm-2 after 30 000 cycles). Theoretical calculations reveal the optimized adsorption of oxygen intermediates via the formed biaxial strain on L10 -Pt2 CuGa surface, and the durability enhancement stems from the stronger Pt-M bonds than those in L11 -PtCu resulted from Pt-Ga covalent interactions.

Inducing Covalent Atomic Interaction in Intermetallic Pt Alloy Nanocatalysts for High‐Performance Fuel Cells

AbstractThe harsh working environments of proton exchange membrane fuel cells (PEMFCs) pose huge challenges to the stability of Pt‐based alloy catalysts. The widespread presence of metallic bonds with significantly delocalized electron distribution often lead to component segregation and rapid performance decay. Here we report L10−Pt2CuGa intermetallic nanoparticles with a unique covalent atomic interaction between Pt−Ga as high‐performance PEMFC cathode catalysts. The L10−Pt2CuGa/C catalyst shows superb oxygen reduction reaction (ORR) activity and stability in fuel cell cathode (mass activity=0.57 A mgPt−1 at 0.9 V, peak power density=2.60/1.24 W cm−2 in H2‐O2/air, 28 mV voltage loss at 0.8 A cm−2 after 30 000 cycles). Theoretical calculations reveal the optimized adsorption of oxygen intermediates via the formed biaxial strain on L10−Pt2CuGa surface, and the durability enhancement stems from the stronger Pt−M bonds than those in L11−PtCu resulted from Pt−Ga covalent interactions.