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Proton exchange membrane fuel cell (PEMFC) parameter extraction is an important issue in modeling and control of renewable energies. The PEMFC problem's main objective is to estimate the optimal value of unknown parameters of the electrochemical model. The main objective function of the optimization problem is the sum of the square errors between the measured voltages and output voltages of the proposed electrochemical optimized model at various loading conditions. Natural rabbit survival strategies such as detour foraging and random hiding are influenced by Artificial rabbit optimization (ARO). Meanwhile, rabbit energy shrink is mimicked to control the smooth switching from detour foraging to random hiding. In this work, the ARO algorithm is proposed to find the parameters of PEMFC. The ARO performance is verified using experimental results obtained from conducting laboratory tests on the fuel cell test system (SCRIBNER 850e, LLC). The simulation results are assessed with four competitive algorithms: Grey Wolf Optimization Algorithm, Particle Swarm Optimizer, Salp Swarm Algorithm, and Sine Cosine Algorithm. The comparison aims to prove the superior performance of the proposed ARO compared with the other well-known competitive algorithms.
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Forced-flow atomic layer deposition nanolamination is employed to fabricate Pt-Ni nanoparticles on XC-72, with the compositions ranging from Pt94Ni6 to Pt67Ni33. Hydrogen is used as a co-reactant for depositing Pt and Ni. The growth rate of Pt is slower than that using oxygen reactant, and the growth exhibits preferred orientation along the (111) plane. Ni shows much slower growth rate than Pt, and it is only selectively deposited on Pt, not on the substrate. Higher ratios of Ni would hinder subsequent stacking of Pt atoms, resulting in lower overall growth rate and smaller particles (1.3-2.1 nm). Alloying of Pt with Ni causes shifted lattice that leads to larger lattice parameter and d-spacing as Ni fraction increases. From the electronic state analysis, Pt 4f peaks are shifted to lower binding energies with increasing the Ni content, suggesting charge transfer from Ni to Pt. Schematic of the growth behavior is proposed. Most of the alloy nanoparticles exhibit higher electrochemical surface area and oxygen reduction reaction activity than those of commercial Pt. Especially, Pt83Ni17 and Pt87Ni13 show excellent mass activities of 0.76 and 0.59 A mgPt -1, respectively, higher than the DOE target of 2025, 0.44 A mgPt -1.
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The structural tailoring of Pt-based catalysts into 1D nanowires for oxygen reduction reactions (ORR) has been a focus of research. Mo(CO)6 is commonly used as a morphological modifier to form nanowires, but it is found that it inevitably leads to Mo doping. This doping introduces unique electrochemical signals not seen in other Pt-based catalysts, which can directly reflect the stability of the catalyst. Through experiments, it is demonstrated that Mo doping is detrimental to ORR performance, and theoretical calculations have shown that Mo sites that are inherently inactive also poison the ORR activity of the surrounding Pt. Therefore, a novel gas-assisted technique is proposed to replace Mo(CO)6 with CO, which forms ultrafine nanowires with an order of magnitude increase in length, ruling out the effect of Mo. The catalyst performs at 1.24 A mgPt -1, 7.45 times greater than Pt/C, demonstrating significant ORR mass activity, and a substantial improvement in stability. The proton exchange membrane fuel cell using this catalyst provides a higher power density (0.7 W cm-2). This study presents a new method for the preparation of ultra-long nanowires, which opens up new avenues for future practical applications of low-Pt catalysts in PEMFC.
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High-temperature proton exchange membrane fuel cell (HT-PEMFC) based on phosphoric acid doped polybenzimidazole membrane (PBI/PA) operating at 120-200 °C can provide insensitivity to carbon monoxide (CO) and simplified managements of water and heat and thus attract significant global attention. However, one signiï¬cant drawback is its low utilization of precious metal catalysts resulted from the PA poisoning and inefficient three-phase boundary. Studies of binder materials in catalyst layers for HT-PEMFC are gradually emerging and there are few literature reviews on this important topic. The purpose of this review is to describe the various types of binders based on their molecular structure and electrochemical properties, with particular emphasis on catalyst layer for fuel cells. Importantly, this review provides a better understanding of relationship between fuel cell performance and the gas permeability and conductivity of different binders. Then, future directions of research and development in binder materials of HT-PEMFC are pointed out.
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Understanding the ice nucleation mechanism in the catalyst layers (CLs) of proton exchange membrane (PEM) fuel cells and inhibiting icing by designing the CLs can optimize the cold start strategies, which can enhance the performance of PEM fuel cells. Herein, mitigating the structural matching and templating effects by adjusting the surface morphology and wettability can inhibit icing on the platinum (Pt) catalyst surface effectively. The Pt(211) surface can inhibit icing because the atomic spacing of (211) crystalline surface is much larger than the characteristic distance of ice crystal, thereby mitigating the structural matching effects. A water overlayer on the Pt surface induced by the strong attraction of Pt can act as a template for ice layers and plays an important role in the icing process. Buckling of water overlayer due to the larger atomic spacing of (211) crystalline surface mitigates the templating effect and inhibits icing. Moreover, the water overlayer on the hydrophobic Pt(211) surface with fewer water molecules also mitigates the templating effect, which makes ice nucleation more difficult than homogeneous nucleation. These findings reveal the ice nucleation mechanisms on the Pt catalyst surface from the molecular level and are valuable for catalyst designs to inhibit icing in CL.
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Non-precious metal-based nitrogen-doped carbon (M-Nx/C) shows great potential as a substitute for precious metal Pt-based catalysts. However, the conventional pyrolytic methods for forming M-Nx/C active sites are prone to issues such as the lack of synergistic interactions among bimetallic atoms and the potential encasement of active sites, leading to compromised catalytic efficiency and hindered mass transfer. In this work, a highly active FeCo-N-C@U-AC electrocatalyst is developed with a high density of active sites, adequate exposure of catalytic sites, and robust mass transfer capability using the chemical vapor-phase deposition (CVD) technique. The resulting catalyst demonstrates impressive oxygen reduction reaction (ORR) catalytic performance and stability, with half-wave potentials of 0.820 V (0.1 M HClO4) and 0.911 V (0.1 M KOH), respectively. It also exhibits significantly enhanced stability, retaining 93.25% and 98.38% of current after continuous 50 000 s of durability testing, surpassing the retention rates of Pt/C (80.31% in HClO4 and 84.96% in KOH electrolytes). Notably, when employed as a cathode catalyst in proton exchange membrane fuel cells (PEMFCs) and zinc-air flow batteries (ZAFBs), the FeCo-N-C@U-AC catalyst delivers peak power densities of 859 and 162 mW·cm-2, respectively, showcasing competitive performance comparable to benchmark Pt/C.
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In this paper, the degradation of PEMFC under different operating conditions in dynamic cycle condition is studied. Firstly, according to the failure mechanism of PEMFC, various operating conditions in dynamic cycle condition are classified, and the health indexes are established. Simultaneously, the rates and degrees of the output voltage decline of the PEMFC under different operating conditions during the dynamic cycling process were compared. Then, a model based on variational mode decomposition and long short-term memory with attention mechanism (VMD-LSTM-ATT) is proposed. Aiming at the performance of PEMFC is affected by the external operation, VMD is used to capture the global information and details, and filter out interference information. To improve the prediction accuracy, ATT is used to assign weight to the features. Finally, in order to verify the effectiveness and superiority of VMD-LSTM-ATT, we respectively apply it to three current conditions under dynamic cycle conditions. The experimental results show that under the same test conditions, RMSE of VMD-LSTM-ATT is increased by 56.11 % and MAE is increased by 28.26 % compared with GRU attention. Compared with SVM, RNN, LSTM and LSTM-ATT, RMSE of VMD-LSTM-ATT is at least 17.26 % higher and MAE is at least 5.65 % higher.
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Exergy analysis evaluates the efficiency of system components by quantifying the rate of entropy generation. In general, the exergy destruction rate or irreversibility rate was directly obtained through the exergy balance equation. However, this method cannot determine the origin of the component's entropy generation rate, which is a very important factor in system design and improvement. In this study, a thorough energy, exergy, and thermoeconomic analysis of a proton-exchange membrane fuel cell (PEMFC) was performed, providing the heat transfer rate, entropy generation rate, and cost loss rate of each component. The irreversibility rate of each component was obtained by the Gouy-Stodola theorem. Detailed and extensive exergy and thermoeconomic analyses of the PEMFC system determined that water cooling units experience the greatest heat transfer among the components in the studied PEMFC system, resulting in the greatest irreversibility and, thus, the greatest monetary flow loss.
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The current limitations of air-cooled proton exchange membrane fuel cells (AC-PEMFCs) in water and heat management remain a major obstacle to their commercialization. A 90 cm2 full-size AC-PEMFC multi-physical field-coupled numerical model was constructed; isothermal and non-isothermal calculations were performed to explore the effects of univariate and multivariate variables on cell performance, respectively. The isothermal results indicate that lower temperature is beneficial to increase the humidity of MEA, and distribution uniformity at lower stoichiometric ratios and lower temperatures is better. The correlation between current density distribution and temperature, water content, and concentration distribution shows that the performance of AC-PEMFCs is influenced by multiple factors. Notably, under high current operation, the large heat generation may lead to high local temperature and performance decline, especially in the under-channel region with drier MEA. The higher stoichiometric ratio can enhance heat dissipation, improve the uniformity of current density, and increase power density. Optimal fuel cell performance is achieved with a stoichiometric ratio of 300, balancing the mixed influence of multiple factors.
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Analyzing degradation heterogeneity of proton exchange membrane fuel cell (PEMFC) while maintaining high practicality is consistently challenging, primarily due to the destructive and costly nature of existing techniques relying on material characterization. In this work, a designed magnetic array integrating 16 sensors within 25 cm2 space is used for direct scanning and imaging of PEMFC performance heterogeneity during its degradation. Results are validated through degradation mechanism analysis and material characterization, confirming its potential in guiding the development of durable materials.
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Proton-exchange membrane fuel cells (PEMFCs) and water electrolysis (PEMWE) are rapidly developing hydrogen energy conversion devices. Catalyst layers and membranes have been studied extensively and reviewed. However, few studies have compared gas diffusion layers (GDLs) in PEMWE and PEMFC. This review compares the differences and similarities between the GDLs of PEMWE and PEMFC in terms of their material and mass transport characteristics. First, the GDL materials are selected based on their working conditions. Carbon materials are prone to rapid corrosion because of the high anode potential of PEMWEs. Consequently, metal materials have emerged as the primary choice for GDLs. Second, the mutual counter-reactions of the two devices result in differences in mass transport limitations. In particular, water flooding and the effects of bubbles are major drawbacks of PEMFCs and PEMWE, respectively; well-designed structures can solve these problems. Imaging techniques and simulations can provide a better understanding of the effects of materials and structures on mass transfer. Finally, it is anticipated that this review will assist research on GDLs of PEMWE and PEMFC.
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Polymer electrolyte membrane fuel cells (PEMFCs) have attracted much attention as highly efficient, eco-friendly energy conversion devices. However, carbon-supported Pt (Pt/C) catalysts for PEMFCs still have several problems, such as low long-term stability, to be widely commercialized in fuel cell applications. To address the stability issues of Pt/C such as the dissolution, detachment, and agglomeration of Pt nanoparticles under harsh operating conditions, we design an interesting fabrication process to produce a highly active and durable Pt catalyst by introducing a robust carbon shell on the Pt surface. Furthermore, this approach provides insights into how to regulate the carbon shell layer for fuel cell applications. Through the application of an appropriate amount of H2 gas during heat treatment, the carbon shell pores, which are integral to the structure, can be systematically modulated to facilitate oxygen adsorption for the oxygen reduction reaction. Simultaneously, the carbon shell functions as a protective barrier, preventing catalyst degradation. In this regard, we investigate an in-depth analysis of the effects of critical parameters including H2 content and the flow rate of H2/N2 mixed gas during heat treatment to prepare better catalysts.
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This article offers a PV-PEMFC-batteries energy management strategy (EMS) that aims to meet the following goals: keep the DC link steady at the standard value, increase battery lifespan, and meet power demand. The suggested multi-source renewable system (MSRS) is made to meet load demand while using extra power to fill batteries. The major energy source for the MSRS is photovoltaic, and fuzzy logic MPPT is used to guarantee that the PV operates at optimal efficiency under a variety of irradiation conditions. The suggested state machine control consists of 15 steps. It prioritizes the proton exchange membrane fuel cell (PEMFC) as a secondary source for charging the battery when power is abundant and the state of charge (SOC) is low. The MSRS is made feasible by meticulously coordinating control and power management. The MSRS is made achievable by carefully orchestrated control and electricity management. The efficacy of the proposed system was evaluated under different solar irradiance and load conditions. The study demonstrates that implementing the SMC led to an average improvement of 2.3% in the overall efficiency of the system when compared to conventional control techniques. The maximum efficiency was observed when the system was operating under high load conditions, specifically when the state of charge (SOC) was greater than the maximum state of charge (SOCmax). The average efficiency achieved under these conditions was 97.2%. In addition, the MSRS successfully maintained power supply to the load for long durations, achieving an average sustained power of 96.5% over a period of 7.5 s. The validity of the modeling and management techniques mentioned in this study are confirmed by simulation results utilizing the MATLAB/Simulink (version: 2016, link: https://in.mathworks.com/products/simulink.html ) software tools. These findings show that the proposed SMC is effective at managing energy resources in MSRS, resulting in improved system efficiency and reliability.
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Gas crossover is critical in proton exchange membrane (PEM)-based electrochemical systems. Recently, single-layer graphene (SLG) has gained great research interest due to its outstanding properties as a barrier layer for small molecules like hydrogen. However, the applicability of SLG as a gas-blocking interlayer in PEMs has yet to be fully understood. In this work, two different approaches for transferring SLG from a copper or a polymeric substrate onto PEMs are compared regarding their application in low-temperature PEM fuel cells. The SLG is sandwiched between two Nafion XL membranes to form a stable composite membrane. The successful transfer is confirmed by Raman spectroscopy and in ex situ hydrogen permeation experiments in the dry state, where a reduction of 50% upon SLG incorporation is achieved. The SLG composite membranes are characterized by their performance and hydrogen-blocking ability in a fuel cell setup at typical operating conditions of 80 °C and with fully humidified gases. The performance of the fuel cell incorporating an SLG composite membrane is equal to that of the reference cell when avoiding the direct etching process from a copper substrate, as remnants from copper etching deteriorate the performance of the fuel cell. For both transfer processes, the hydrogen crossover reduction of SLG composite membranes is only 15-19% (1.5 barabs) in the operating fuel cell. Further, hydrogen pumping experiments suggest that the barrier function of SLG impairs the water transport through the membrane, which may affect water management in electrochemical applications. In summary, this work shows the successful transfer of SLG into a PEM and confirms the effective hydrogen-blocking capability of the SLG interlayer. However, the hydrogen-blocking ability is significantly reduced when running the cell at the typical humidified operating conditions of PEM fuel cells, which follows from a combination of reversible interlayer alteration upon humidification and irreversible defect formation upon PEM fuel cell operation.
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In Proton Exchange Membrane Fuel Cells (PEMFCs), the presence of residual water within the Gas Diffusion Layer (GDL) poses challenges during cold starts and accelerates degradation. A computational model based on the Lattice Boltzmann Method (LBM) was developed to consider the capillary pressure inside the PEMFC and to analyze the exact geometries of the GDLs, which were obtained using the Computed Tomography scan. The novelty of this study is to suggest a methodology to compare the quantitative water removal performance of the GDLs without long-term experimental testing. Two different samples of GDLs were considered, pristine and aged. The results of quantitative measurements revealed the amount of water columns (breakthroughs) inside each sample. Considering the volume of 12,250,000 µm3 for each sample, the pristine and the aged samples are prone to have 774,200 µm3 (6.32%) and 1,239,700 µm3 (10.12%) as water columns in their porous domain. Micro-structural properties such as connectivity, mean diameter, effective diffusivity, etc. were also compared to observe the impacts of aging on the properties of the GDL.
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The membrane electrode assembly (MEA) is the core component of proton exchange membrane fuel cells (PEMFCs), which is the place where the reaction occurrence, the multiphase material transfer and the energy conversion, and the development of MEA with high activity and long stability are crucial for the practical application of PEMFCs. Currently, efforts are devoted to developing the regulation of MEA nanostructure engineering, which is believed to have advantages in improving catalyst utilization, maximizing three-phase boundaries, enhancing mass transport, and improving operational stability. This work reviews recent research progress on platinum group metal (PGM) and PGM-free catalysts with multidimensional nanostructures, catalyst layers (CLs), and nano-MEAs for PEMFCs, emphasizing the importance of structure-function relationships, aiming to guide the further development of the performance for PEMFCs. Then the design strategy of the MEA interface is summarized systematically. In addition, the application of in situ and operational characterization techniques to adequately identify current density distributions, hot spots, and water management visualization of MEAs is also discussed. Finally, the limitations of nanostructured MEA research are discussed and future promising research directions are proposed. This paper aims to provide valuable insights into the fundamental science and technical engineering of efficient MEA interfaces for PEMFCs.
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Proton exchange membranes are an essential component of proton-exchange membrane fuel cells (PEMFC). Their performance is directly related to the development of ionic channel networks through hydration. Current sensing atomic force microscopy (CSAFM) can map the local conductance and morphology of a sample surface with sub-nano resolution simultaneously by applying a bias voltage between the conducting tip and sample holder. In this study, the ionic channel network variation of Nafion by hydration has been quantitatively characterized based on the basic principles of electrodynamics and CSAFM. A nano-sized PEMFC has been created using a Pt-coated tip of CSAFM and one side Pt-coated Nafion, and studied under different relative humidity (RH) conditions. The results have been systematically analyzed. First, the morphology of PEMFC under each RH has been studied using line profile and surface roughness. Second, the CSAFM image has been analyzed statistically through the peak value and full-width half-maximum of the histograms. Third, the number of protons moving through the ionic channel network (NPMI) has been derived and used to understand ionic channel network variation by hydration. This study develops a quantitative method to comprehend variations in the ionic channel network by calculating the movement of protons into the ionic channel network based on CSAFM images. To verify the method, a comparison is made between the NPMI and the changes in proton conductivity under different RH conditions and it reveals a good agreement. This developed method can offer a quantitative approach for characterizing the morphological structure of PEM. Also, it can provide a quantitative tool for interpretating CSAFM images.
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FeâNâC is the most promising alternative to platinum-based catalysts to lower the cost of proton-exchange-membrane fuel cell (PEMFC). However, the deficient durability of FeâNâC has hindered their application. Herein, a TiN-doped FeâNâC (FeâNâC/TiN) is elaborately synthesized via the sol-gel method for the oxygen-reduction reaction (ORR) in PEMFC. The interpenetrating network composed by FeâNâC and TiN can simultaneously eliminate the free radical intermediates while maintaining the high ORR activity. As a result, the H2O2 yields of FeâNâC/TiN are suppressed below 4%, ≈4 times lower than the FeâNâC, and the half-wave potential only lost 15 mV after 30 kilo-cycle accelerated durability test (ADT). In a H2âO2 fuel cell assembled with FeâNâC/TiN, it presents 980 mA cm-2 current density at 0.6 V, 880 mW cm-2 peak power density, and only 17 mV voltage loss at 0.80 A cm-2 after 10 kilo-cycle ADT. The experiment and calculation results prove that the TiN has a strong adsorption interaction for the free radical intermediates (such as *OH, *OOH, etc.), and the radicals are scavenged subsequently. The rational integration of Fe single-atom, TiN radical scavenger, and highly porous network adequately utilize the intrinsic advantages of composite structure, enabling a durable and active Pt-metal-free catalyst for PEMFC.
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In the cathode of proton exchange membrane fuel cells (PEMFCs), Fe and N co-doped carbon (Fe-N-C) materials with atomically dispersed active sites are one of the satisfactory candidates to replace Pt-based catalysts. However, Fe-N-C catalysts are vulnerable to attack from reactive oxygen species, resulting in inferior durability, and current strategies failing to balance the activity and stability. Here, this study reports Fe and Ce single atoms coupled catalysts anchored on ZIF-8-derived nitrogen-doped carbon (Fe/Ce-N-C) as an efficient ORR electrocatalyst for PEMFCs. In PEMFC tests, the maximum power density of Fe/Ce-N-C catalyst reached up to 0.82 W cm-2, which is 41% larger than that of Fe-N-C. More importantly, the activity of Fe/Ce-N-C catalyst only decreased by 21% after 30 000 cycles under H2/air condition. Density functional theory reveals that the strong coupling between the Fe and Ce sites result in the redistribution of electrons in the active sites, which optimizes the adsorption of OH* intermediates on the catalyst and increases the intrinsic activity. Additionally, the admirable radical scavenging ability of the Ce sites ensured that the catalysts gained long-term stability. Therefore, the addition of Ce single atoms provides a new strategy for improving the activity and durability of oxygen reduction catalysts.
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Proton-exchange membrane fuel cell technology is a key component in the future zero-carbon energy system, generating power from carbon-free fuels, such as green hydrogen. However, the high Pt loading in conventional fuel cell electrodes to maintain electrocatalytic activity and durability, especially on the cathode for oxygen reduction, is the Achilles heel for the worldwide deployment of fuel cell technologies. To minimize Pt consumption for oxygen reduction, we synthesized Pt-Co-based electrocatalysts with meticulous structuring from micrometer to the atomic scale based on reaction pathways. The resulting Pt-Co-based electrocatalysts contain only 1.9 wt% Pt, which is 20 times lower than the conventional Pt-C catalysts for fuel cells. By utilizing electrospinning and in situ synthesis, we anchored three-dimensionally structured zeolitic imidazolate frameworks on continuously connected nanofibrous electrospun mats. The Pt-Co@Pt-free nanowire (PC@PFN) electrocatalysts contain Pt-Co nanoparticles (NPs) and non-Pt elements, Co-containing sites comprising NPs, nanoclusters, and N-coordinated Co single atoms. Despite the ultralow Pt loading in PC@PFN, the mass activity exceeds the U.S. Department of Energy 2025 target by 2.8 times and retains 85.5% of the initial activity after 80,000 durability test cycles, possibly owing to synergistic reaction pathways between Pt and non-Pt sites.