Recent progress of electrocatalysts for hydrogen proton exchange membrane fuel cells

Due to stringent environmental regulations and the limited resources of fossil-based fuels, there is an urgent demand for clean and eco-friendly energy conversion devices. These criteria appear to be met by hydrogen proton exchange membrane fuel cells (PEMFCs). PEMFCs have attracted tremendous attention on account of their excellent performance with tunable operability and good portability. Nonetheless, their practical applications are hugely influenced by the scarcity and high cost of platinum (Pt) used as electrocatalysts at both cathode and anode. Pt is also susceptible to easy catalyst poisoning. Herein, this paper reviews the progress of the research regarding the development of electrocatalysts practically used in hydrogen PEMFCs, where the corner-stone reactions are cathodic oxygen reduction reaction (ORR) and anodic hydrogen oxidation reaction (HOR). To reduce the costs of PEMFCs, lessening or eliminating the use of Pt is of prime importance. For current and forthcoming laboratory/large-scale PEMFCs, there is much interest in developing substitute catalysts based on cheaper materials. As such are non-platinum (non-Pt), non-platinum group metals (non-PGMs), metal oxides, and non-metal electrocatalysts. Hence, high-performance, state-of-the-art, and novel structured electrocatalysts as replacements for Pt are needed.     

Magnetically modified electrocatalysts for oxygen evolution reaction in proton exchange membrane (PEM) water electrolyzers

Green hydrogen production can only be realized via water electrolysis using renewable energy sources. Proton exchange membrane water electrolyzers have been demonstrated as the technology of choice for mass production of green hydrogen due to their scalability and potential high efficiency. However, the technology is still relatively expensive due to the catalyst materials cost and operational limitations due to mass transfer and activation polarizations. During the oxygen evolution reaction, oxygen bubbles stick to the electrode surface and this causes a low reaction rate and high mass transfer losses. In this study, the commonly used electrocatalyst for oxygen evolution reactions; IrO₂, is modified by introducing magnetic Fe₃O₄ to achieve greater bubble separation at the anode during operation. The prepared composite catalysts were characterized using Scanning Electron Microscope, Energy Dispersive X-Ray Analysis, X-Ray Powder Diffraction, X-ray photoelectron spectroscopy and Brunauer–Emmett–Teller characterization methods. The modified composite electrocatalyst samples are magnetized to investigate the magnetic field effect on oxygen evolution reaction performance in proton exchange membrane water electrolyzers. 90% IrO₂ - 10% Fe₃O₄ and 80% IrO₂ - 20% Fe₃O₄ samples are tested via linear sweep voltammetry both ex-situ and in-situ in a proton exchange membrane water electrolyzer single cell. According to the linear sweep voltammetry tests, the magnetization of the 80% IrO₂ - 20% Fe₃O₄ sample resulted in 15% increase in the maximum current density. Moreover, the single cell electrolyzer test showed a four-fold increase in current density by employing the magnetized 80% IrO₂ - 20% Fe₃O₄ catalyst.     

Numerical studies on an air-breathing proton exchange membrane (PEM) fuel cell stack

Air-breathing proton exchange membrane (PEM) fuel cells provide for fully or partially passive operation and have gained much interest in the past decade, as part of the efforts to reduce the system complexity. This paper presents a detailed physics-based numerical analysis of the transport and electrochemical phenomena involved in the operation of a stack consisting of an array of vertically oriented air-breathing fuel cells. A comprehensive two-dimensional, nonisothermal, multi-component numerical model with pressurized hydrogen supply at the anode and natural convection air supply at the cathode is developed and validated with experimental data. Systematic parametric studies are performed to investigate the effects of cell dimensions, inter-cell spacing and the gap between the array and the substrate on the performance of the stack. Temperature and species distributions and flow patterns are presented to elucidate the coupled multiphysics phenomena. The analysis is used to determine optimum stack designs based on constraints on desired performance and overall stack size.     

Microwave assisted,facile synthesis of Pt/CNT catalyst for proton exchange membrane fuel cell application

The present study aims at developing a high performing Pt/CNT catalyst for ORR in PEM fuel cell adopting modified chemical reduction route using a mixture of NaBH₄ and ethylene glycol (EG) as reducing agent. In order to select the most suitable reduction conditions to realize high performing catalyst, heating of the reaction mixture is done following two methods, conventional heating (CH) or microwave (MW) irradiation. The synthesized Pt/CNT catalysts were extensively characterized and evaluated in-situ as ORR catalyst in PEM fuel cell. A comparison of their performance with the standard, commercial Pt/C catalyst was also made. The results showed deposition of smaller Pt nanoparticles with uniform distribution and higher SSA for Pt/CNT-MWH compared to Pt/CNT-CH. In-situ electrochemical characterization studies revealed higher ESA, lower charge transfer resistance, lower activation over-potential loss and higher peak power density compared to the cathode with Pt/CNT-CH and Pt/C. This study suggests the viability of MW assisted, metal particle deposition as a simple, yet effective method to prepare high performing Pt/CNT catalyst for ORR in PEM fuel cell.     

Heat sources in proton exchange membrane (PEM) fuel cells

In order to model accurately heat transfer in PEM fuel cell, a particular attention had to be paid to the assessment of heat sources in the cell. Although the total amount of heat released is easily computed from its voltage, local heat sources quantification and localization are not simple. This paper is thus a discussion about heat sources/sinks distribution in a single cell, for which many bold assumptions are encountered in the literature. The heat sources or sinks under consideration are: (1) half-reactions entropy, (2) electrochemical activation, (3) water sorption/desorption at the GDL/membrane interfaces, (4) Joule effect in the membrane and (5) water phase change in the GDL.A detailed thermodynamic study leads to the conclusion that the anodic half-reaction is exothermic , instead of being athermic as supposed in most of the thermal studies. As a consequence, the cathodic half-reaction is endothermic , which results in a heat sink at the cathode side, proportional to the current. In the same way, depending on the water flux through the membrane, sorption can create a large heat sink at one electrode and an equivalent heat source at the other. Water phase change in the GDL - condensation/evaporation - results in heat sources/sinks that should also be taken into account. All these issues are addressed in order to properly set the basis of heat transfer modeling in the cell.     

High performance electrocatalysts supported on graphene based hybrids for polymer electrolyte membrane fuel cells

In this study, new electrocatalysts for PEM fuel cells, based on Pt nanoparticles supported on hybrid carbon support networks comprising reduced graphene oxide (rGO) and carbon black (CB) at varying ratios, were designed and prepared by means of a rapid and efficient microwave-assisted synthesis method. Resultant catalysts were characterized ex-situ for their structure, morphology, electrocatalytic activity. In addition, membrane-electrode assemblies (MEAs) fabricated using resultant electrocatalysts and evaluated in-situ for their fuel cell performance and impedance characteristics. TEM studies showed that Pt nanoparticles were homogeneously decorated on rGO and rGO-CB hybrids while they had bigger size and partially agglomerated distribution on CB. The electrocatalyst, supported on GO-CB hybrid containing 75% GO (HE75), possessed very encouraging results in terms of Pt particle size and dispersion, catalytic activity towards HOR and ORR, and fuel cell performance. The maximum power density of 1090 mW cm^?2 was achieved with MEA (Pt loading of 0.4 mg cm^?2) based on electrocatalyst, HE75. Therefore, the resultant hybrid demonstrated higher Pt utilization with enhanced FC performance output. Our results, revealing excellent attributes of hybrid supported electrocatalysts, can be ascribed to the role of CB preventing rGO sheets from restacking, effectively modifying the array of graphene and providing more available active catalyst sites in the electrocatalyst material.     

Transition metal carbides and nitrides as oxygen reduction reaction catalyst or catalyst support in proton exchange membrane fuel cells (PEMFCs)

Fuel cells are potentially efficient, silent, and environmentally friendly tools for electrical power generation. One of the obstacles facing the development and the commercialization of fuel cells is the dependence on the precious metal catalyst, i.e., Platinum (Pt) and Pt - alloy, especially at the cathode where high catalyst loading used to compensate the sluggish oxygen reduction reaction (ORR). Pt is not only an expensive and rare element but also has insufficient durability. The development of an efficient non-precious catalyst, i.e., electrochemically active, chemically and mechanically stable, and electrically conductive, is one of the basic requirements for the commercialization of fuel cells. The bonding to carbon and nitrogen to form metal carbides and nitrides modify the nature of the d-band of the parent metal, thus improve its catalytic properties relative to the parent metals to be similar to those of group VIII noble metals. In this article, we summarize the progress in the development of the transition metal carbides (TMCs) and transition metals nitrides (TMNs) relative to their application as catalysts for the ORR in fuel cells. The preparation of TMCs and TMNs via different routes which significantly affects its activity is discussed. The ORR catalytic activity of the TMCs and TMNs as a non-precious catalyst or catalyst support in fuel cells is discussed and compared to that of the Pt-based catalyst in this review article. Moreover, the recent progress in the preparation of the nano-sized (which is a critical factor for increasing the activity at low temperature) TMCs and TMNs are discussed.     

A performance and degradation study of Nafion 212 membrane for proton exchange membrane fuel cells

The operational characteristics of the Nafion^® 212 membrane (N212) are investigated and compared to that of Nafion^® 112 (N112), in proton exchange membrane fuel cells (PEMFCs). The consequences of the membranes’ degradation are also investigated, after accelerated aging experiments using Fenton's method. Studies were performed by single cell polarization and impedance measurements, as a function of the cell and gas humidification temperatures and the gases pressures. Polarization curves show that the cell with N212 presents higher performance than that with N112, when operating under air cathode. FTIR analyses indicated that the chemical structure of Nafion does not change after accelerated degradation tests for both membranes. In spite of this, significant differences were observed in the morphology, mainly for N212. The electrochemical studies confirmed that the degradation of the membranes leads to a reduction of the fuel cell performance by increasing the gas crossover, mainly H₂. Results also show that the N212 membrane may be less durable than N112.     

Carbon-supported Pd-Pt cathode electrocatalysts for proton exchange membrane fuel cells

A series of carbon-supported Pd-Pt alloy (Pd-Pt/C) catalysts for oxygen reduction reaction (ORR) with low-platinum content are synthesized via a modified sodium borohydride reduction method. The structure of as-prepared catalysts is characterized by powder X-ray diffraction (XRD) and transmission electron microscope (TEM) measurements. The prepared Pd-Pt/C catalysts with alloy form show face-centered-cubic (FCC) structure. The metal particles of Pd-Pt/C catalysts with mean size of around 4-5 nm are uniformly dispersed on the carbon support. The electrocatalytic activities for ORR of these catalysts are investigated by rotating disk electrode (RDE), cyclic voltammetry (CV), single cell measurements and electrochemical impedance spectra (EIS) measurements. The results suggest that the electrocatalytic activities of Pd-Pt/C catalysts with low platinum are comparable to that of the commercial Pt/C with the same metal loading. The maximum power density of MEA with a Pd-Pt/C catalyst, the Pd/Pt mass ratio of which is 7:3, is about 1040 mW cm⁻².     

Study on electrochemical and mass transfer coupling characteristics of proton exchange membrane (PEM) fuel cell based on a fin-like electrode surface

Proton exchange membrane (PEM) Fuel cells are widely used because of its environmental protection and high efficiency. In the present study, a novel fin-like structure of the electrode surface is investigated by establishing the theoretical model and numerical simulating. For this purpose, the influence of different fin spacing and pressure boost on the performance of the PEM fuel cell is analyzed by numerical simulation. Results show that increasing pressure of cathode or both side experiences greater performance improvement compared to the other cases, and the maximum values of power density during both conditions is founding for fin density 1/1, followed by fin density 1/12, then last the basic model. Furthermore, the analysis shows that increasing CL surface area combined with cathode pressurization is the best strategy for fuel cell performance optimization. The fin structure under the condition of cathode pressurization can effectively reduce the transmission resistance and over potential of the fuel cell by theoretical calculation, which is coinciding well with the simulation results.     

Influence of the rated power in the performance of different proton exchange membrane (PEM) fuel cells

Fuel cells are clean generators that provide both electrical and thermal energy with a high global efficiency level. The characteristics of these devices depend on numerous parameters such as: temperature, fuel and oxidizer pressures, fuel and oxidizer flows, etc. Therefore, their influence should be evaluated to appropriately characterize behaviour of the fuel cell, in order to enable its integration in the electric system.     

Effects of sulfonated polyether-etherketone (SPEEK) and composite membranes on the proton exchange membrane fuel cell (PEMFC) performance

Sulfonated polyether-etherketone (SPEEK) has a potential for proton exchange fuel cell applications. However, its conductivity and thermohydrolytic stability should be improved. In this study the proton conductivity was improved by addition of an aluminosilicate, zeolite beta. Moreover, thermohydrolytic stability was improved by blending poly-ether-sulfone (PES). Sulfonated polymers were characterized by H-NMR. Composite membranes prepared were characterized by Electrochemical Impedance Spectroscopy (EIS) for their proton conductivity. Degree of sulfonation (DS) values calculated from H-NMR results, and both proton conductivity and thermohydrolytic stability was found to strongly depend on DS. Therefore, DS values were controlled time in the range of 55–75% by controlling the reaction time. Zeolite beta fillers at different SiO₂/Al₂O₃ ratios (20, 30, 40, 50) were synthesized and characterized by XRD, EDX, TGA, and SEM. The proton conductivity of plain SPEEK membrane (DS = 68%) was 0.06 S/cm at 60 °C and the conductivity of the composite membrane containing of zeolite beta filled SPEEK was found to increase to 0.13 S/cm. Among the zeolite Beta/SPEEK composite membranes the best conductivity results were achieved with zeolite beta having a SiO₂/Al₂O₃ ratio of 50 at 10 wt% loading.     

Investigation of tungsten carbide supported Pd or Pt as anode catalysts for PEM fuel cells

In this contribution, we present results of electrochemical characterization of prepared tungsten carbide supported palladium and platinum and Vulcan XC-72 supported palladium. These catalysts were employed as anode catalysts in PEMFC and results are compared to commercial platinum catalyst. Platinum seems to be irreplaceable as a proton exchange membrane fuel cell (PEMFC) catalyst for both the anode and the cathode, yet the high price and limited natural resources are holding back the commercialization of the PEMFCs. Tungsten carbide is recognized as promising catalyst support having the best conductivity among interstitial carbides. Higher natural resources and significantly lower price make palladium good candidate for replacement of the platinum catalyst. The presented results show that all prepared catalysts are very active for the hydrogen oxidation reaction. Linear sweep voltammetry curves of Pd/C and Pd/WC show existence of peaks at 0.07 V vs. RHE, which is assigned to absorbed hydrogen. H₂|Pd/WC|Nafion117|Pt/C|O₂ fuel cell has almost the same efficiency and similar power output as commercial platinum catalyst.     

Performances prediction study for proton exchange membrane fuel cells

In this work, we propose to study the influence of the membrane physical properties on the performance of a single PEM cell through the polarization curve. A thermal approach describing the main heat transfer aspects was also discussed. For this study, we have developed and used a simulation tool called Performances Prediction Fuel Cell tool (2PFC tool) based on simplified charge, mass and even heat transfer equations. This tool aims to visualize the main evolutions in the heart of a single cell, and the results should help users to understand the variation of some operating conditions and component properties on the output cell voltage by offering a variety of sensitivity parameter studies. For this sensitivity analysis, three separated simulations are launched. The first simulation regards the effect of the resistive losses and charge transfer coefficient on the cell voltage. The second simulation concerns the influence of the water content of the membrane and the cell operating temperature on it proton conductivity. The last simulation takes in consideration the effect of water activity variation on the proton membrane conductivity, and the results proved the direct and strong relation of the charge transfer coefficient and of the water content of the membrane on the output cell voltage. In the thermal approach part, we have proposed to study the temperature distribution between two cathodes with the presence of an implemented cooling channel.     

A simple electric circuit model for proton exchange membrane fuel cells

A simple and novel dynamic circuit model for a proton exchange membrane (PEM) fuel cell suitable for the analysis and design of power systems is presented. The model takes into account phenomena like activation polarization, ohmic polarization, and mass transport effect present in a PEM fuel cell. The proposed circuit model includes three resistors to approach adequately these phenomena; however, since for the PEM dynamic performance connection or disconnection of an additional load is of crucial importance, the proposed model uses two saturable inductors accompanied by an ideal transformer to simulate the double layer charging effect during load step changes. To evaluate the effectiveness of the proposed model its dynamic performance under load step changes is simulated. Experimental results coming from a commercial PEM fuel cell module that uses hydrogen from a pressurized cylinder at the anode and atmospheric oxygen at the cathode, clearly verify the simulation results.     

Physically stable proton exchange membrane with ordered electrolyte for elevated temperature PEM fuel cell

Dimensional change and humidity-induced stress of the proton exchange membrane were demonstrated to be main reasons for membrane physical failure during the long-term fuel cell operation. In this work, UV laser ablation was proposed to prepare physically stable polyimide supports to reduce the dimensional swelling and humidity-induced stress of the proton exchange membrane under variable humidities. Long-range ordered straight holes with definable open pattern and diameter of 50–200 μm were formed through the polyimide support. Composite proton exchange membrane prepared from the straight-hole polyimide support presented desirable performance and high durability in fuel cells. When Nafion fraction in the composite membrane increased to 48.67%, the proton conductivities of the composite membranes were equal to or greater than that of the conventional Nafion membrane with activation energies lower than that of the Nafion 211 membrane. The dimensions of the composite membranes are very stable in both low and elevated temperature conditions. The proportion of humidity-induced stress to the yield strength for the composite membrane is 0.20%–0.21%, much lower than that of the conventional Nafion membrane (24.77%). As a result, the composite proton exchange membrane prepared from the straight-hole polyimide presented high durability in the fuel cell operation. In the open circuit voltage accelerated test under in situ accelerating RH cyclic test, the irreversible OCV reduction rate of the composite membranes was 2.41–2.72 × 10⁻⁵ V/cycle, 37.1%–41.8% lower than that of the conventional Nafion 211 membrane.     

The parametric optimum analysis of a proton exchange membrane (PEM) fuel cell and its load matching

Based on the irreversible model of a PEM fuel cell working at steady state, expressions for the power output, efficiency and entropy production rate of the PEM fuel cell are analytically derived by using the theory of electrochemistry and non-equilibrium thermodynamics. The effects of multi-irreversibilities resulting from electrochemical reaction, heat transfer and electrical resistance on the key parameters of the PEM fuel cell are analyzed. The curves of the power output, efficiency and entropy production rate of the PEM fuel cell varying with the electric current density are represented through numerical calculation. The general performance characteristics of the PEM fuel cell are revealed and the optimum criteria of the main performance parameters are determined. Moreover, the optimal matching condition of the load resistance is obtained from the relations between the load resistance and the power output and efficiency. The effects of the leakage resistance on the performance of the PEM fuel cell are expounded and the optimally operating states of the PEM fuel cell are further discussed.     

Modelling of proton exchange membrane fuel cell performance based on semi-empirical equations

Using semi-empirical equations for modeling a proton exchange membrane fuel cell is proposed for providing a tool for the design and analysis of fuel cell total systems. The focus of this study is to derive an empirical model including process variations to estimate the performance of fuel cell without extensive calculations. The model take into account not only the current density but also the process variations, such as the gas pressure, temperature, humidity, and utilization to cover operating processes, which are important factors in determining the real performance of fuel cell. The modelling results are compared well with known experimental results. The comparison shows good agreements between the modeling results and the experimental data. The model can be used to investigate the influence of process variables for design optimization of fuel cells, stacks, and complete fuel cell power system.     

Study on the CCM breakdown voltage of proton exchange membrane fuel cells

Proton exchange membrane (PEM) short circuits are one of the failure forms of fuel cells. In this paper, the change in breakdown voltage (BV) after the preparation of PEMs into catalyst coated membranes (CCMs) is studied, and the impact of the catalyst layer (CL) and its composition on the BV of the CCM is analysed. The results show that the BV of the CCM is significantly lower than that of the uncoated PEM. The higher the platinum (Pt) loading of the coated CL is, the lower the BV. Further research finds that the BV of the single-side CL-coated CCM only decreases when the CL side is connected to the positive pole of the power supply, while it is comparable to that of the PEM when the CL side is connected to the negative pole. The experimental results demonstrate that the Pt and carbon particles in the CCM undergo electrochemical reactions during the breakdown process when the CL is connected to the positive pole, which eventually leads to thermal breakdown. Therefore, when the BV is chosen for detecting whether the CCM preparation process causes PEM damage, single-side CL-coated CCM should be adopted, and the CL should be connected to the negative pole of the power supply.