Performance optimization of ultra-low platinum loading membrane electrode assembly prepared by electrostatic spraying

To improve the utilization of platinum and reduce the manufacturing cost of proton exchange membrane fuel cell (PEMFC), the electrostatic spraying was used to prepare the cathode catalyst layer of membrane electrode assembly (MEA) with platinum loading varying from 0.1 to 0.01 mg cm^?2. The performance of fuel cell was tested and analyzed by electrochemical impedance and polarization curve. Our results show that the platinum carbon (Pt/C) particles deposited by electrostatic spraying were well dispersed and the microporous structure of catalyst layer (CL) were relatively uniform. Replacing the CCS type MEA (catalyst coated on gas diffusion layer substrate) with the CCM type MEA (catalyst coated on proton exchange membrane) can reduce its electrochemical impedance and improve the power density of fuel cell. Compared to the Pt/C catalyst with a platinum mass fraction of 60%, a lower platinum-carbon ratio catalyst is more conducive to the uniform dispersion of catalyst particles and efficient utilization of platinum in the preparation of MEA with ultra-low platinum loading. However, their difference in peak power density decreases with the increase of platinum loading. Besides, increasing the back pressure can improve the performance of fuel cell, when the back pressure increased to 0.15 Mpa and the feeding gases were set as H₂/O₂, the peak power density of 0.56 W cm^?2 was obtained by the MEA with cathode platinum loading of 0.01 mg cm^?2, which is corresponding to the cathode platinum utilization of 56 kW·g_Pt^?1_cathode.     

High performance membrane electrode assemblies by optimization of coating process and catalyst layer structure in direct methanol fuel cells

High performance membrane electrode assemblies (MEAs) for direct methanol fuel cells (DMFCs) are developed by changing the coating process, optimizing the structure of the catalyst layer, adding a pore forming agent to the cathode catalyst layer, and adjusting the hot-pressing conditions, such as pressure and temperature. The effects of these MEA fabrication methods on the DMFC performance are examined using a range of physicochemical and electrochemical analysis tools, such as FE-SEM, electrochemical impedance spectroscopy (EIS), polarization curves, and differential scanning calorimetry (DSC) of the membrane. EIS and polarization curve analysis show that an increase in the thickness and porosity of the cathode catalyst layer plays a key role in improving the cell performance with reduced cathode reaction resistance, whereas the MEA preparation methods have no significant effects on the anode impedance. In addition, the addition of magnesium sulfate as a pore former reduces the cathode reaction transfer resistance by approximately 30 wt%, resulting in improved cell performance.     

Ir-Pt/C composite with high metal loading as a high-performance anti-reversal anode catalyst for proton exchange membrane fuel cells

Voltage reversal induced by hydrogen starvation can severely corrode the anode catalyst support and deteriorate the performance of proton exchange membrane fuel cells. A material-based strategy is the inclusion of an oxygen evolution reaction catalyst (e.g., IrO₂) in the anode to promote water electrolysis over harmful carbon corrosion. In this work, an Ir-Pt/C composite catalyst with high metal loading is prepared. The membrane-electrode-assembly (MEA) with 80 wt% Ir-Pt(1:2)/C shows a first reversal time (FRT) of up to 20 hours, which is about ten times that of MEA with 50 wt% Ir-Pt(1:2)/C does. Furthermore, the MEA with 80 wt% Ir-Pt(1:2)/C exhibits a minimum cell voltage loss of 6 mV@1 A/cm² when the FRT is terminated in 2 hours, in which the MEA with 50 wt% Ir-Pt(1:2)/C exhibits a voltage loss of 105 mV@1 A/cm². Further physicochemical and electrochemical characterizations demonstrate that the destruction of anode catalyst layer caused by the voltage reversal process is alleviated by the use of the composite catalyst with high metal loading. Hence, our results reveal that the combination of OER catalyst on the Pt/C with high metal loading is a promising approach to alleviate the degradation of anode catalyst layer during the voltage reversal process for PEMFCs.     

High performance membrane electrode assembly with ultra-low platinum loading prepared by a novel multi catalyst layer technique

An ultra-low platinum loading membrane electrode assembly (MEA) with a novel double catalyst layer (DCL) structure was prepared by using two layers of platinum catalysts with different loadings. The inner layer consisted of a high loading platinum catalyst and high Nafion content for keeping good platinum utilization efficiency and the outer layer contained a low loading platinum catalyst with low Nafion content for obtaining a proper thickness thereby enhancing mass transfer in the catalyst layers. Polarization characteristics of MEAs with novel DCL, conventional DCL and single catalyst layer (SCL) were evaluated in a H₂–air single cell system. The results show that the performance of the novel DCL MEA is improved substantially, particularly at high current densities. Although the platinum loadings of the anode and cathode are as low as 0.04 and 0.12 mg cm⁻² respectively, the current density of the novel DCL MEA still reached 0.73 A cm⁻² at a working voltage of 0.65 V, comparable to that of the SCL MEA. In addition, the maximum power density of the novel DCL MEA reached 0.66 W cm⁻² at 1.3 A cm⁻² and 0.51 V, 11.9% higher than that of the SCL MEA, indicative of improved mass transfer for the novel MEA. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) tests revealed that the novel DCL MEA possesses an efficient electrochemical active layer and good platinum utilization efficiency.     

Membrane electrode assemblies with low noble metal loadings for hydrogen production from solid polymer electrolyte water electrolysis

High performance membrane electrode assemblies (MEAs) with low noble metal loadings (NMLs) were developed for solid polymer electrolyte (SPE) water electrolysis. The electrochemical and physical characterization of the MEAs was performed by I–V curves, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). Even though the total NML was lowered to 0.38 mg cm⁻², it still reached a high performance of 1.633 V at 2 A cm⁻² and 80 °C, with IrO₂ as anode catalyst. The influences of the ionomer content in the anode catalyst layer (CL) and the cell temperature were investigated with the purpose of optimizing the performance. SEM and EIS measurements revealed that the MEA with low NML has very thin porous cathode and anode CLs that get intimate contact with the electrolyte membrane, which makes a reduced mass transport limitation and lower ohmic resistance of the MEA. A short-term water electrolysis operation at 1 A cm⁻² showed that the MEA has good stability: the cell voltage maintained at ∼1.60 V without distinct degradation after 122 h operation at 80 °C and atmospheric pressure.     

Self-humidified operation of a PEM fuel cell using a novel silica composite coating method

A proton exchange membrane fuel cell operating with no external humidification support was successfully reported using a novel silica composite layer on the anode side (Pt/C/SiO₂/Nafion). The nanosilica derived from tetramethoxy silane (TMOS) provided excellent porous morphology to retain water and hydrate protons. This layer provides a well-humidified environment for protons and easy proton transfer from the catalyst surface to the membrane electrolyte. The characteristics of the silica composite layer were investigated by various characterization methods: SEM, XRD, TEM, XPS, EIS, and TGA. A single cell fabricated with the anode containing this new silica composite layer showed a performance of 0.9 W/cm² which is two folds greater when tested with the commercial catalyst MEA (0.45 W/cm²). MEA delivered a constant output power (at 0.6 V) under dry and humidified gas conditions which shows excellent electrochemical stability and durability.     

The effects of Nafion ionomer content in PEMFC MEAs prepared by a catalyst-coated membrane (CCM) spraying method

We analyzed the effects of ionomer content on the proton exchange membrane fuel cell (PEMFC) performance of membrane electrode assemblies (MEAs) fabricated by a catalyst-coated membrane (CCM) spraying method in partially humidified atmospheric air and hydrogen. When high loading Pt/C catalysts (45.5 wt.%) were used, we observed that catalytic activity was not directly proportional to electrochemical active surface area (EAS). This suggests that ionic conductivity through ionomers in catalyst layers is also an important factor affecting MEA performance. In addition, the effects of mass transport were experimentally evaluated by manipulating the air stoichiometry ratio at the cathodes. MEA performance was more sensitive to flow rates under conditions of higher ionomer content. Due to the combined effect of EAS, ionic conductivity, and mass transfer characteristics (all of which varied according to the ionomer content), an MEA with 30 wt.% ionomer content at the cathode (25 wt.% at the anode) was shown to yield the best performance.     

Effect of metal particle size and Nafion content on performance of MEA using Ir-V/C as anode catalyst

Ir and Ir-V nanoparticles were synthesized in ethylene glycol using IrCl₃ and NH₄VO₃ as the Ir and V precursors, respectively. These nanoparticles were evaluated as anode catalysts in proton exchange membrane fuel cells (PEMFCs). A thermal treatment of the catalysts at 200 °C in a reducing atmosphere leads to very high electrocatalytic activity for the hydrogen oxidation reaction. The fuel cell performance reveals an optimal Nafion ionomer content of 25% in the catalyst layer used for the MEA fabrication. The electrocatalytic effects related to the change in the electrocatalyst structure are discussed based on the data obtained by X-ray diffraction (XRD) and transmission electron microscopy (TEM). In addition, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques are used in-situ to assess the kinetics of hydrogen oxidation on the surface of these catalysts. A maximum power density of 1016.6 mW cm⁻² was obtained at 0.598 V and 70 °C with an anode catalyst loading of 0.4 mg (Ir) cm⁻². This performance is 50.7% higher than that for commercially available Pt/C catalysts under the same conditions. In addition, we also tested the anode catalyst with a low loading of 0.1 mg (Ir) cm⁻², the maximum power density is 33.8% higher than that of the commercial Pt/C catalyst with a loading of 0.4 mg (Pt) cm⁻².     

Performance of an ultra-low platinum loading membrane electrode assembly prepared by a novel catalyst-sprayed membrane technique

Membrane electrode assemblies (MEAs) with ultra-low platinum loadings are attracting significant attention as one method of reducing the quantity of precious metal in polymer electrolyte membrane fuel cells (PEMFCs) and thereby decreasing their cost, one of the key obstacles to the commercialization of PEMFCs. In the present work, high-performance MEAs with ultra-low platinum loadings are developed using a novel catalyst-sprayed membrane technique. The platinum loadings of the anode and cathode are lowered to 0.04 and 0.12 mg cm⁻², respectively, but still yield a high performance of 0.7 A cm⁻² at 0.7 V. The influence of Nafion content, cell temperature, and back pressures of the reactant gases are investigated. The optimal Nafion content in the catalyst layer is ca. 25 wt.%. This is significantly lower than for low platinum loading MEAs prepared by other methods, indicating ample interfacial contact between the catalyst layer and membrane in our prepared MEAs. Scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) measurements reveal that our prepared MEA has very thin anode and cathode catalyst layers that come in close contact with the membrane, resulting in a MEA with low resistance and reduced mass transport limitations.     

Long-term durability test for direct methanol fuel cell made of hydrocarbon membrane

A long-term durability test has been conducted for a direct methanol fuel cell (DMFC) using the commercial hydrocarbon membrane and Nafion ionomer bonded electrodes for 500 h. Membrane electrode assembly (MEA) made by a decal method has experienced a performance degradation about 34% after 500 h operation. Cross-sectional analysis of the MEA shows that the poor interfacial contact between the catalyst layers and membrane in the MEA has further deteriorated after the durability test. Therefore, the internal resistance of a cell measured by electrochemical impedance spectroscopy (EIS) has considerably increased. The delamination at the interfaces is mainly attributed to incompatibility between polymeric materials used in the MEA. Furthermore, X-ray diffraction (XRD) analysis reveals that the catalyst particles have grown; thereby decreasing the electrochemical surface area. Electron probe micro analysis (EPMA) shows a small amount of Ru crossover from anode to cathode; and its effect on the performance degradation has been analyzed.     

An impedance study for the anode micro-porous layer in an operating direct methanol fuel cell

This study presents the benefit to an operating direct methanol fuel cell (DMFC) by coating a micro-porous layer (MPL) on the surface of anode gas diffusion layer (GDL). Taking the membrane electrode assembly (MEA) with and without the anodic MPL structure into account, the performances of the two types of MEA are evaluated by measuring the polarization curves together with the specific power density at a constant current density. Regarding the cell performances, the comparisons between the average power performances of the two different MEAs at low and high current density, various methanol concentrations and air flow rates are carried out by using the electrochemical impedance spectroscopy (EIS) technique. In contrast to conventional half cell EIS measurements, both the anode and cathode impedance spectra are measured in real-time during the discharge regime of the DMFC. As comparing each anode and cathode EIS between the two different MEAs, the influences of the anodic MPL on the anode and cathode reactions are systematically discussed and analyzed. Furthermore, the results are used to infer complete and reasonable interpretations of the combined effects caused by the anodic MPL on the full cell impedance, which correspond with the practical cell performance.     

A study of water transport as a function of the micro-porous layer arrangement in PEMFCs

Electrochemical losses as a function of the micro-porous layer (MPL) arrangement in Proton Exchange Membrane Fuel Cells (PEMFCs) are investigated by electrochemical impedance spectroscopy (EIS). Net water flux across the polymer membrane in PEMFCs is investigated for various arrangements of the MPL, namely with MPL on the cathode side alone, with MPL on both the cathode and the anode sides and without MPL. EIS and water transport are recorded for various operating conditions, such as the relative humidity of the hydrogen inlet and current density, in a PEMFC fed by fully-saturated air. The cell with an MPL on the cathode side alone has better performance than two other types of cells. Furthermore, the cell with an MPL on only the cathode increases the water flux from cathode to anode as compared to the cells with MPLs on both electrodes and cells without MPL. Oxygen-mass-transport resistances of cells in the presence of an MPL on the cathode are lower than the values for the other two cells, which indicates that the molar concentration of oxygen at the reaction surface of the catalyst layer is higher. This suggests that the MPL forces the liquid water from the cathode side to the anode side and decreases the liquid saturation in GDL at high current densities. Consequently, the MPL helps in maintaining the water content in the polymer membrane and decreases the cathode charge transfer and oxygen-mass transport resistances in PEMFCs, even when the hydrogen inlet has a low relative humidity.     

A novel self-humidifying membrane electrode assembly with water transfer region for proton exchange membrane fuel cells

A novel self-humidifying membrane electrode assembly (MEA) with the active electrode region surrounded by a unactive “water transfer region (WTR)” was proposed to achieve effective water management and high performance for proton exchange membrane fuel cells (PEMFCs). By this configuration, excess water in the cathode was transferred to anode through Nafion membrane to humidify hydrogen. Polarization curves and power curves of conventional and the self-humidifying MEAs were compared. The self-humidifying MEA showed power density of 85 mW cm⁻² at 0.5 V, which is two times higher than that of a conventional MEA with cathode open. The effects of anode hydrogen flow rates on the performance of the self-humidifying MEA were investigated and its best performance was obtained at a flow rate of 40 ml min⁻¹. Its performance was the best when the environmental temperature was 40 °C. The performance of the self-humidifying MEA was slightly affected by environmental humidity. The area of WTR was optimized, and feasible area ratio of the self-humidifying MEA was 28%.     

Feasibility of ultra-low Pt loading electrodes for high temperature proton exchange membrane fuel cells based in phosphoric acid-doped membrane

Factors as the Pt/C ratio of the catalyst, the binder content of the electrode and the catalyst deposition method were studied within the scope of ultra-low Pt loading electrodes for high temperature proton exchange membrane fuel cells (HT-PEMFCs). The Pt/C ratio of the catalyst allowed to tune the thickness of the catalytic layer and so to minimize the detrimental effect of the phosphoric acid flooding. A membrane electrode assembly (MEA) with 0.05 mg_Ptcm⁻² at anode and 0.1 mg_Ptcm⁻² at cathode (0.150 mg_Ptcm⁻² in total) attained a peak power density of 346 mW cm⁻². It was proven that including a binder in the catalytic layer of ultra-low Pt loading electrodes lowers its performance. Electrospraying-based MEAs with ultra-low Pt loaded electrodes (0.1 mg_Ptcm⁻²) rendered the best (peak power density of 400 mW cm⁻²) compared to conventional methods (spraying or ultrasonic spraying) but with the penalty of a low catalyst deposition rate.     

Self-humidification of a PEM fuel cell using a novel Pt/SiO2/C anode catalyst

In this work, a membrane electrode assembly (MEA) for proton exchange membrane fuel cell (PEMFC) operating under no external humidification has been successfully fabricated by using a composite Pt/SiO₂/C catalyst at the anode. In the composite catalyst, amorphous silica, which originated from the hydrolysis of tetraethyl orthosilicate (TEOS), was immobilized on the surface of carbon powder to enhance the stability of silica and provide a well-humidified surrounding for proton transport in the catalyst layer. The characteristics of silica in the composite catalyst were investigated by XRD, SEM and XPS analysis. The single cell tests showed that the performance of the novel MEA was comparable to MEAs prepared using a standard commercial Pt/C catalyst with 100% external humidification, when both were operated on hydrogen and air. However, in the absence of humidification, the MEA using Pt/SiO₂/C catalyst at the anode continued to show excellent performance, while the performance of the MEA containing only the Pt/C catalyst rapidly decayed. Long-term testing for 80 h further confirmed the high performance of the non-humidified MEA prepared with the composite catalyst. Based on the experimental data, a possible self-humidifying mechanism was proposed.     

Improving cell performance and alleviating performance degradation by constructing a novel structure of membrane electrode assembly (MEA) of DMFCs

The conventional electrodes of direct methanol fuel cells (DMFCs) usually encounter a problem that the catalysts sink into the diffusion layer after a period of operation, causing a lowered catalyst utilization and degraded cell performance. Aiming to alleviate this problem, in this work a novel anode electrode structure is proposed, in which a microporous layer containing Nafion polymer is added between the catalyst layer and the microporous layer with PTFE. The presence of the Nafion-contained layer can expand the three-phase interface region of the electrochemical reactions and improve the utilization of the catalyst. The single cell test showed that the peak power densities of the novel membrane electrode assembly (MEA) fed with 0.5 M and 2 M methanol solutions reached 38.35 mW cm⁻² and 101.82 mW cm⁻², which increased by 100.42% and 15.27% compared with those of conventional single microporous layer. Electrochemical impedance spectroscopy (EIS) measurements indicated the charge transfer resistance of the conventional MEA structure was increased by 303.78%, while the new one was decreased by 47.91% after continuously operating for 48 h. The anode electrochemical active surface area (ECSA) values of the novel MEA and the conventional MEA were 52.6 m² g^-1 and 44.3 m² g^-1. These experimental results showed that the performance of the double microporous layer MEA was higher than that of the conventional MEA. This new microporous layer structure is promising to be used in fuel cells to improve cell performance and alleviate performance degradation after long-term operating.     

Operation of a proton exchange membrane fuel cell under non-humidified conditions using a membrane–electrode assemblies with composite membrane and electrode

Composite membranes with hydrophilic substances can retain water and allow the operation of proton exchange membrane fuel cells (PEMFCs) under non-humidified conditions. In this work, thin Nafion composite membranes with silica are prepared to operate a PEMFC with dry fuel and oxidant. In addition, the role of silica in the catalyst layer as a water retainer is studied. In particular, the anode and the cathode are modified separately to elucidate the effect of silica. The incorporation of silica in the membrane and the catalyst layer enhances single-cell performance under non-humidified operation. The cell performance of membrane–electrode assemblies using the composite membrane and electrode is higher than that of a MEA using commercial Nafion 111 membrane under non-humidified conditions.     

Enhancement of water retention in the membrane electrode assembly for direct methanol fuel cells operating with neat methanol

It is desirable to operate a direct methanol fuel cell (DMFC) with neat methanol to maximize the specific energy of the DMFC system, and hence increasing its runtime. A way to achieve the neat-methanol operation is to passively transport the water produced at the cathode through the membrane to the anode to facilitate the methanol oxidation reaction (MOR). To achieve a performance of the MOR similar to that under the conventional diluted methanol operation, both the water transport rate and the local water concentration in the anode catalyst layer (CL) are required to be sufficiently high. In this work, a thin layer consisting of nanosized SiO₂ particles and Nafion ionomer (referred to as a water retention layer hereafter) is coated onto each side of the membrane. Taking advantage of the hygroscopic nature of SiO₂, the cathode water retention layer can help maintain the water produced from the cathode at a higher concentration level to enhance the water transport to the anode, while the anode retention layer can retain the water that is transported from the cathode. As a result, a higher water transport rate and a higher water concentration at the anode CL can be achieved. The formed membrane electrode assembly (MEA) with the added water retention layers is tested in a passive DMFC and the results show that this MEA design yields a much higher power density than the MEA without water retention layers does.     

Effect of primary parameters on the performance of PEM fuel cell

A one-dimensional, steady-state and isothermal model for a proton exchange membrane (PEM) fuel cell has been developed to investigate the effects of various parameters such as the molar fraction of nitrogen gas, relative humidity, temperature, pressure, membrane thickness, anode and cathode stoichiometric flow ratio and the distribution of oxygen in the cathode catalyst while water transfer in membrane is produced by diffusion, pressure gradient and electro-osmotic drag. The most critical problems to overcome in the proton exchange membrane (PEM) fuel cell technology are the water and thermal management. The results show that the cell performance increases as operating pressure and temperature are increased. The performance of cell can decrease by decreasing the relative humidity of inlet gases and increasing the membrane thickness. Increasing the anode and cathode stoichiometric flow ratio can also improve the cell performance. As the oxygen concentration becomes zero in about 8 percent depth of cathode catalyst layer, the thickness of cathode catalyst layer can be reduced 92 percent without any potential loss in output voltage. The cathode activation loss also becomes high by increasing the molar fraction of nitrogen gas. The modeling results agree very well with experimental results.     

A novel cathode structure with double catalyst layers and low Pt loading for proton exchange membrane fuel cells

A novel cathode structure (NCS) was developed, which consisted of an inner and an outer catalyst layer (CL). It showed an improved platinum (Pt) utilization (above 50%), a lowered CL/gas diffusion layer interfacial resistance, and a decreased mass transport polarization compared with the traditional cathode structure (TCS). A hydrogen/air proton exchange membrane fuel cell employing NCS yielded an output power density up to 0.76 W cm⁻² with cathode Pt loading as low as 0.28 mg cm⁻². The enhanced performance of NCS is attributed to synergistic effect of the two catalyst supports in outer CL, which provides abundant pores to relieve water flooding and facilitates heat-induced proton conductor migration from the inner to outer CL, forming a hydrophilic proton conduction network. Moreover, the thin and compact inner CL can meet the demand of rich active sites and catalyst migration toward the regions nearest to the membrane under high current densities.