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.     

Design of a deflected membrane electrode assembly for PEMFCs

Simulations were performed of a proton exchange membrane fuel cell (PEMFC) in which the membrane electrode assembly (MEA) was deflected such that the adjacent shoulders of the channel assembly were at different heights. The effect on cell performance of varying the MEA deflection was examined while maintaining the same reacting area and boundary conditions at high operating current densities. A three-dimensional, non-isothermal model was employed with a single straight channel. Both humidification and phase transportation were included in the model to obtain the total water management for systems operating at different current densities. The cell performance was found to increase significantly at a certain, optimal deflection. The cathode overpotential decreased significantly with increasing MEA deflection as the reactants became more evenly distributed over the reacting area. A preliminary investigation of the deflection behavior of different MEA materials under clamping pressures taken from the literature indicated that MEA materials can be deflected up to the optimal deflection condition provided the clamping pressure is within the elastic limit of the gas diffusion electrode (GDE).     

Single-step fabrication of ABPBI-based GDE and study of its MEA characteristics for high-temperature PEM fuel cells

Single-step fabrication of a Poly(2,5-benzimidazole) (ABPBI)-based gas diffusion electrode (GDE) by directly adding a carbon-supported-catalyst to a homogeneous ABPBI solution prior to deposition and its membrane electrode assembly (MEA) were investigated for high-temperature proton exchange membrane (PEM) fuel cell applications. The ABPBI and LiCl dosages of the catalyst layer were varied. The characterizations of the resulting electrodes and/or MEA for the gas permeability, electrical resistance, specific electrochemical surface area, AC impedance, cyclic voltammetry and high-temperature PEM fuel cell performance were carried out. The high-temperature PEM fuel cell was successfully demonstrated at temperatures of up to 180 °C under ambient pressure operation. The fuel cell performance was evaluated by using dry hydrogen/oxygen gases, which added the advantage of eliminating the complicated humidification system of Nafion cells. The obtained results revealed that a catalyst layer with an ABPBI content of 15 wt.% and an ABPBI/LiCl ratio of 1:2 was sufficient to obtain the optimal cell performance with better electrochemical properties of low cell impedance, high electrochemical activity, low contact resistance and short activation time.     

Durability improvement at high current density by graphene networks on PEM fuel cell

This study presents a novel structure of catalyst layers of membrane electrode assemblies (MEAs) by adding graphene to platinum on carbon black (Pt/C) to improve the durability at high current density operation (3 A cm⁻²). Graphene displays outstanding low electrical resistance and has the advantage of high electron mobility. It is also used in lithium ion batteries to improve electrical performance such as high rate charge/discharge capability and cycle-life stability. In this study, three MEAs are compared, and graphene is used as an excellent conductive additive in catalyst layers for better electrons transport at high current density operation. The MEA coated Pt/C mixed with 0.1 wt% graphene shows best durability for 0.3 V h⁻¹ which is almost 3.7 times better than that of without graphene additive (1.1 V h⁻¹). The graphene additive effectively extends the durability of the MEA. Furthermore, the MEAs are analyzed by AC impedance. The impedance arc of the MEA coated with Pt/C only is getting worse, but those two coated with graphene show similar and smaller impedance arcs after high current density operation for 80 h.     

Diagnosis of membrane electrode assembly degradation with drive cycle test technique

One of important factors determining the lifetime of proton exchange membrane fuel cells (PEMFCs) is degradation and failure of membrane electrode assembly (MEA). The lack of effective mitigation methods is largely due to the currently limited understanding of the degradation mechanisms for fuel cell MEAs. This study adopted the accelerating degradation technique to analyze durability of MEA using drive cycle test protocol developed by Chinese NERC Fuel Cell & Hydrogen Technology to assess the long-term durability of fuel cells for vehicular application. During 900 h durability test of the MEA, the polarization curve, cyclic voltammetry (CV), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) were performed as diagnostics during and on completion the test. The experimental results show that the performance degradation rate of the cell is about 70 μV h⁻¹ at the operating current density of 500 mA cm⁻², failure of the proton exchange membrane is the decisive factor leading to the failure of the MEA. And the damage of the micro-structural of catalytic layer, crucial for electrochemical reaction, is the decisive factor for the performance degradation.     

Cold pre-compression of membrane electrode assembly for PEM fuel cells

Direct compression from the land structure of bipolar plate in a PEM fuel cell is considered as an important factor for the higher performance under the land than under the channel areas. Therefore the objective of this study is to determine if a cold pre-compression treatment on the whole membrane electrode assembly (MEA) area may have a significant positive effect on the overall performance of the cell. Five different levels of cold pre-compression have been applied and the experimental results show that the overall performance of the cell first increases with the level of compression to a maximum, and then decreases. These results clearly show that cold pre-compression of the MEA can significantly enhance the performance of the entire cell and there exists an optimal level of compression. Results of electrochemical impedance spectroscopy (EIS) show that the cold pre-compression results in a significant reduction in charge transfer resistance, especially in the high current density region. Further study by the cyclic voltammetry (CV) shows that the electro-chemical area (ECA) is changed with the different cold pre-compressed MEAs and there exists an optimal compression that results in the maximum ECA.     

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.     

Nickel-polyaniline composite electrodes for hydrogen evolution reaction in alkaline media

In this work, nickel-based electrodes were prepared using a composite electrodeposition technique in a nickel bath containing suspended polyaniline (PAni) particles. The electrodes were characterized by Raman spectroscopy and scanning electron microscopy. The catalytic activity of the composite electrodes for the hydrogen evolution reaction (HER) was measured by cathodic polarization and electrochemical impedance spectroscopy in KOH and KOH with 1 M sucrose at room temperature. The Ni–PAni electrodes showed a high active surface area that contributed to the increase in the current density of HER and to the decrease in overpotential value as compared to Ni electrodes.     

Impact of porous transport layer compression on hydrogen permeation in PEM water electrolysis

Gas permeation through a membrane electrode assembly (MEA) is an important issue in the development of polymer electrolyte membrane (PEM) water electrolyzers, because it can cause explosions and efficiency losses. The influence of operating pressure, temperature and MEA modifications on the permeation was already investigated. However, most of the studies pay no attention to the compression of the porous transport layer (PTL) of the MEA when assembling it in a test cell to carry out the experiments.This paper deals with the impact of the PTL compression on hydrogen permeation and cell voltage. Polarization, impedance and permeation measurements are used to demonstrate that the compression significantly affects the MEA's properties. Measurements show either a linear or nonlinear correlation between current density and hydrogen permeation, depending on the compression.The results indicate that the compression of the PTL must be taken into account for developing MEAs and comparing different permeation measurements.     

Electrolytic production of hydrogen from aqueous acidic methanol solutions

The electrochemical production of hydrogen (H₂) from liquid methanol in acidic aqueous media was investigated in a proton exchange membrane (PEM) electrolyser, comprising a two-compartment glass cell with a membrane electrode assembly (MEA) composed of a Nafion^® 117 membrane and gas diffusion electrodes (GDE). Methanol electrolysis was studied at concentrations ranging from 0 to 16 M, where 0 M corresponds to water electrolysis. The influence of catalysts (Pt and Pt–Ru), catalyst support (C or black), operating temperatures (23, 50 and 75 °C) and operating modes (dry and wet cathode) were evaluated in the static mode. A theoretical thermodynamic analysis of the system was done as a function of temperature. The limiting current densities, kinetic parameters, including the Tafel slopes and current exchange density, and apparent activation energies were determined.     

Analysis and proposition of limiting current density measurement protocol

Limiting current density at different temperatures, backpressures, and balance gases can be used to separate molecular diffusion resistance, Knudsen diffusion resistance and local transport resistance of membrane electrode assembly (MEA). However, the measurement of limiting current density has no unified protocol. The diverse choices in the literature, either in the control of current or voltage or in the atmosphere like relative humidity and O₂ concentrations, make it difficult to compare the results and identify the true bottleneck hindering the mass transport. In this work, the current-voltage curves obtained by current scanning/stepping and voltage scanning/stepping methods under dilute O₂ of different concentrations and a wide range of relative humidity were measured and analyzed systematically. It is found that the voltage stepping method is superior to the other three ways of control for the reliable determination of the limiting current density. Aided with simultaneous electrochemical impedance spectroscopy measurement, the limiting current density can be determined with pinpoint accuracy. When the limiting current density is just used to qualitatively evaluate different MEA, the voltage scanning method can be used instead for its high time efficiency. The selection of the atmosphere also plays an important role in suppressing the distortion from excessive water and reducing the spurious contribution from proton conduction resistance. It is found that O₂ concentrations at 0.5 vol% and relative humidity at 90% can give the best estimation of O₂ transport resistance in membrane electrode assembly.     

A Facile Route for Polymer Electrolyte Membrane Fuel Cell Electrodes with in situ Grown Pt Nanowires

Novel Gas Diffusion Electrodes (GDEs) for Polymer Electrolyte Membrane Fuel Cells (PEMFCs) were prepared by in situ growing Pt nanowires on carbon paper using a facile deposition method at room temperature. Pt nanowires, with a length 100–150 nm, were uniformly coated on the carbon fiber surfaces in carbon paper. This route was much simpler than the traditional method for preparing GDEs because there were no processes needed to make the ink or print the catalysis layer. Membrane Electrode Assemblies (MEAs) were made with the as-prepared GDEs and tested in a 25 cm² PEMFC fed by hydrogen/air. The impedance spectroscopy and polarization curve measurement showed that the as-prepared GDE possessed a lower charge transfer resistance and a higher power density than did the conventional one with ELAT^® GDE LT120EW. The excellent performance obtained and the simple steps made the process a promising technique for preparing GDEs in PEMFCs for commercial applications.     

Double microporous layer cathode for membrane electrode assembly of passive direct methanol fuel cells

A novel membrane electrode assembly (MEA) is described that utilizes a double microporous layer (MPL) structure in the cathode of a passive direct methanol fuel cell (DMFC). The double MPL cathode uses Ketjen Black carbon as an inner-MPL and Vulcan XC-72R carbon as an outer-MPL. Experimental results indicate that this double MPL structure at the cathode provides not only a higher oxygen transfer rate, but enables more effective back diffusion of water; thus, leading to an improved power density and stability of the passive DMFC. The maximum power density of an MEA with a double MPL cathode was observed to be ca. 33.0 mW cm⁻², which is found to be a substantial improvement over that for a passive DMFC with a conventional MEA. A. C. impedance analysis suggests that the increased performance of a DMFC with the double MPL cathode might be attributable to a decreased charge transfer resistance for the cathode oxygen reduction reaction.     

Study of catalyst sprayed membrane under irradiation method to prepare high performance membrane electrode assemblies for solid polymer electrolyte water electrolysis

In this work, a catalyst sprayed membrane under irradiation (CSMUI) method was investigated to develop high performance membrane electrode assembly (MEA) for solid polymer electrolyte (SPE) water electrolysis. The water electrolysis performance and properties of the prepared MEA were evaluated and analyzed by polarization curves, electrochemistry impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The characterizations revealed that the CSMUI method is very effective for preparing high performance MEA for SPE water electrolysis: the cell voltage can be as low as 1.564 V at 1 A cm⁻² and the terminal voltage is only 1.669 V at 2 A cm⁻², which are among the best results yet reported for SPE water electrolysis with IrO₂ catalyst. Also, it is found that the noble metal catalysts loadings of the MEA prepared by this method can be greatly decreased without significant performance degradation. At a current density of 1 A cm⁻², the MEA showed good stability for water electrolysis operating: the cell voltage remained at 1.60 V without obvious deterioration after 105 h operation under atmosphere pressure and 80 °C.     

Performance enhancement of membrane electrode assemblies with plasma etched polymer electrolyte membrane in PEM fuel cell

In this work, a surface modified Nafion 212 membrane was fabricated by plasma etching in order to enhance the performance of a membrane electrode assembly (MEA) in a polymer electrolyte membrane fuel cell. Single-cell performance of MEA at 0.7 V was increased by about 19% with membrane that was etched for 10 min compared to that with untreated Nafion 212 membrane. The MEA with membrane etched for 20 min exhibited a current density of 1700 mA cm⁻² at 0.35 V, which was 8% higher than that of MEA with untreated membrane (1580 mA cm⁻²). The performances of MEAs containing etched membranes were affected by complex factors such as the thickness and surface morphology of the membrane related to etching time. The structural changes and electrochemical properties of the MEAs with etched membranes were characterized by field emission scanning electron microscopy, Fourier transform-infrared spectrometry, electrochemical impedance spectroscopy, and cyclic voltammetry.     

Characterisation tools development for PEM electrolysers

Electrochemical impedance spectroscopy (EIS), current interrupt (CI) and current mapping (CM) were investigated as in-situ characterisation tools for PEM electrolysers. A 25 cm² cell with titanium anode and carbon cathode plates were utilised in this study. A commercial MEA consisting of 1 mg IrO₂/cm² on the anode and 0.3 mg Pt/cm² on the cathode was used. The electrocatalyst was deposited on Nafion^® membranes. The electrochemical losses in a PEM electrolyser namely: activation, ohmic and mass transfer losses were identified using EIS and CI and both the advantages and disadvantages of the methods were discussed. The current distribution over the membrane electrode assembly (MEA) at different current densities was measured using the current mapping method. It is also shown that under the given experimental conditions the current density decreases along the serpentine flow field.     

A polymer electrolyte fuel cell life test: 3 years of continuous operation

Implementation of polymer electrolyte fuel cells (PEMFCs) for stationary power applications requires the demonstration of reliable fuel cell stack life. One of the most critical components in the stack and that most likely to ultimately dictate stack life is the membrane electrode assembly (MEA). This publication reports the results of a 26,300 h single cell life test operated with a commercial MEA at conditions relevant to stationary fuel cell applications. In this experiment, the ultimate MEA life was dictated by failure of the membrane. In addition, the performance degradation rate of the cell was determined to be between 4 and 6 μV h⁻¹, at the operating current density of 800 mA cm⁻². AC impedance analysis and DC electrochemical tests (cyclic voltammetry and polarization curves) were performed as diagnostics during and on completion the test, to understand materials changes occurring during the test. Post mortem analyses of the fuel cell components were also performed.     

Measurement of liquid water content in cathode gas diffusion electrode of polymer electrolyte fuel cell

Water management in cathode gas diffusion electrode (GDE) of polymer electrolyte fuel cell (PEFC) is essential for high performance operation, because liquid water condensed in porous gas diffusion layer (GDL) and catalyst layer (CL) blocks oxygen transport to active reaction sites. In this study, the average liquid water content inside the cathode GDE of a low-temperature PEFC is experimentally and quantitatively estimated by the weight measurement, and the relationship between the water accumulation rate in the cathode GDE and the cell voltage is investigated. The liquid water behavior at the cathode is also visualized using an optical diagnostic, and the effects of operating conditions and GDL structures on the water transport in the cathode GDE are discussed. It is found that the liquid water content in the cathode GDE increases remarkably after starting the fuel cell operation due to the water production at the CL. At a high current density, the cell voltage drops suddenly after starting the operation in spite of a low water content in the cathode GDE. When the GDL thickness is increased, much water accumulates near the cathode CL and the fuel cell shuts down immediately after the operation. In the final section of this paper, the structure of cathode GDL that has several grooves for water removal is proposed to prevent water flooding and improve fuel cell performance. This groove structure is effective to promote the removal of the liquid water accumulated near the active catalyst sites.     

Performance of an air-breathing direct methanol fuel cell

An air-breathing direct methanol fuel cell (DMFC) is attractive for portable-power applications. There are, however, several barriers that must be overcome before DMFCs reach commercially viability. This study shows that the cell power density is strongly affected by the fabrication conditions of the membrane electrode assembly (MEA) and by the technique used for assembly of the cell components. The results indicate that reducing the pressure and the thickness of catalyst layer in the MEA fabrication process can significantly improve power density. The production of water at the cathode, especially at a high power density, is shown to have a strong impact on the operation of an air-breathing DMFC since water blocks the feeding of air to the cathode. The power density (≧20 mW cm⁻²) of an air-breathing DMFC is found to drop to nearly half of its initial value after 30–40 min of operation in a short-term stability test. This appears to be one of the major limitations for potable electronic applications. Despite the many practical difficulties associated with an air-breathing DMFC, an attempt is also made to highlight the importance of the component assembly technique using a small cell pack with four integrated unit cells.     

Modeling electrochemical performance in large scale proton exchange membrane fuel cell stacks

The processes, losses, and electrical characteristics of a Membrane-Electrode Assembly (MEA) of a Proton Exchange Membrane Fuel Cell (PEMFC) are described. In addition, a technique for numerically modeling the electrochemical performance of a MEA, developed specifically to be implemented as part of a numerical model of a complete fuel cell stack, is presented. The technique of calculating electrochemical performance was demonstrated by modeling the MEA of a 350 cm², 125 cell PEMFC and combining it with a dynamic fuel cell stack model developed by the authors. Results from the demonstration that pertain to the MEA sub-model are given and described. These include plots of the temperature, pressure, humidity, and oxygen partial pressure distributions for the middle MEA of the modeled stack as well as the corresponding; current produced by that MEA. The demonstration showed that models developed using this technique produce results that are reasonable when compared to established performance expectations and experimental results.