Review of hydrogen crossover through the polymer electrolyte membrane

Proton exchange membrane fuel cell (PEMFC) is considered to be a promising, clean, and efficient energy conversion device. At present, the main challenges faced by the application of PEMFC in the automotive are cost and durability. Hydrogen from anode to the cathode through polymer electrolyte membrane (i.e. crossover hydrogen) affects the durability of fuel cells. In this paper, the existing literature on hydrogen crossover is reviewed and summarized from consequences, causes, mitigation measures, and detection methods. The influences of hydrogen crossover on the components and performance are discussed. The causes are analyzed from structural permeation and membrane degradation. The methods of alleviating the degradation of the membrane are summarized. The electrochemical and non-electrochemical monitoring methods are described, and the segmented current method is explained separately. The existing problems and research prospects are put forward, which lays a foundation for further research on hydrogen crossover and improvement fuel cell durability.     

Numerical analysis of gas crossover effects in polymer electrolyte fuel cells (PEFCs)

The gas crossover phenomenon in polymer electrolyte fuel cells (PEFCs) is an indicator of membrane degradation. The objective of this paper is to numerically investigate the effects of hydrogen and oxygen crossover through the membrane in PEFCs. A gas crossover model is newly developed and implemented in a comprehensive multi-dimensional, multi-phase PEFC model developed earlier. A parametric study is carried out to investigate the effects of the crossover diffusion coefficients for hydrogen and oxygen as well as the membrane thickness. The simulation results demonstrate that the hydrogen crossover induces an additional oxygen reduction reaction (ORR) and consequently causes an additional voltage drop, while the influence of oxygen crossover on PEFC performance is relatively insignificant because it leads to the hydrogen/oxygen chemical reaction at the anode side. Finally, using the time-dependent gas crossover data that are available in the literature (measured in days), we conduct gas crossover simulations to examine the effects of increased gas crossover due to membrane degradation on PEFC performance and successfully demonstrate decaying polarization curves with respect to time. This study clearly elucidates the detailed mechanisms of the hydrogen and oxygen crossover phenomena and their effect on PEFC performance and durability.     

Effects of gas diffusion layer structure on the open circuit voltage and hydrogen crossover of polymer electrolyte membrane fuel cells

The clamping pressure of polymer electrolyte membrane fuel cells for vehicle applications should be typically high enough to minimize contact resistance. However, an excessive compression pressure may cause a durability problem. In this study, the effects of gas diffusion layer (GDL) structure on the open circuit voltage (OCV) and hydrogen crossover have been closely examined. Results show that the performances of fuel cells with GDL-1 (a carbon fiber felt substrate with MPL having rough surface) and GDL-3 (a carbon fiber paper substrate with MPL having smooth surface) are higher than that with GDL-2 (a carbon fiber felt substrate with MPL having smooth surface) under low clamping torque conditions, whereas when clamping torque is high, the GDL-1 sample shows the largest decrease in cell performance. Hydrogen crossover for all GDL samples increases with the increase of clamping torque, especially the degree of increase of GDL-1 is much greater than that of the other two GDL samples. The OCV reduction of GDL-1 is much greater than that of GDL-2 and GDL-3. It is concluded that the GDL-3 is better than the other two GDLs in terms of fuel cell durability, because the GDL-3 shows the minimum OCV reduction.     

Potential of hydrolyzed oxymethylene dimethyl ether for the suppression of fuel crossover in polymer electrolyte fuel cells

Fuel crossover is a crucial issue for polymer electrolyte fuel cells (PEFCs) supplied directly with liquid fuels. Therefore, finding a type of fuel with a low fuel crossover rate is required. In this study, we investigated fuel crossover characteristics for oxymethylene dimethyl ether (OME), which has attracted attention for use in engines, and compared it with methanol. Cell performance tests and exhaust gas analyses showed that fully hydrolyzed OME (h-OME), which consisted of methanol and formaldehyde, yields high cell performance at high fuel concentrations, due to the low fuel crossover rate, compared with a direct methanol fuel cell (DMFC). To clarify a factor suppressing fuel crossover, h-OME's effective diffusion coefficient in the membrane was measured. Although an effective diffusion coefficient for fuels like methanol commonly increases with increased fuel's concentration, h-OME's effective diffusion coefficient decreased with increased fuel concentration, leading to a low fuel crossover rate at high h-OME concentrations.     

Fuel crossover and internal current in polymer electrolyte membrane fuel cell from water visualization using X-ray radiography

The fuel crossover and internal current in a polymer electrolyte membrane fuel cell undergo a chemical reaction in the cell without power generation. These are the main phenomena for reduced cell voltage at low current density. This fuel crossover also degrades the fuel cell performance, efficiency, and durability. Thus, observation of these phenomena is important for understanding and developing a polymer electrolyte membrane fuel cell. Using X-ray radiography, the water distribution and membrane swelling, which indicate fuel crossover and internal current, in an operating polymer electrolyte membrane fuel cell under open-circuit conditions were examined. The X-ray images effectively demonstrated the transient changes of each phenomenon, which are related to the properties of each component and the operating conditions.     

Degradation of polymer electrolyte membranes

One of the predominant failure modes of polymer electrolyte membrane (PEM) fuel cells is the degradation of the PEM, especially when the fuel cell is used for transportation applications. Numerous studies have been carried out regarding this issue but many aspects of the degradation are not yet understood. This paper reviews the available literature regarding membrane degradation, and attempts to classify the degradation modes into three categories: mechanical, thermal and chemical/electrochemical. The factors that contribute to each mode are discussed, along with detailed mechanisms for some degradations. Some possible mitigation strategies are also explored.     

Pt-based electrocatalysts for polymer electrolyte membrane fuel cells prepared by supercritical deposition technique

Pt-based electrocatalysts were prepared on different carbon supports which are multiwall carbon nanotubes (MWCNTs), Vulcan XC 72R (VXR) and black pearl 2000 (BP2000) using a supercritical carbon dioxide (scCO₂) deposition technique. These catalysts were characterized by using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and cyclic voltammetry (CV). XRD and HRTEM results demonstrated that the scCO₂ deposition technique enables a high surface area metal phase to be deposited, with the size of the Pt particles ranging from 1 to 2 nm. The electrochemical surface areas (ESAs) of the prepared electrocatalysts were compared to the surface areas of commercial ETEK Pt/C (10 wt% Pt) and Tanaka Pt/C (46.5 wt% Pt) catalysts. The CV data indicate that the ESAs of the prepared Pt/VXR and Pt/MWCNT catalysts are about three times larger than that of the commercial ETEK catalyst for similar (10 wt% Pt) loadings. Oxygen reduction activity was investigated by hydrodynamic voltammetry. From the slope of Koutecky–Levich plots, the average number of electrons transferred in the oxygen reduction reaction (ORR) was 3.5, 3.6 and 3.7 for Pt/BP2000, Pt/VXR and Pt/MWCNT, correspondingly, which indicated almost complete reduction of oxygen to water.     

The dependence of performance degradation of membrane electrode assembly on platinum loading in polymer electrolyte membrane fuel cell

The durability of membrane electrode assemblies (MEAs) with varying amounts of Pt loading on the cathode of polymer electrolyte membrane fuel cells was investigated using load cycling as an accelerated degradation test (ADT). The single-cell performance of the MEA as determined by the ADT declined by approximately 34, 48, and 78%, when cathode Pt loading in the MEA was reduced to 0.3, 0.2, and 0.1 mg cm⁻², respectively. The increase in MEA performance declined at higher cathode Pt loading conditions, and the degradation rate of MEA performance was also diminished. To characterize the electrochemical and structural properties of the MEAs, cyclic voltammograms, electrochemical impedance spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and field-emission scanning electron microscopy were utilized before and after ADT.     

Crossover effects of the land/channel width ratio of bipolar plates in polymer electrolyte membrane fuel cells

The crossover effect of the land/channel width ratio of bipolar plates in polymer electrolyte membrane fuel cells is experimentally investigated in this study. To isolate the effect of the land/channel width ratio, three different types of bipolar plates of a fixed sum and channel width are specially prepared. With three different bipolar plates, measurements are taken of electrochemical performance, inlet pressure, and hydrogen crossover rate. When the stoichiometric ratio of hydrogen is 1.5, the standard type of bipolar plate, BP2 (land width = 0.75 mm, channel width = 1.05 mm) show the best performance. However, according to increasing stoichiometric ratio of hydrogen, BP3 (land width = 1.12 mm, channel width = 0.68 mm) has the best performance, especially at the medium and high current range. For the crossover rate, the biggest amount of hydrogen gas crossover to the cathode in BP3. This is because of the anode inlet pressure caused by the largest land/channel ratio of BP3.     

Cold start analysis of polymer electrolyte membrane fuel cells

Cold start is critical to the commercialization of polymer electrolyte membrane fuel cell (PEMFC) for practical applications such as backup power and automotive applications. In this study, various numerically simulated PEMFC cold start processes are analyzed. The success of the cold start process depends on the competition between how fast the cell is heated up to the freezing point temperature and how fast ice is formed and built up in the pores of the cathode catalyst layer (CL) blocking oxygen transport to the reaction sites; the success of the cold start process thus depends on the product water (i) that is absorbed into the ionomer in the CL and membrane, (ii) that is taken away in vapour form by the gas flows (can be neglected), and (iii) that is frozen into ice in the CL pores. It is found that the membrane thickness and the ionomer volume fraction in the CL play pivotal roles in reducing the amount of ice formation. A thicker membrane leads to a larger water capacity but a slower water absorption process, and increasing the ionomer volume fraction in the CL enlarges the ionomer water capacity and enhances the membrane water absorption. Starting the cell under the potentiostatic condition is confirmed to be superior to the galvanostatic condition. Heating up the external surfaces and the inlet air enhances the temperature increment of the cell. However, the external heating methods have negligible improvement in reducing the amount of ice formation. Even though heating the inlet air is more effective in increasing the cell temperature than heating the outer surfaces, the heat capacity of the inlet air is low.     

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.     

Performance of membrane electrode assemblies using PdPt alloy as anode catalysts in polymer electrolyte membrane fuel cell

Pd-based nanoparticles, such as 40 wt.% carbon-supported Pd₅₀Pt₅₀, Pd₇₅Pt₂₅, Pd₉₀Pt₁₀ and Pd₉₅Pt₅, for anode electrocatalyst on polymer electrolyte membrane fuel cells (PEMFCs) were synthesized by the borohydride reduction method. PdPt metal particles with a narrow size distribution were dispersed uniformly on a carbon support. The membrane electrode assembly (MEA) with Pd₉₅Pt₅/C as the anode catalyst exhibited comparable single-cell performance to that of commercial Pt/C at 0.7 V. Although the Pt loading of the anode with Pd₉₅Pt₅/C was as low as 0.02 mg cm⁻², the specific power (power to mass of Pt in the MEA) of Pd₉₅Pt₅/C was higher than that of Pt/C at 0.7 V. Furthermore, the single-cell performance with Pd₅₀Pt₅₀/C and Pd₇₅Pt₂₅/C as the anode catalyst at 0.4 V was approximately 95% that of the MEA with the Pt/C catalyst. This indicated that a Pd-based catalyst that has an extremely small amount of Pt (only 5 or 50 at.%) can be replaced as an anode electrocatalyst in PEMFC.     

Relative humidity control in polymer electrolyte membrane fuel cells without extra humidification

The performance of polymer electrolyte membrane fuel cells is highly influenced by the water content in the membrane. To prevent the membrane from drying, several researchers have proposed extra humidification on the input reactants. But in some applications, the extra size and weight of the humidifier should be avoided. In this research a control technique, which maintains the relative humidity on saturated conditions, is implemented by adjusting the air stoichiometry; the effects of drying of membrane and flooding of electrodes are considered, as well. For initial analysis, a mathematical model reveals the relationship among variables that can be difficult to monitor in a real machine. Also prediction can be tested optimizing time and resources. For instance, the effects of temperature and humidity can be analyzed separately. For experimental validation, tests in a fault tolerant fuel cell are conducted.     

Low methanol crossover and high performance of DMFCs achieved with a pore-filling polymer electrolyte membrane

We compared the performance of the membrane electrode assembly for direct methanol fuel cells (DMFCs) composed of a pore-filling polymer electrolyte membrane (PF membrane) with that composed of a commercial Nafion-117 membrane. In DMFC tests, the methanol crossover flux was 23% lower in the PF membrane than in the Nafion-117 membrane even though the thickness of the PF membrane was 43% that of Nafion-117. This led to a higher DMFC performance and the lower overpotential of the cathode of the PF membrane. Feeding an aqueous 10 M methanol solution at 50 °C produced a low cathode overpotential, as low as 0.40 V at 0.2 A in the PF membrane, whereas the potential was 0.65 V at 0.2 A in the Nafion-117 membrane. In contrast, the ohmic loss and anode overpotential were almost the same in the two membranes. We confirmed that a reduction in methanol crossover using the PF membrane results in lower cathode overpotential and higher DMFC performance. In addition, the electro-osmotic coefficient was estimated as 1.3 in the PF membrane and 2.6 in Nafion-117, based on a water mass-balance model and values showing that the PF membrane prevents the flooding of the cathode at a low gas flow rate using. A highly concentrated methanol solution can be applied as a fuel without decreasing DMFC performance using PF membranes.     

Life prediction of membrane electrode assembly through load and potential cycling accelerated degradation testing in polymer electrolyte membrane fuel cells

Accelerated degradation tests (ADTs) are commonly used to assess the durability of membrane electrode assembly (MEA) components consisting of polymer electrolyte membrane fuel cells (PEMFC) under harsh stress conditions, estimating their lifetime in actual use condition and uncovering their vital degradation mechanisms. ADTs apply mechanically, chemically, or thermally combined stressors to efficiently investigate the durability of MEAs. However, combined stressors for ADTs might cause biased lifetime prediction because major deterioration mechanisms of MEA components are mixed with each other. This work proposes a method to accurately predict the lifetime of MEA through empirical modeling of its performance degradation through ADTs under potential cycle (carbon corrosion) and load cycle tests (electrocatalysts). To simulate operation modes of fuel cell electric vehicles, MEAs are tested under continuous on-off cycle testing (24 h operating and 1 h break) for 5000 h. Degradation patterns of MEAs are first modeled by the empirical model. The relationship between ADTs (potential and load cycle) and continuous on-off condition is then closely examined to accurately predict MEA lifetime under actual operation environments. The proposed idea has a potential to resolve critical durability issues of MEAs by identifying intermingling effects from other constituents.     

Tunable aggregation of short-side-chain perfluorinated sulfonic acid ionomers for the catalyst layer in polymer electrolyte membrane fuel cells

We control the aggregation of short-side-chain (SSC) perfluorinated sulfonic acid (PFSA) ionomers for catalyst-layer (CL) inks by using a dispersion solvent of dipropylene glycol (DPG) and water. By increasing the fraction of PFSA backbone preferable DPG content in a dispersion solvent, the size of SSC-PFSA aggregates decreases exponentially from microscale to nanoscale, affecting the catalyst-ionomer agglomerates’ size and distribution in the CL inks. The surface morphology and porosity properties of the resulting CL are investigated, and the fuel cell performances are studied at two different humidity conditions (50 and 100% RH). Compared to the previous study with long-side-chain (LSC) PFSA ionomers, the SSC-PFSA ionomers show the optimized performance at higher DPG content, where the solvating power is intermediate for SSC-PFSA ionomers having shorter hydrophilic side chain than LSC-PFSA ionomers.     

Correlation between performance of polymer electrolyte membrane fuel cell and degradation of the carbon support in the membrane electrode assembly using image processing method

Long-time operation and various conditions cause the membrane electrode assembly (MEA) of polymer electrolyte membrane fuel cells (PEMFCs) to degrade, which results in decreased performance. The degradation of the MEA appears as various symptoms, such as the loss of carbon support and agglomeration of the Pt catalyst. In this paper, damage on the surface of the MEA by long-time operation and various conditions is induced intentionally by high-temperature conditions in a thermostat chamber. The MEA surface damage is photographed by scanning electron microscopy (SEM), and the loss of the carbon support that fixes the platinum catalyst is judged. Image processing is used to analyze damage on the MEA surface, and binarization processing is applied to the image processing method. SEM imagery is taken at magnifications of 100 × and the trends in quantified surface damage on the MEA according to the degradation temperature are analyzed. The correlation between the quantitative damage on the MEA surface and the performance of the PEMFC is checked. As a result, the tendency of decreasing PEMFC performance is derived from increasing quantified damage on the MEA surface.     

Water transport in polymer electrolyte membrane fuel cells

Polymer electrolyte membrane fuel cell (PEMFC) has been recognized as a promising zero-emission power source for portable, mobile and stationary applications. To simultaneously ensure high membrane proton conductivity and sufficient reactant delivery to reaction sites, water management has become one of the most important issues for PEMFC commercialization, and proper water management requires good understanding of water transport in different components of PEMFC. In this paper, previous researches related to water transport in PEMFC are comprehensively reviewed. The state and transport mechanism of water in different components are elaborated in detail. Based on the literature review, it is found that experimental techniques have been developed to predict distributions of water, gas species, temperature and other parameters in PEMFC. However, difficulties still remain for simultaneous measurements of multiple parameters, and the cell and system design modifications required by measurements need to be minimized. Previous modeling work on water transport in PEMFC involves developing rule-based and first-principle-based models, and first-principle-based models involve multi-scale methods from atomistic to full cell levels. Different models have been adopted for different purposes and they all together can provide a comprehensive view of water transport in PEMFC. With the development of computational power, application of lower length scale methods to higher length scales for more accurate and comprehensive results is feasible in the future. Researches related to cold start (startup from subzero temperatures) and high temperature PEMFC (HT-PEMFC) (operating at the temperatures higher than 100 °C) are also reviewed. Ice formation that hinders reactant delivery and damages cell materials is the major issue for PEMFC cold start, and enhancing water absorption by membrane electrolyte and external heating have been identified as the most effective ways to reduce ice formation and accelerate temperature increment. HT-PEMFC that can operate without liquid water formation and membrane hydration greatly simplifies water management strategy, and promising performance of HT-PEMFC has been demonstrated.     

Hybrid electrode effects on polymer electrolyte membrane fuel cells

Research on membrane electrode assemblies (MEA) is focused on reducing cost and increasing durability in polymer electrolyte membrane fuel cells (PEMFC). Development of the electrode structure and reduction of platinum (Pt) contents are studied to improve the efficiency of Pt catalysts. We studied the combined effects of improved electrode structure and reduced Pt loading. To enhance the performance of an MEA, a commercial Pt/C catalyst with micro graphite (MG) was used. The 40 wt% Pt/C catalyst content was reduced about 5, 15, 30 and 60 wt% at the cathode. MG was added as a reduced weight percent of Pt/C. Cell performance was significantly dependent on the content of MG. The MEA with 15 wt% of MG was seen to best performance compare with other MEA. These results showed that the catalyst with mixed MG improved both performance and cost savings with reduced Pt content of PEMFC.