Research on two‐phase flow considering hydrogen crossover in the membrane for a polymer electrolyte membrane fuel cell

Hydrogen crossover has an important effect on the performance and durability of the polymer electrolyte membrane fuel cell (PEMFC). Severe hydrogen crossover can accelerate the degradation of membrane and thus increase the possibility of explosion. In this study, a two‐phase, two‐dimensional, and multiphysics field coupling model considering hydrogen crossover in the membrane for PEMFC is developed. The model describes the distributions of reactant gases, current density, water content in membrane, and liquid water saturation in cathode electrodes of PEMFC with intrinsic hydrogen permeability, which is usually neglected in most PEMFC models. The conversion processes of water between gas phase, liquid phase, and dissolved water in PEMFC are simulated. The effects of changes in hydrogen permeability on PEMFC output performance and distributions of reactant gases and water saturation are analyzed. Results showed that hydrogen permeability has a marked effect on PEMFC operating under low current density conditions, especially on the open circuit voltage (OCV) with the increase of hydrogen permeability. On the contrary, the effect of hydrogen permeability on PEMFC at high current density is negligible within the variation range of hydrogen permeability in this study. The nonlinear relations of OCV with hydrogen diffusion rate are regressed.     

Effects of crossover hydrogen on platinum dissolution and agglomeration

The durability of catalysts in the polymer-electrolyte membrane fuel cell (PEMFC) is identified as a critical limiting factor for wide commercialization of fuel cells. Even though much progress has been made in understanding the degradation mechanisms, the phenomena of Pt dissolution and agglomeration and their contributing factors are not fully understood. In the present investigation, the effects of crossover hydrogen on Pt degradation are studied using an accelerated stress test (AST). The end-of-test (EOT) membrane-electrode-assemblies (MEAs) were characterized by X-ray diffraction (XRD), scanning-electron microscopy (SEM), and energy-dispersive X-ray (EDX). The results provided mechanistic understanding of Pt dissolution and agglomeration: Pt growth and agglomeration were found to be less severe with more crossover hydrogen due likely to the chemical reduction of Pt oxides by crossover hydrogen and the subsequently decrease in the amount of Pt ions formed via the oxide pathway.     

Hydrogen crossover through perfluorosulfonic acid membranes with variable side chains and its influence in fuel cell lifetime

In this study, hydrogen crossover in long side chain Nafion 211 membrane and short side chain Aquivion membrane is studied under different conditions. It is found that both temperature and relative humidity significantly influence the hydrogen crossover in the polymer electrode membranes (PEMs). The difference in hydrogen crossover behavior between Nafion 211 membrane and Aquivion membrane is revealed. The influence of hydrogen crossover on the fuel cell lifetime is also investigated under open circuit voltage (OCV). It is proved hydrogen crossover in the PEM would lead to possible degradation of the PEM and the decrease of electro-chemical surface area in the catalyst of the single cell. Single cell assembled with Aquivion membrane shows slower OCV and ECSA decay compared to the Nafion 211 single cell. Our results suggest that the PEM fuel cell lifetime is closely related to the hydrogen crossover in the PEM. The current study also highlights the possibility of improving the fuel cell durability by rational design of the PEM morphology.     

Analysis of surface and interior degradation of gas diffusion layer with accelerated stress tests for polymer electrolyte membrane fuel cell

The effects of surface and interior degradation of the gas diffusion layer (GDL) on the performance and durability of polymer electrolyte membrane fuel cells (PEMFCs) have been investigated using three freeze-thaw accelerated stress tests (ASTs). Three ASTs (ex-situ, in-situ, and new methods) are designed from freezing ?30 °C to thawing 80 °C by immersing, supplying, and bubbling, respectively. The ex-situ method is designed for surface degradation of the GDL. Change of surface morphology from hydrophobic to hydrophilic by surface degradation of GDL causes low capillary pressure which decreased PEMFC performance. The in-situ method is designed for the interior degradation of the GDL. A decrease in the ratio of the porosity to tortuosity by interior degradation of the GDL deteriorates PEMFC performance. Moreover, the new method showed combined effects for both surface and interior degradation of the GDL. It was identified that the main factor that deteriorated the fuel cell performance was the increase in mass transport resistance by interior degradation of GDL. In conclusion, this study aims to investigate the causes of degraded GDL on the PEMFC performance into the surface and interior degradation and provide the design guideline of high-durability GDL for the PEMFC.     

Anode bleeding experiments to improve the performance and durability of proton exchange membrane fuel cells

Cost, durability, efficiency and fuel utilization are important issues that remain to be resolved for commercialization of proton exchange membrane fuel cells (PEMFC). Anode flow mode, which includes recirculation, dead-ended and exit bleeding operation, plays an important role in fuel utilization, durability, performance and the overall cost of the fuel cell system. Depending on the flow mode, water and nitrogen accumulation in the anode leads to voltage transients and local fuel starvation, which causes cell potential reversal and carbon corrosion in the cathode catalyst layers. Controlled anode exit bleeding can avoid the accumulation of nitrogen and water and improve fuel utilization. In this study, we present a method to control the bleed rate with high precision in experiments and demonstrate that hydrogen utilization as high as 0.9988 for a 25 cm² single cell and 0.9974 for an 8.17 cm² single cell can be achieved without significant performance loss. In the experiments, anode pressure is kept at 1 bar higher than the cathode pressure to decrease nitrogen crossover from the cathode, decreasing the crossover from the cathode. Moreover, four load cycle profiles are applied to observe the cumulative loss in the electrochemical surface area (ECSA), which are acquired from cyclic voltammetry (CV) analysis. Experiments confirm that the ECSA loss and severe voltage transients are indicative of fuel starvation induced by prolonged dead-ended or low exit-bleed operation modes whereas bleed rates that are larger than the predicted crossover rate are sufficient to operate the fuel cell without voltage transients and detrimental ECSA loss.     

A review of low-temperature proton exchange membrane fuel cell degradation caused by repeated freezing start

Proton exchange membrane fuel cell (PEMFC) has advantages of zero emission, fast response and high-power density. There are still obstacles such as manufacturing cost, life span, infrastructure construction and subzero temperature star-up restricting commercialization of PEMFC. The low-temperature start-up is one of them that needs to be solved in the field of fuel cell vehicle. This paper presents research progresses involving PEMFC degradation caused by the low-temperature start-up. Degradation phenomena and mechanism under component-level caused by repeated freezing start, influencing factors and mitigation strategies are summarized and reviewed. Conclusions are made that frequent ice freezing and melting causes the membrane electrode assembly damaged irreversibly, the quality of cold start and low temperature influence the degradation strongly and purge after shutdown, better materials and optimal fuel cell structure design are helpful to reduce the impact of cold start on fuel cell performances. It is suggested that future work should be focused on optimizing strategies of the shutdown purge, promoting the quality of cold start, enhancing properties of the materials, improving internal structure design of stack and developing low-temperature attenuation models.     

Recent development in design a state-of-art proton exchange membrane fuel cell from stack to system: Theory,integration and prospective

As an efficient energy converter, the proton exchange membrane fuel cell (PEMFC) is developed to couple various applications, including portable applications, transportation, stationary power generation, unmanned underwater vehicles, and air independent propulsion. PEMFC is a complex system consisting of different components that can be influenced by many factors, such as material properties, geometric designs operating conditions, and control strategies. The interaction between components and subsystems could affect the performance, durability, and lifespan of PEMFC system. To design a high performance, long lifespan, high durability PEMFC, it's essential to comprehensively understand the coupling effect of different factors on the overall performance and durability of PEMFCs. This review will present existing research on basis of four aspects, involving fuel cell stack design, subsystems design and management, mass transfer enhancement, and system integration. Firstly, the multi-physics intergradation and component design of PEMFC are reviewed with the designing mechanisms and recent progress. Besides, mass transfer enhancement methods are discussed by bipolar plate design and membrane electrode assembly optimization. Then, water management, thermal management, and fuel management are summarized to provide design guidance for PEMFC. The specifications design and system management for various engineering applications are briefly presented.     

Degradation analysis of the core components of metal plate proton exchange membrane fuel cell stack under dynamic load cycles

The durability of metal plate proton exchange membrane fuel cell (PEMFC) stack is still an important factor that hinders its large-scale commercial application. In this paper, we have conducted a 1000 h durability test on a 1 kW metal plate PEMFC stack, and explored the degradation of the core components. After 1000 h of dynamic load cycles, the voltage decay percentage of the stack under the current densities of 1000 mA cm^?2 is 5.67%. By analyzing the scanning electron microscopy (SEM) images, the surfaces of the metal plates are contaminated locally by organic matter precipitated from the membrane electrode assembly (MEA). The SEM images of the catalyst coated membrane (CCM) cross section indicate that the MEA has undergone severe degradation, including the agglomeration of the catalyst layer, and the thinning and perforation of the PEM. These are the main factors that cause the rapid increase in hydrogen crossover flow rate and performance decay of the PEMFC stack.     

Understanding and approaches for the durability issues of Pt-based catalysts for PEM fuel cell

The state-of-art understanding of durability issues (the degradation reasons and mechanisms, the influence of working conditions, etc.) of Pt-based catalysts for proton exchange membrane fuel cell (PEMFC) and the approaches for improving and studying catalyst durability are reviewed. Both carbon support and catalytic metals degrade under PEMFC conditions, respectively, through the oxidation of carbon and the agglomerate and the detachment from support materials of catalytic metals, especially under unnormal working conditions; furthermore, the degradation of carbon support and catalytic metals interact with and exacerbate one another. The working temperature, humidity, cell voltage (the electrode potential and the mode applied on the electrode), etc. can influence the catalyst durability. Carbons with high graphitization degree as support materials and alloying Pt with some other metals are proved to be effective ways to improve the catalyst durability. Time-effective and reliable methods for studying catalyst durability are indispensable for developing PEMFC catalysts.     

The influence of degradation effects in proton exchange membrane fuel cells on life cycle assessment modelling and environmental impact indicators

Although proton exchange membrane fuel cell (PEMFC) systems are expected to have lower environmental impacts in the operational phase, compared to conventional energy conversion systems, there are still certain economic, operational, and environmental setbacks. Durability under a wide range of operating conditions presents a challenge because degradation processes affect the PEMFC efficiency. Typically, life cycle assessment (LCA) of PEMFC systems do not include performance degradation. Thus, a novel semi-empirical PEMFC model is developed, which includes degradation effects caused by different operational regimes (dynamic and steady-state). The model is integrated into LCA through life cycle inventory (LCI) to achieve a more realistic and accurate evaluation of environmental impacts. Verification of the model clearly showed that the use of existing LCI models underestimates the environmental impacts. This is especially evident when green hydrogen is used in PEMFC operational phase, where manufacturing phase and maintenance (stack replacements) become more influential. Input parameters of the model can be modified to reflect technological improvements (e.g. platinum loading or durability) and evaluate the effects of future scenarios.     

Degradation prediction of proton exchange membrane fuel cell using auto-encoder based health indicator and long short-term memory network

As durability of proton exchange membrane fuel cell (PEMFC) remains as the main obstacle for its larger scale commercialization, predicting PEMFC degradation progress is thus an effective way to extend its lifetime. To realize reliable prediction, a novel health indicator (HI) extraction method based on auto-encoder is proposed in this paper, with which PEMFC future voltage can be predicted by long short-term memory network (LSTM). The effectiveness and robustness of proposed approach is investigated with test data simulating vehicle operation conditions, and accurate prediction performance can be observed, with the maximum root mean square error (RMSE) of 0.003513. Moreover, by comparing with two commonly prognostic methods including attention-based gated recurrent unit network and polarization model-LSTM, the proposed method can provide better predictions under various operating conditions. Furthermore, with the proposed method, the degradation mechanism of PEMFC can also be analyzed. Therefore, the proposed prognostic method can predict reliable PEMFC degradation progress and its corresponding degradation mechanisms, which will be beneficial in practical PEMFC systems for taking appropriate strategies to guarantee PEMFC durability.     

Carbon monoxide poisoning of proton exchange membrane fuel cells

Proton exchange membrane fuel cell (PEMFC) performance degrades when carbon monoxide (CO) is present in the fuel gas; this is referred to as CO poisoning. This paper investigates CO poisoning of PEMFCs by reviewing work on the electrochemistry of CO and hydrogen, the experimental performance of PEMFCs exhibiting CO poisoning, methods to mitigate CO poisoning and theoretical models of CO poisoning. It is found that CO poisons the anode reaction through preferentially adsorbing to the platinum surface and blocking active sites, and that the CO poisoning effect is slow and reversible. There exist three methods to mitigate the effect of CO poisoning: (i) the use of a platinum alloy catalyst, (ii) higher cell operating temperature and (iii) introduction of oxygen into the fuel gas flow. Of these three methods, the third is the most practical. There are several models available in the literature for the effect of CO poisoning on a PEMFC and from the modeling efforts, it is clear that small CO oxidation rates can result in much increased performance of the anode. However, none of the existing models have considered the effect of transport phenomena in a cell, nor the effect of oxygen crossover from the cathode, which may be a significant contributor to CO tolerance in a PEMFC. In addition, there is a lack of data for CO oxidation and adsorption at low temperatures, which is needed for detailed modeling of CO poisoning in PEMFCs. Copyright © 2001 John Wiley & Sons, Ltd.     

Simulation study on magnetic field distribution of PEMFC

As a promising next-generation energy source, proton exchange membrane fuel cell (PEMFC) still suffers from durability and reliability issues, where PEMFC performance will decay during its operation. In this study, a three-dimensional, multi-component and multi-physics PEMFC model is developed to investigate the effect of PEMFC performance degradation on its external magnetic field. By comparing simulation results and experimental data, the capability of the developed model in simulating magnetic field due to PEMFC current is demonstrated. With developed model, different PEMFC degradation mechanisms, including flooding, dehydration, PEMFC aging are simulated, and the amplitudes and distributions of magnetic field under different mechanisms are investigated. Moreover, considering local defects may happen in practical PEMFC systems, its influence on magnetic field distribution is also studied. From the results, the correlation between PEMFC performance degradation and its magnetic field distribution is clarified, which will be beneficial for researches utilizing PEMFC magnetic field for analyzing PEMFC performance variation.     

Introducing a novel technique for measuring hydrogen crossover in membrane-based electrochemical cells

Hydrogen crossover that is the unwanted hydrogen permeation across the membrane driven by the difference of gas concentrations causes a critical concern of safety and efficiency for electrochemical cells, such as fuel cells and electrolyzer cells. Although the hydrogen crossover measurement in fuel cells that employ platinum based catalysts is simple and widely used in laboratory settings, it is questionable to apply existing limiting current method to water electrolyzer cells and alkaline exchange membrane (AEM) systems, which is due to the typical catalyst materials used and membrane properties, respectively. In this work, we demonstrate the operation of a compact and low-cost method of measuring hydrogen crossover that works for both AEM and proton exchange membrane (PEM) systems. The method entails a tandem configuration that utilizes an upstream crossover cell with a downstream cell in hydrogen pump configuration to measure the crossover in the cell of interest. We have successfully measured the hydrogen crossover with different membranes at various differential pressures. The developed method can be applied to catalyst-free membranes (both PEM and AEM) as well as PGM free catalyst containing cells. It will be a promising technique for measuring hydrogen crossover in-situ for a real operating membraned-based electrochemical cell or stack.     

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.     

Uncertainty analysis and robust control of fuel delivery systems considering nitrogen crossover phenomenon

In this paper, the fuel delivery subsystem (FDS) with hydrogen recirculation and anode bleeding is applied in proton exchange membrane fuel cell (PEMFC) system, which is utilized to supply hydrogen to the anode of stack and recirculate fuel back to the supply line. As the diffusion of nitrogen from cathode to anode is inevitable in a real PEMFC during long-term operation. To prevent system performance decline due to nitrogen accumulation. Therefore, this paper firstly develops a control-oriented nonlinear dynamic FDS model involving gas diffusion. Additionally, the FDS is very sensitive to operating environment, uncontrolled operation conditions may cause stack degradation. Specifically, a method based on Monte Carlo simulation is proposed to identify the key parameter boundaries. Then the gas distribution in FDS due to nitrogen crossover is analyzed in detail. After this, a hybrid robust methodology based on sliding mode algorithm is also proposed to maintain adequate hydrogen pressure supply, suitable hydrogen and nitrogen content in the system in presence of nitrogen crossover and renewed uncertainties. Finally, the performance of the presented controller is compared with nonlinear PID (NPID) control and nonlinear multi-input-multi-output (NMIMO) control through a hardware-in-the-loop test bench. Experimental results show that the hybrid controller is accurate and suitable for control purpose, the nitrogen content is restricted to the given range and the variation of output voltage is limited to the desired boundaries, the feasibility and effectiveness are validated.     

Hydrogen circulation system model predictive control for polymer electrolyte membrane fuel cell-based electric vehicle application

Polymer electrolyte membrane fuel cell (PEMFC) is one of the promising solutions overcoming future energy crisis and environment pollution in the automotive industry. However, PEMFC is vulnerable to the circulation of hydrogen mass flow rate and pressure, which may cause the degradation of the PEMFC's anode components and reduction of output performance over time. Thus, the control of the hydrogen supply system draws attention currently and is critical for the durability and stability of the PEMFC system. In this study, a model predictive control (MPC) approach for hydrogen circulation system is developed to regulate the hydrogen flow circulating. A model of the hydrogen supply system that contains a flow control valve, a supply manifold, a return manifold and a hydrogen circulating pump is firstly developed to describe the behavior of the hydrogen mass flow dynamics in the PEMFC. Subsequently, a hydrogen circulating pump MPC scheme is designed based on the piecewise linearized model of hydrogen circulation as well as the switched MPC controllers. By predicting the pressure of the return manifold and the angle velocity of the pump, the proposed MPC approach can manipulate the hydrogen circulating pump to achieve efficient and stable operation of the PEMFC.     

Intensifying vehicular proton exchange membrane fuel cells for safer and durable,design and operation

The explosion in a proton exchange membrane fuel cell (PEMFC) powered forklift in Louisiana, USA in May 2018 and the resulting fatality highlights the need for the improved safety of this technology. Apart from the safety concerns, PEMFC durability has been an important issue towards its further commercialization. Both the safety and durability concerns associated with this technology can be attributed to the temporal degradation of its components. In this study, we have developed a mathematical model that relates the microscale PEMFC degradation to the probability of a macroscale explosion in a Fuel Cell Electric Vehicle (FCEV). Using the model and the inherent safety principle of intensification, it was observed that increasing the operating temperature of the PEMFC system can significantly improve both its safety and durability while intensifying membrane design parameters i.e. membrane thickness and membrane conductivity do not provide any significant improvements. A key inference from this study is that the durability (expressed in voltage loss) and safety (expressed in explosion probability) of a PEMFC system are not perfectly correlated.     

Degradation of a polymer exchange membrane fuel cell stack with Nafion membranes of different thicknesses: Part I. In situ diagnosis

The durability of polymer exchange membrane (PEM) fuel cells, under a wide range of operational conditions, has been attracting intensive attention, as durability is one of the largest barriers for commercialization of this promising technology. In the present work, membrane electrode assembly (MEA) degradation of a four-cell stack with Nafion membranes of different thicknesses, including N117, N115, NR212, and NR211, was carried out for 1000 h under idle conditions. By means of several on-line electrochemical measurements, the performance of the individual cells was analyzed at different times during the degradation process. The results indicate that the cells with thinner membranes have a lower open circuit voltage (OCV) due to the higher fuel crossover. Before degradation, the thickness of the membranes correlates with performance of the cell. However, with the advancement of degradation, the performance of cells with thinner membranes degraded much faster than those with thicker membranes, especially after 800 h of operation. The fast performance degradation for thinner membranes is evident by a dramatic increase in hydrogen crossover indicating membrane thinning or pinhole formation.     

A data-driven digital-twin prognostics method for proton exchange membrane fuel cell remaining useful life prediction

Prognostics and health management of proton exchange membrane fuel cell (PEMFC) systems have driven increasing research attention in recent years as the durability of PEMFC stack remains as a technical barrier for its large-scale commercialization. To monitor the health state during PEMFC operation, digital twin (DT), as a smart manufacturing technique, is applied in this paper to establish an ensemble remaining useful life prediction system. A data-driven DT is constructed to integrate the physical knowledge of the system and a deep transfer learning model based on stacked denoising autoencoder is used to update the DT with online measurement. A case study with experimental PEMFC degradation data is presented where the proposed data-driven DT prognostics method has applied and reached a high prediction accuracy. Furthermore, the predicted results are proved to be less affected even with limited measurement data.