Proton Exchange Membrane Fuel Cell Cold Start Research Articles

Ice Formation during PEM Fuel Cell Cold Start: Acceptable or Not?

Proton exchange membrane (PEM) fuel cell faces the inevitable challenge of the cold start at a sub-freezing temperature. Understanding the underlying degradation mechanisms in the cold start and developing a better starting strategy to achieve a quick startup with no degradation are essential for the wide application of PEM fuel cells. In this study, the comprehensive in situ non-accelerated segmented techniques are developed to analyze the icing processes and obtain the degradation mechanisms under the conditions of freeze-thaw cycle, voltage reversal, and ice formation in different components of PEM fuel cells for different freezing time. A detailed degradation mechanism map in the cold start of PEM fuel cells is proposed to demonstrate how much degradation occurs under different conditions, whether the ice formation is acceptable under the actual operating conditions, and how to suppress the ice formation. Moreover, an ideal starting strategy is developed to achieve the cold start of PEM fuel cells without degradation. This map is highly valuable and useful for researchers to understand the underlying degradation mechanisms and develop the cold start strategy, thereby promoting the commercialization of PEM fuel cells.

Order reduction, simplification and parameters identification for cold start model of PEM fuel cell

The cold-start of proton exchange membrane fuel cell (PEMFC) has been one of the leading technical challenges for fuel cell vehicle commercialization. It is essential to understand the mechanism and process of a cold start to improve the cold start ability of the PEM fuel cell. In this study, a one-dimensional cold start transient model of PEMFC was developed for transfer species, heat, charge and water phase change during the cold start process. Based on the 1-D spatially distributed model, a reduced nonlinear cold-start model of the PEMFC is presented. Then the parameter identification is conducted to validate the model accuracy based on the experiment data. The identification result shows that the reduced model captures the detailed model's multiplicity behaviours, and good agreement is observed during cold start simulation with experiment results. In contrast, the computation time is reduced significantly. Thus, the proposed order reduction model can be used to investigate real-time estimation and develop model-based control strategies for automotive PEMFC cold start.

Strategy optimization of proton exchange membrane fuel cell cold start

<p indent="0mm">Under the background of “carbon peaking and carbon neutrality” goals, the proton exchange membrane fuel cell (PEMFC) vehicle attracts extensive attention due to its high energy conversion efficiency, long range and zero emission. However, the challenge of cold start in low temperature environments becomes a large obstacle to its commercialization and application. The current cold start performance of typical commercial fuel cell vehicles cannot reach the optimal target yet. Several problems such as the lack of complete mechanical systems of water transport and phase change and the absence of simulation models for on-board fuel cells at system level still exist. Thus, researchers have carried out a great number of experiments and simulations to study the mechanism of degradation, water transport, phase change and heat transfer as well as start-up strategy optimization of PEMFC cold start. By measuring the output performance, it is found that the degradation of performance is attributed to the formation of ice which covers the reaction active region, blocks the gas channel and increases the electrical contact resistance. Researchers also believe that the reduction of durability is owing to the volume change of water-ice phase change which leads to the damage of the structure by characterizing the microstructure of the fuel cell. With the help of transparent cells, neutron imaging and simulations of multiphase PEMFC models, the distribution, transport and phase change of water and ice during cold start have been studied. The results indicate that the electrochemical product water first saturates the PEM and the catalyst layer (CL) as membrane water. Then the water remains liquid in the form of supercooled water at low temperatures, and finally flows out of the cell or freezes suddenly. By studying the heat transfer process both in plane and through plane during cold start, researchers find that at central regions of the single cell and in the middle part of the stack, the temperature rises fastest. They also find that the irreversible reaction heat generated by cathodic oxygen reduction reaction (ORR) is the main source of heat generation. Based on the cold start mechanism of PEMFCs, researchers have developed various self-start and auxiliary start strategies. The start-up mode and control strategies have been optimized. The internal structure and materials of each part have been improved. And a series of auxiliary startup strategies such as gas purging, heater heating, reaction heating, gas heating as well as coolant heating have been proposed. A large number of simulations and experiments are carried out to verify the advantages of these strategies. Through these excellent cold start strategies, the commercialization and promotion process of PEMFC vehicles can be accelerated.

Study on the Degradation Mechanism of the Proton Exchange Membrane Fuel Cell Based on a Constant Voltage Cold Start Mode

Abstract The constant voltage cold start of the proton exchange membrane fuel cell (PEMFC) is usually operated at a low start-voltage in order to ensure high heat generation, which can shorten the process of the PEMFC cold start. However, the effect of constant voltage cold start on the durability of PEMFC is still unclear. Thus, in this work, the PEMFC is tested repeatedly at a low start-voltage to simulate its actual operating state in the vehicle. Then, the effect of the PEMFC durability under constant voltage cold start is investigated by polarization curve, cyclic voltammetry, electrochemical impedance spectroscopy, transmission electron microscope, and ion chromatography. After the repeatedly cold start, the output performance of the PEMFC decreases significantly. According to the characterization results, the degradation mechanism of the PEMFC at the constant voltage cold start is demonstrated to be that the PEMFC start-up repeatedly at low start-voltage leads to the decomposition of membrane polymer structure and promotes the crossover of H2. Meanwhile, the PEMFC start-up repeatedly at low start-voltage also leads to the agglomeration of catalysts, which reduces the active area of catalysts and ultimately results in the degradation of fuel cell performance. Above all, this study proves that the durability of PEMFC can be shortened by the constant voltage cold start at 0.1 V, which provides a reference for the development of the PEMFC cold start control strategy.

Numerical study of subfreezing temperature cold start of proton exchange membrane fuel cells with zigzag-channeled flow field

An automotive proton exchange membrane fuel cell (PEMFC) engine needs to be capable of surviving from sub-freezing temperatures. Cold starting up a PEMFC engine presents great technical challenge due mainly to the intra-electrode ice formation that is closely related to the involved multi-physical transport. The flow field configuration to some extent dictates the reactants and product transport and is thus of important influence on PEMFC cold start performance. The present work carefully analyzes the cold start process of PEMFCs with zigzag-channeled flow field (ZZFF). A transient three-dimensional numerical model is established and experimentally validated first, and then we make comparisons of cold-start performance between zigzag and straight channel flow-field PEMFCs to reveal the effects of ZZFF. It is found that the ZZFF better distributes the reactants/product and current density in the PEMFC as it enhances the transport along the flow direction in-between the under-land and under-channel regions inside the cell. The process of cold starting the ZZFF PEMFC is found to generate slightly less heat, which is not good to cold start. Therefore, the ZZFF enhances the survivability of PEMFC engine cold starting from subfreezing temperatures, whereas it slightly degrades the quick self-startup ability of PEMFC engine. Case study with PEMFCs of more zigzagged flow fields further corroborates the effects of ZZFF configuration on PEMFC cold start performance.

An Online Self Cold Startup Methodology for PEM Fuel Cells in Vehicular Applications

This paper puts forward an adaptive cold start strategy for a proton exchange membrane fuel cell (PEMFC) based on maximum power mode. The proposed strategy consists of a water evacuation process after PEMFC shutdown and a self-heating process at PEMFC cold startup. To maximize the performance of the suggested strategy, an optimal operating condition for the cold start procedure is sought first. In this respect, an experimental parametric study is performed to explore the impact of fan velocity, micro-short circuit, anode pressure, and purge procedure on the PEMFC cold start performance. After laying down the proper conditions, the proposed cold start procedure is implemented on a test bench for experimental validations. The self-heating process is based on an online adaptive algorithm that maximizes the PEMFC's internal heat depending on its operating parameters’ variation. In fact, this algorithm attempts to keep the current density at high levels, leading to PEMFC's performance improvement achieved by membrane hydration and temperature increase. The experimental results confirm the effectiveness of the proposed strategy, which presents a fast and cost-effective PEMFC's cold start.

Numerical study of cold start performance of proton exchange membrane fuel cell with coolant circulation

It has been well recognized that cold start is one of the key issues of proton exchange membrane fuel cell (PEMFC) used as the engine of vehicles. Coolant circulation is usually launched synchronously with the fuel cell during cold start to avoid sudden large temperature variation, which greatly increases the cell thermal mass, lowers the heating rate, and worsens the cell performance. Considering the flow and heat transfer of coolant circulation, a three-dimensional, transient, multi-disciplinary model for cold start is built up. The numerical results agree reasonably well with experimental data, indicating that the model can be used for the investigation of PEMFC cold start processes. The analysis of circulation parameter effects shows that increasing the coolant flow rate or coolant tank capacity has little influence on the cell voltage, but will increase the non-uniformity of temperature distribution along flow direction. At lower start-up temperature, this non-uniformity is more obvious. With higher coolant flow rate, although the distribution of current density becomes more evenly, the ice formation amount increases and its distribution and location are greatly affected.

Experimental Investigation of Proton Exchange Membrane Fuel Cell with Metal Foam Flow Field

&lt;div class="section abstract"&gt;&lt;div class="htmlview paragraph"&gt;Compared with conventional flow field, metal foam has been increasingly used for gas distributor in the PEM (proton exchange membrane) fuel cell due to its high porosity and conductivity, which significantly enhances the species transport under high current density condition. In this study, the cell performances with metal foam and graphite parallel flow field are compared under normal and subzero temperature conditions. Besides, electrochemical impedance spectroscopy (EIS) is recorded to characterize the Ohmic, polarization and polarization resistance. Under normal condition, the cell with metal foam exhibits three times better performance than the one with parallel flow field. Meanwhile, the effects of inlet gas humidity and flow rates on cell performance are also studied, indicating that the cathode flooding easily occurs due to its difficult water removal. However, the high flow rate can greatly ease the cathode water flooding. Under subzero temperature condition, metal foam cell shows higher startup voltage and better ice storage capability. In addition, the effects of start-up temperature and current density on cold start performance of PEM fuel cell are studied and the high frequency resistance (HFR) is also utilized to characterize the water content and ice formation/melting in cell. The experimental results show that low initial water content, high startup temperature, and low startup current density are beneficial to PEM fuel cell cold start performance. Overall, the results shown in this study will facilitate a further understanding of the PEM fuel cell with metal foam flow field.&lt;/div&gt;&lt;/div&gt;

Experimental investigation of the effect of membrane water content on PEM fuel cell cold start

In this study, the effect of membrane water content on proton exchange membrane (PEM) fuel cell cold start is investigated experimentally in detail. The cyclic voltammetry (CV) and high frequency resistance (HFR) are introduced to character electrochemical active surface area (ECSA) of the electrode and water content in the cell. Under normal condition, it is found that ECSA decreases with the decrement of membrane water content and a critical point of water content exists for the ECSA sharp decrement. Under cold start operation, low initial water content aggravates the voltage drop when the load is applied. The high initial water content leads to a rapid membrane water saturation, causing a short shutdown time, while the low initial water content may lead to a bad cold start performance. For the excessive low initial water content, the voltage reversal due to water electrolysis and carbon corrosion is also considered. Besides, the HFR is also recorded during cold start operation to estimate ice formation in the cell. It is indicated that a proper initial membrane water content after purge is significantly vital for PEM fuel cell cold start to achieve the balance of ECSA and ice storage capacity.

Investigation of the effect of micro-porous layer on PEM fuel cell cold start operation

Abstract The effect of micro-porous layer (MPL) on proton exchange membrane (PEM) fuel cell cold start is investigated experimentally with theoretical analysis. Under normal condition, the anode and cathode MPLs can improve the independency on inlet gas humidification on the corresponding side. For potentiostatic startup, the humidity independence enhanced by anode MPL improves the cell performance at around −7 °C. Cathode MPL can promote the water back diffusion and hinder the ice formation on the catalyst layer (CL) surface at low temperature (e.g. −10 °C). Besides, anode MPL also contributes to reducing the blockage tendency at very low temperature (e.g. −15 °C or lower). For galvanostatic startup, water electrolysis and carbon corrosion may occur which leads to the voltage reversal when the cell cannot achieve the desired current density, which may produce more waste heat. Low water content will aggravate the voltage reversal and carbon corrosion.

Experimental investigation on PEM fuel cell cold start behavior containing porous metal foam as cathode flow distributor

Metal foam has been regarded as one of the most important replacement for the conventional flow distributor of commercial fuel cells in recent years. One critical issue for the commercialization of proton exchange membrane (PEM) fuel cell is the successful startup from subzero temperatures. In this study, experimental tests on a PEM fuel cell using nickel metal foam as the cathode flow distributor are carried out to investigate the cold start performance. The cold start performance is also compared to a PEM fuel cell with parallel flow channels. Both galvanostatic and potentiostatic control are considered. The results show that under normal operating conditions the metal foam PEM fuel cell exhibits higher maximum net power density than the cell with parallel flow channels, whereas the parallel channel case exhibits slightly better performance at lower current densities. For cold start tests, metal foam is superior to the conventional parallel flow channel under galvanostatic control, due to its extremely porous structure, uniform mass and heat distribution. It is more difficult for PEM fuel cell under potentiostatic control to successfully start up due to possible ice blockage at the outlet.

Experimental and theoretical analysis of ionomer/carbon ratio effect on PEM fuel cell cold start operation

The effect of ionomer/carbon (I/C) ratio on proton exchange membrane (PEM) fuel cell cold start is investigated experimentally with theoretical water transport analysis. The scanning electron microscope (SEM) images show larger agglomerates and smaller effective reaction area by increasing the I/C ratio from 0.7 to 1.7. For normal operation, increasing the I/C ratio can improve the humidity tolerance, especially in the cathode. For cold start >−10 °C, a lower I/C ratio leads to better performance because the core reaction area is shifted towards the membrane, leading to more membrane water absorption and slower ice formation. For <−15 °C, the total water production is low and almost the same for the different I/C ratios because the ice formation takes place before effective membrane water absorption; and although the cathode catalyst layer (CL) and micro-porous layer (MPL) can provide sufficient space to store all the ice, higher I/C ratios (e.g. 1.2) still cause more ice formation in GDL and flow channel because the core reaction area becomes closer to GDL. The results show that the CL design has significant effect on the cold start performance, and there is a potential for further improvement.

A Comprehensive Review of Solutions and Strategies for Cold Start of Automotive Proton Exchange Membrane Fuel Cells

Proton exchange membrane fuel cell (PEMFC) can be a significant eco-friendly alternative power source for vehicles. However, under subfreezing conditions, cell degradation and irreversible performance decay can occur because of ice formation and repetitive thaw/freeze cycles. These problems have limited the further commercialization of PEMFC in cold weather countries. Thus, many improvements have been made to repair the freeze protection and rapid cold startup problems in PEMFC vehicles. In this paper, a comprehensive review dedicated to engineers of the recent research progress on the PEMFC cold start problems is presented. Systems and methods for fuel cell shutdown are summarized and classified into two categories: purge solution and material to avoid freezing. Regarding the system and solutions for PEMFC cold startup, different heating solutions are classified into two main groups depending on their heating sources and categorized as internal and external heating methods. This paper concludes with a detailed review of cold startup strategies based on an exhaustive survey of journal papers and patents.

Maximum power cold start mode of proton exchange membrane fuel cell

Successful and fast cold start is important for proton exchange membrane (PEM) fuel cell in vehicular applications in addition to the desired maximum power in any case. In this study, the maximum power cold start mode is investigated in details and compared with other cold start modes based on a multiphase stack model. It is found that for the maximum power cold start mode, the current density is generally kept at high levels, and the performance improvement caused by the membrane hydration and temperature increment may not be observable. Therefore, before the melting point, the performance drops continuously. The maximum power cold start mode could better balance the heat generation and ice formation, leading to improved cold start survivability than that in the constant voltage and constant current modes, with a fast start-up generally guaranteed. Once the survivability can be ensured, the initial water content needs to be higher for fast cold start, suggesting that over purging should be avoided. The maximum power mode is suggested to be optimal for PEM fuel cell cold start based on the modeling results.

Non-isothermal melting of ice in the gas-diffusion layer of a proton-exchange-membrane fuel cell

Non-isothermal ice melting in the fibrous gas-diffusion layer (GDL) of a proton-exchange-membrane fuel cell (PEMFC) is investigated using differential scanning calorimetry (DSC). Non-isothermal ice-melting rates and ice-melting times are obtained from heat-flow measurements in water-saturated Toray GDLs at heating rates of 1, 2.5, 5, 10, and 25K/min. In all cases, ice-melting times decrease nonlinearly with increasing heating rate. Nevertheless, melting temperatures remain at 272.9±0.5 and 272.7±0.4K for bulk ice and ice within the GDL, respectively, reiterating that melting is thermodynamic-based at a rate limited by heat transfer. The slight GDL ice melting-point depression is consistent with the Gibbs–Thomson equation for equilibrium melting using an average pore diameter of 30μm. Ice-melting endotherms are predicted from overall DSC energy balances coupled with a moving-boundary Stefan problem, where an ice-melting front within a GDL propagates with volume-averaged properties through an effective medium. Agreement between DSC experiment and theory is excellent. The proposed model accurately predicts ice-melting endotherms for Toray GDLs with two ice saturations and for bulk ice. Further, a pseudo-steady-state analysis obtains an analytical expression for ice-melting time, which is controlled by the time for heat addition to the propagating solid/liquid interface. Significantly, the new expression elucidates parameters controlling ice melting and allows for better design of both GDL materials and heating strategies to enhance the success of PEMFC cold-start.

A Review of Experiments on Cold Start of PEM Fuel Cells

This paper evaluate previous experimental studies on sub-freezing start up of proton exchange membrane (PEM) fuel cell system, and identify issues for further investigation. In a successful cold start, product water from electrochemical reaction in the cathode must be removed from the cell before it turns into ice and causing voltage drop and shutdown also leads to permanent damage to fuel cell components. Successful single PEM fuel cell start up was achieved from temperature as low as-30°C. Some researchers found that cold start of a 30 W stack from-20°C was possible only with aid of external energy. Successful self-start up a 2 kW stack from temperature-5°C was reported but the time taken was unacceptably long and attempts to start up the stack at lower temperatures were failed. Based on the current state of research, further research is necessary to fully understand the operation and mechanism of PEM fuel cell cold start.

Effect of Cathode Pore Volume on PEM Fuel Cell Cold Start

Start-up of a proton exchange membrane (PEM) fuel cell from subzero temperatures, commonly referred to as cold start, remains a major challenge for automotive applications. In this work, we theoretically and experimentally study the effect of catalyst layer (CL) pore volume (or, more directly, CL thickness) on the cold-start performance of a PEM fuel cell for both isothermal and nonisothermal operations. Special attention is directed to determining the limits of a cold-start performance with an ultrathin CL . The cold-start product water or the operational time approaches a minimum nonzero asymptote as the CL is gradually made infinitesimally thin. For a PEM fuel cell with standard cell thermal mass, e.g., , and with moderately low initial membrane water content , successful start-up from at can be achieved for CL thicknesses of and above, whereas a CL thickness of is required for successful self-start-up from . However, successful start-up can be achieved even with a thick CL, given certain adjustments to cell design and material properties. In particular, we study the effects of cell thermal mass and membrane water diffusivity and present a design map for self-start-up of a CL PEM fuel cell from various subfreezing temperatures.

Conductivity of aromatic-based proton exchange membranes at subzero temperatures

Stable proton exchange membrane (PEM) with good proton conductivity at subzero temperatures is important for the development of PEM fuel cell cold start. In this work, subfreezing conductivity was reported for several aromatic-based PEMs including sulfonated polyimides (SPIs) with three values of ion-exchange capacity (IEC), sulfonated poly(ether ether ketone) (SPEEK) and disulfonated poly(arylene ether sulfone) copolymer (SPSU) as well as Nafion ® 212. Measurements were performed using the electrochemical impedance spectroscopy (EIS) technique. The results showed that only fully hydrated SPEEK (IEC, 1.75) and SPSU (IEC, 2.08) had comparable conductivities with Nafion ® 212 at subzero temperatures. Considering implement of gas purge before subzero storage of PEM fuel cell, the conductivity for those PEMs humidified by water vapor at activity of 0.75 was also investigated. The state of water in aromatic-based PEMs was quantified by differential scanning calorimetry (DSC), and its correlation with conductivity of the membrane was also discussed.