Low temperature operation and influence parameters on the cold start ability of portable PEMFCs

The start up behaviour of PEM fuel cells below 0 °C is one of the most challenging tasks to be solved before commercialisation. The automotive industry started to develop solutions to reduce the start up time of fuel cell systems in the middle of the nineties. The strategies varied from catalytic combustion of hydrogen on the electrode catalyst to fuel starvation or external stack heating via cooling loops to increase the stack temperature.Beside the automotive sector the cold start ability is as well important for portable PEMFC applications for outdoor use. But here the cold start issue is even more complicated, as the fuel cell system should be operated as passive as possible.Below 0 °C freezing of water inside the PEMFC could form ice layers in the electrode and in the gas diffusion layer. Therefore the cell reaction is limited or even inhibited. Product water during the start up builds additional barriers and leads to a strong decay of the output power at isothermal operating conditions.In order to find out which operational and hardware parameters affect this decay, potentiostatic experiments on single cells were performed at isothermal conditions. These experiments comprise investigations of the influence of membrane thickness and different GDL types as well as the effect of gas flow rates and humidification levels of the membrane. As pre stage to physical based models, empirical based prediction models are used to gain a better understanding of the main influence parameters during cold start. The results are analysed using the statistical software Cornerstone 4.0.The experience of single cell investigations are compared to start up behaviour of portable fuel cell stacks which are operated in a climate chamber at different ambient temperatures below 0 °C. Additional flow sharing problems in the fuel cell stack could be seen during cold start up experiments.     

Investigation on sub-zero start-up of polymer electrolyte membrane fuel cell using un-assisted cold start strategy

The technical barriers for commercialization of polymer electrolyte membrane fuel cell (PEMFC) are the startup ability and survivability at sub-zero temperatures. Ice formation causes cold start fail and volume change damages the cell components leading to performance decay. Many strategies are used to assist successful cold start and to reduce the performance decay. But, unassisted cold start is very crucial and needs attention. Here, an experimental protocol is reported for successful unassisted cold start using low temperature gas purging at various temperatures (-5,-8,-10,-15, and -20 °C) as well as to recover temporary performance decay. The stability of the membrane electrode assembly is also studied in freeze/thaw and sequential cold start cycles. At temperature −10 °C, there is small performance decay after the 6th freeze/thaw cycle. However, the subsequent cold start cycle shows significant performance decay after the 6th cycle. Changes in microstructures and loss of hydrophobicity in the gas diffusion layer are attributed to the performance decay in both freeze/thaw and sequential cold start cycles. The effect of cold start temperature on the performance of a PEMFC in subsequent freeze/thaw cycles is also studied. It shows that depending upon the start-up temperature, the preferential ice formation can affect the performance decay characteristics.     

Rapid cold start of proton exchange membrane fuel cells by the printed circuit board technology

Cold start from subzero temperature is one of the key barriers, which prevents proton exchange membrane fuel cell (PEMFC) from further commercialization. In this paper, we have applied the printed circuit board (PCB) technology to study the current density distributions of PEMFC and optimized the technology under rapid cold start. The results show that increasing the initial load, and the setup temperature can help to lower the cold start time and achieve rapid warm-up of PEMFC. The cell can be rapidly cold started for 10 s at −5 °C and 55 s at −10 °C under 0.2 V operation condition, but it failed at −15 °C and −20 °C. The inlet region and middle region produce half of the total current before the overall peak current density is reached, which is important for the successful cold start. Based on these characteristics, we optimized the rapid cold start strategy by co-operation of hot reactant gas and waste heat generation of PEMFC. It becomes possible to start up the PEMFC at temperatures down to −20 °C with about 20 min.     

Water management characteristics of electrospun micro-porous layer in PEMFC under normal temperature and cold start conditions

Micro-porous layer (MPL) is the key component in proton exchange membrane fuel cell for water management. Electrospinning technique, providing a novel nanofiber structure, is recently used to fabricate MPL which gave improved fuel cell performance at normal temperature operation. However, underlying causes are not well understood, and no attempt has been made to study its effects on the cold start performance. In this work, electrospun MPL using non-toxic solvent was fabricated, and water management characteristics under both normal temperature and cold start conditions were compared with commercial MPL using the same catalyst coated membrane (CCM). Electrospun MPL outperformed the commercial MPL at 70 °C under high relative humilities due to marked reduction in mass transport losses. Under cold start conditions, fuel cell with electrospun MPL generated electricity for a longer time, possibly due to better interfacial connection, which facilitated water removal from catalyst layer.     

Statistic analysis of operational influences on the cold start behaviour of PEM fuel cells

For portable fuel cell systems a multitude of applications have been presented over the past few years. Most of these applications were developed for indoor use, and not optimised for outdoor conditions. The key problem concerning this case is the cold start ability of the polymer electrolyte membrane fuel cell (PEMFC). This topic was first investigated by the automotive industry, which has the same requirements for alternative traction systems as for conventional combustion engines.The technical challenge is the fact that produced water freezes to ice after shut-down of the PEMFC and during start-up when the temperature is below 0 °C.To investigate the basic cold start behaviour isothermal, potentiostatic single cell experiments were performed and the results are presented.The cold start behaviour is evaluated using the calculated cumulated charge transfer through the membrane which directly corresponds with the amount of produced water in the PEMFC. The charge transfer curves were mathematically fitted to obtain only three parameters describing the cold start-up with the cumulated charge transfer density and the results are analysed using the statistical software Cornerstone 4.0.The results of the statistic regression analyses are used to establish a statistic-based prediction model of the cold start behaviour which describes the behaviour of the current density during the experiment. The regression shows that the initial start current mainly depends on the membrane humidity and the operation voltage. After the membrane humidity has reached its maximum, the current density drops down to zero. The current decay also depends on the constant gas flows of the reactant gases.Ionic conductivity of the membrane and charge transfer resistance were investigated by a series of ac impedance spectra during potentiostatic operation of the single cell at freezing temperatures. Cyclic voltammetry and polarisation curves between cold start experiments show degradation effects by ice formation in the porous structures which lead to significant performance loss.     

Investigation of mechanical vibration effect on proton exchange membrane fuel cell cold start

A three-axis vibration platform is first constructed and utilized in the investigation of the effects of mechanical vibration on the cold start performance of a proton exchange membrane (PEM) fuel cell. In addition, an intermittent pattern of purging is adopted to improve the purging efficiency. The applied vibrations are found to promote water dispersion, but ultimately do not enhance water removal. Under subzero conditions (−13 °C), the vibration of the fuel cell improves cold start performance via delayed freezing, especially when vibrating at the fuel cell natural frequency (10 Hz). With an increase in vibration amplitude, the freezing rate is found to be slow and eventually plateau. Finally, the vibration in the vertical axis is found to play a positive role in improving cold start performance; the effects of other orientations depend on the startup temperature. The result of cold start under vibration might indirectly prove the existence of super-cooled water.     

Efficient and stable subzero operation of a PEM fuel cell with a composite anode using hydrogen-methanol composition during freeze/thaw cycles

The present research deals with the adaptation of hydrogen-air fuel cells with proton exchange membrane (PEMFC) to autonomous periodic operation at subzero ambient temperatures. The main goal of the research is to limit the influence of subzero temperatures on component integrity and electrochemical performance stability of PEMFC in the cause of the freeze-thaw (F/T) cycling test. The MEAs stability in cycling from subzero (−35 °C) to operating temperature (+35 °C) was ensured without any specific preparatory operations modeling the PEMFC stop and “cold start” procedure. This is provided through the use of hydrogen-methanol compositions (no more than 4 vol % of methanol vapor) as fuel and a composite anode. Advanced membrane-electrode assembly (MEA) based on the composite anode layer (Pt⁴⁰/C + Pt²⁰/10 wt%–SnO₂/C) for efficient and stable subzero operation during F/T cycling. High stability of electrochemical performance of the MEA with the composite anode at subzero ambient temperatures is shown. Advantages of use a two-component fuel PEMFC for autonomous periodic operation at subzero ambient temperatures are highlighted.     

Study on the performance and characteristics of fuel cell coupling cathode channel with cooling channel

Water flooding in the cathode channel of the proton exchange membrane fuel cell (PEMFC), which reduce the current density output and affect fuel cell lifetime. Hence, to suppress water flooding, a novel channel is proposed in this study, that is to perforate hole between the cooling channel and cathode channel. A 3D numerical model is used to investigate the influence of the parameters including the hole's dimension, position, numbers, the operation conditions of the PEMFC and the slope angle (θ) of the incline cooling channel. The numerical results indicate that the optimal single hole parameters are 0.4 mm long, 0.5 mm wide and 20 mm position, which can maximum the current density output of the PEMFC. Increasing the hole numbers for novel channels can improve water removal. In addition, in comparison with the conventional channel with θ = 0.20° at 1.8 cathode stoichiometry, the H5 (novel channel with five holes) with θ = 0.20° decreases by 43.10% in the maximum water saturation of cathode channel, while increases by 12.54% in current density output. What's more, all the novel channel structure research hardly raises the pressure drop of channels.     

Experimental investigation on dynamic characteristics of proton exchange membrane fuel cells at subzero temperatures

Cold start and operation of a proton exchange membrane fuel cell (PEMFC) at the cold temperatures are crucial to the commercialization of it in the field of transportation. A 32 cm² two cell stack is prepared to conduct the experiments at subzero temperatures, including cold start processes and cell performance testing, aiming of the characteristics of the cell. The startup study under subfreezing temperatures is conducted by galvanostatic method at various operation conditions, i.e. ambient temperature (−3 and −5 °C), current density and anode stoichiometry. The results show that the voltage evolutions are proportional to the operating current densities under the former two conditions, but the relationship becomes the opposite at the last condition. It is also found that the time constant for the cell to reach steady status is no more than 100 s and highly depends on the startup mode. In addition, the performance of the cell is tested at the temperature of 0 °C and −3 °C. The comparison of pre-humidification and normal operations indicate that the initial water content of membrane affects the cell performance.     

Cold-start icing characteristics of proton-exchange membrane fuel cells

Understanding the icing characteristics of proton-exchange membrane fuel cells (PEMFCs) is essential for optimizing their cold-start performance. This study examined the effects of start-up temperature, current density, and microporous layer (MPL) hydrophobicity on the cold-start performance and icing characteristics of PEMFCs. Further, the cold-start icing characteristics of PEMFCs were studied by testing the PEMFC output voltage, impedance, and temperature changes at different positions of the cathode gas diffusion layer. Observation of the MPL surface after cold-start failure allowed determination of the distribution of ice formation at the catalytic layer/MPL interface. At fuel cell temperatures below 0 °C, supercooled water in the cell was more likely to undergo concentrated instantaneous freezing at higher temperatures (−4 and −5 °C), whereas the cathode tended to freeze in sequence at lower temperatures (−8 °C). In addition, a more hydrophobic MPL resulted in two successive instantaneous icing phenomena in the fuel cell and improved the cold-start performance.     

Experimental study on rapid cold start-up performance of PEMFC system

The cold start-up of a proton exchange membrane fuel cell is considered one of the main factors affecting the commercialization of fuel cell vehicles. In this study, an automotive fuel cell system was designed and tested for cold start-up at low temperatures. In the absence of PTC (Positive Temperature Coefficient) heating device, the stack was directly loaded to generate heat, which provided the cold start-up characteristics of system at low temperatures. Cold start-up process and purging control strategies were analyzed at −20 °C and −30 °C. It was found that the fuel cell system could produce 50% power in 25 s at −20 °C, the coolant temperature's heating rate was 0.78 °C/s, the coolant outlet temperature could reach 20 °C within 40 s and no apparent low voltage of single cell occurred. While, the cell close to the end plate had low cell voltage and reverse polar phenomena throughout the −30 °C cold start-up process. The heating rate of the coolant temperature was 0.44 °C/s, and the temperature of coolant outlet reached 20 °C within 90 s. The purging time ranged from 180 to 260 s according to the voltage drop value of stack and the ohmic resistance of stack was 360–470 mΩ after the high-volume air purging at different tests. After 30 cold start-up tests, the rated point performance of the stack declined by about 1%, and the consistency of cell voltages did not change significantly. Future work will focus on optimizing cold start-up strategy and speeding up purging time to minimize the performance impact of the cold start-up.     

Internal behavior of segmented fuel cell during cold start

In order to improve cold start capability and survivability of proton exchange membrane fuel cell (PEMFC), a fundamental understanding of its internal behavior is required. In this study, the cold start processes of a PEMFC with different operating conditions have been investigated, and the characteristics of current density and temperature distributions are studied through in-situ experiments with a printed circuit board (PCB). It is found that the start ability of PEMFC is strong at −3 and −5 °C, but weak at −7 and −10 °C. Also the self-start ability can be enhanced by decreasing the initial current load. Polarization curves show almost no degradation after successful cold start at −3 and −5 °C, while the PEMFC degrades a lot after failed cold start at low temperature like −10 °C. Also electrochemical impedance spectroscopy (EIS) shows a big degradation after galvanostatic mode cold starts. Local current density of segmented cell results shows that the highest current density is initially near the inlet region and then quickly moves downstream, reaching to the region near the middle eventually during the successful cold start process. However, during the failed cold start process, the highest current density is initially near the inlet region of the flow channels and quickly moves down stream, reaching the upper left corner region (A1) before shut down eventually. For both successful and failed cold starts, the highest temperature can be observed near the middle of the cell after the reaching of the highest current density.     

Performance of planar free-breathing PEMFC at temperatures below freezing

For practical fuel cell applications it is vital to know how the fuel cell operates in varying ambient conditions, especially when passive control methods are used. In this contribution, the effect of subzero temperatures with constant current density and cold-start behavior of planar free-breathing PEMFC were studied in a temperature chamber. The temperature levels used in constant current measurements varied between 0 and −27.5 °C. The cell maintained stable operation without irreversible performance losses at higher current densities as the heat generation was high enough to prevent the product water from freezing inside the cell. However, ice formation on the outer part of the cathode side of the cell was observed. At low temperature and current density level, the freezing of product water inside the cell led into irreversible performance loss. The cold-start measurements showed that the cell is capable of starting operation at −5 °C without irreversible performance losses when the cell is initially dry. The cell was capable of starting operation also at −10 °C when the starting procedure was slow enough, but a slight irreversible performance loss was encountered.     

Parametric studies of a double-cell stack of PEMFC using Grafoil™ flow-field plates

A parametric study of a double-cell stack of a proton exchange membrane fuel cell (PEMFC) using Grafoil™ flow-field plates is performed. A self-made membrane–electrode assembly (MEA) is used to integrate the PEMFC. Emphasis is placed on the effect of the transport parameters such as cell temperature, pressure and humidity of the reaction side, and flow-field geometry on the performance of the stack. Potential–current and power–current curves are presented. At a fixed dew point of the incoming reactants, say T_dp=30 °C, increasing the cell operating temperature past a threshold value of about 50 °C reduces the cell performance due to membrane dehydration. At a fixed cell operating temperature, a high flow back-pressure increases the cell performance through enhancing the reaction on both electrodes of the fuel cell. Moreover, the cell performance for the pressurised cathode side is better than that for the pressurised anode side due to the favourable back-diffusion of water in the membrane. Finally, empirical correlations are developed to describe the electrode process of the PEMFC stack under various operating conditions.     

Performance improvement of proton exchange membrane fuel cells with compressed nickel foam as flow field structure

In order to improve the performance of proton exchange membrane fuel cell (PEMFC), the compressed nickel foam as flow field structure was applied to the fuel cell. The fuel cell test system was built and the performance of fuel cells with nickel foam flow field with different thicknesses were tested and analyzed by electrochemical active surface area (EASA), electrochemical impedance and polarization curve. And its operating parameters were optimized to improve the performance of PEMFC. Our results show that the membrane electrode assembly (MEA) can show a larger catalytic active area and uniformity of gas diffusion can be improved by using the nickel foam flow field instead of the conventional graphite serpentine flow field, and the impedance characteristic of 110PPI nickel foam can be improved by increasing the compression ratio of the original material. What's more, the polarization characteristic and power output performance of PEMFC with nickel foam flow field were improved by optimizing the operating parameters. Using the optimized operating parameters (cell temperature = 80 °C; humidification temperature = 75 °C; stoichiometric ratio = 2; back pressure = 0.23 Map), a peak power density of 1.89 W cm⁻² was obtained with an output voltage of 0.46 V.     

Investigation on cold start of polymer electrolyte membrane fuel cells with different cathode serpentine flow fields

The flow velocity and pressure distribution of the three cathode flow fields are simulated in this study. Larger pressure drop and more rapid flow rate reduce residual water, resulting in minimal ice formation during the cold start process. The simulation results show that the single variable cross section serpentine flow field has the largest pressure drop and the most rapid flow rate.The evolution of the temperature and the segment current density characteristics of three different cathode flow fields during cold start process is studied by printed circuit board technology. The results show that the 2 to 1 serpentine flow field has the best cold start performance and the best current density uniformity when cold start at constant voltage mode above −5 °C. However, the single variable cross section serpentine flow field has the best performance when cold start temperature is below −5 °C. Based on these results, cold start at −30 °C can be realized in 97s by using hot antifreeze liquid.     

Effect of different control strategies on rapid cold start-up of a 30-cell proton exchange membrane fuel cell stack

Many places experience extreme temperatures below −30 °C, which is a great challenge for the fuel cell vehicle (FCV). The aim of this study is to optimize the strategy to achieve rapid cold start-up of the 30-cell stack at different temperature conditions. The test shows that the stack rapidly starts within 30 s at an ambient temperature of −20 °C. Turning on the coolant at −25 °C show stability of the cell voltage at both ends due to the end-plate heating, however, voltage of intermediate cells fluctuates sharply, and successful start-up is completed after 60 s. The cold start strategy changes to load-voltage cooperative control mode when the ambient temperature reduced to −30 °C, the voltage of multiple cells in the middle of the stack fluctuate more drastic, and start-up takes 113 s. The performance and consistency of the stack did not decay after 20 cold start-up experiments, which indicates that our control strategies effectively avoided irreversible damage to the stack caused by freeze-thaw process.     

Proton exchange membrane fuel cell performance investigation considering internal heterogeneity of current density – A novel method study

The remaining useful lifetime (RUL) of proton exchange membrane fuel cell (PEMFC) has been influenced by the heterogeneous distribution. In this presented paper, a novel method considering the internal heterogeneity is proposed and investigated to manage the proton exchange membrane fuel cell (PEMFC) operation thus prolonging the remaining useful lifetime. This method including the mathematic steps of quantification, normalization, and coordinate transformation, converts the conventional power-current density curve into a novel power-heterogeneity curve. The electro-thermal mapping device is applied to measure the physical-field heterogeneity of a single cell during the polarization curve tests under different temperature conditions. This method is validated by the results in the current region of 750–860 mA cm^?2 of the polarization curves under temperature conditions of 50 °C and 60 °C. The novel method shows the effectiveness to make the fuel cell operate at a lower heterogeneity extent meanwhile a similar performance.     

Polarization characteristics and property distributions of a proton exchange membrane fuel cell under cathode starvation conditions

Property distribution and polarization characteristics of a proton exchange membrane fuel cell (PEMFC) under cathode starvation conditions were investigated numerically and experimentally for a unit cell. The polarization curves of a lab‐scale PEMFC were measured with increasing current density for different cell temperatures (40°C, 50°C, and 60°C) at a relative humidity of 100%. To investigate the local temperature, water content and current density on the membrane, and gas velocity in the channel of the PEMFC, numerical studies using the es‐pemfc module of the commercial flow solver STAR‐CD, which were matched with experimental data, were conducted. Temperature, current density on the membrane, and water content in the MEA were examined to investigate the effect of cell temperature on performance under the cathode starvation condition. At cathode starvation conditions, the performance of a higher cell temperature condition might drop significantly and the mean temperature on the membrane increase abruptly with increasing cell temperature or current density. Copyright © 2009 John Wiley & Sons, Ltd.     

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.