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.     

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 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.     

不同操作和环境条件下的PEMFC低温冷启动数值模拟研究

基于COMSOL建立质子交换膜燃料电池低温冷启动一维瞬态多物理场耦合模型,该模型考虑气态水和膜态水在0 ℃以下结冰来研究恒电压输出、恒电流输出、膜态水初始含量以及环境温度等不同操作和环境条件对质子交换膜燃料电池低温冷启动性能的影响。结果表明,恒电压输出模式下,低电压操作相对于高电压能产生更多的热,温度上升更快,但结冰速率也会激增,从而导致性能衰减更快;恒电流输出模式相较于恒电压能达到更高的温度,但需更好的气体传质能力;如果低温冷启动之前吹扫不足导致膜水含量较高,膜的储水能力下降,这将造成输出性能下降更快,不利于冷启动的成功进行;启动时环境温度的不同会直接影响燃料电池低温冷启动成功与否,仅依赖被动加热成功启动的初始环境温度存在极限值。     

Quantitative analysis on cold start process of a PEMFC stack with intake manifold

To systematically explore the low-temperature operating characteristics of polymer electrolyte membrane fuel cell (PEMFC) stack, a three-dimensional PEMFC stack model with intake manifold is developed in this study. The characteristics of different cold start modes in the stack are compared and analyzed. The distribution and transmission characteristics of water, ice, and heat in each cell of the stack are analyzed in detail. The location of water accumulation in each cell of the stack is also explored. Finally, finite difference sensitivity is calculated for the cumulated charge transfer density to quantify the effects of operating parameters on the cold start process at low temperature. And how these parameters affect the operation of the PEMFC stack at low temperature is investigated. The results show that inconsistency exists in stack operation due to the position particularity of the intermediate cell. Irreversible heat is the main heat source for the cold start of the stack, and the cathode catalyst layer is the main heat-generating component. The heat production proportion of cathode catalyst layer can reach 90%, which decreases with the increment of current density and the running time, especially for the edge cell. The initial ionomer water content is most sensitive to the cold start process of the stack, followed by the porosity of cathode catalyst layer. These parameters are sensitive to the cold start process mainly because of the change in volumetric exchange current density and oxygen concentration.     

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.     

Effect of membrane electrode assembly design on the cold start process of proton exchange membrane fuel cells

A transient multiphase model for cold start process is developed considering micro-porous layer (MPL), super-cooled water freezing mechanism and ice formation in cathode channel. The effect of MPL's hydrophobicity on the output performance and ice/water distribution is investigated under various startup temperatures, structural properties, membrane thicknesses and surrounding heat transfer coefficients. Under the maximum power startup mode, it is found that the hydrophobicity disparity of MPL has negligible influences when started from ?15 °C, but it strongly affects the overall performance when started from ?10 °C, especially after the cell survives the cold start. Decreasing the MPL's hydrophobicity leads to higher current density, meanwhile, it facilitates the super-cooled water's removal, which in turn reduces the ice formation in catalyst layer. However, excessive water accumulation happens if the generated water is hindered from getting into gas diffusion layer (GDL) due to the significant hydrophobicity gap. Weakening the GDL's hydrophobicity contributes to the water removal since the generated water is easier to diffuse out. A thinner membrane benefits the cold start owing to the reduction of ohmic loss and improvement of membrane hydration, and is more sensitive to the hydrophobicity of MPL. Ice formation in cathode channel is identified under various surrounding heat transfer coefficients.     

Research on PEMFC resistance relaxation characteristics and degradation under thermal cycles with different residual water locations

The storage problem at low temperatures is one of the technical barriers to commercialization in the future for the polymer electrolyte membrane fuel cell (PEMFC). In this study, the resistance relaxation characteristic under different pretreatment methods before low-temperature storage of PEMFC is analyzed. The effect of residual water in different PEMFC locations on its storage performance after thermal cycles are investigated. The evolution curves of resistance after the purging process are different under equilibrium, cold, and hot purge and the percentage drop of cell resistance at relaxation stage under three methods are 14.5%, 66.3%, and 73.1%. It is found that the most likely reason for relaxation is membrane water structure reorganization. The voltage of the cell with no purge and purged to the end of the first stage becomes smaller at low current density after 20 freeze/thaw cycles. The charge transfer resistances of the cell with no purge, purged to the end of the first stage, and purged to the end of the second stage increase by 8.2%, 15.6%, and 7.4%, respectively. And the cell purged to the end of the first stage has the largest decay rate of electrochemical surface area. The result implies that the performance degradation after freeze/thaw cycles is associated with the water in the ionomer of catalyst layers, which freezes between ionomers and Pt particles at low temperatures.     

Experimental and theoretical investigations on a proton exchange membrane fuel cell starting up at subzero temperatures

Ice/frost formation in a proton exchange membrane fuel cell (PEMFC) operating under subzero temperatures can lead to its shutdown during start up. Isothermal potentiostatic and galvanostatic tests were performed on 220 cm² single cells under a wide range of operating conditions in order to investigate the “cold start” behaviour. Different parameters have been investigated: the initial water contained in the membrane, the operating voltage, the cell temperature and current. An optimal wetting level of the fuel cell (FC) core for which cumulated heat generated by the electrochemical reaction is maximal, has been observed. Water management analysis from the membrane coupled with cell resistance measurement allowed to formulate a phenomenological interpretation of the overall FC performance evolution. FC starving is not only due to ice formation in the cathode layer pores, thus hindering oxygen transport. It is also due to ice formation in active reaction sites increasing the electrical resistance of the cell. Both factors dramatically reduce FC performance under load. The relative balance of each effect has been assessed. After each shutdown and start up at subfreezing temperature, a polarization curve at rated conditions was carried out to quantify the FC performance degradation. Performances reduce less than 1% per cold start at rated current density.     

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.     

Effects of operating and design parameters on PEFC cold start

During startup from subzero temperatures the water produced in a polymer electrolyte fuel cell (PEFC) forms ice/frost in the cathode catalyst layer (CL), blocking the oxygen transport and causing cell shutdown once all CL pores are plugged with ice. This paper describes an experimental study on the effects of operating and design parameters on PEFC cold-start capability. The amount of total product water in mg cm⁻² during startup is used as an index to quantify the cold-start capability. The newly developed isothermal cold-start protocol is used to explore the basic physics of cold start, and the effects of purge methods prior to cold start, startup temperature and current density, and the membrane thickness are shown. The experimental data also confirm the current density effect predicted earlier by a multiphase model of PEFC cold start.     

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.     

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.     

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.     

Effects of reactants/coolant non-uniform inflow on the cold start performance of PEMFC stack

The failure at equally distributing reactants among different channels within the stack leads to uneven reaction and gas concentration distribution in the catalyst layers, which consequently impacts the performance and durability of proton exchange membrane fuel cell stacks (PEMFCs). A three-dimensional, transient, non-isothermal cold start model for PEMFCs with parallel flow-field configuration and coolant circulation is developed in this work to investigate the effects of non-uniform distribution of reactants/coolant inflow rates on the cold start process. The results show that the effect of non-uniform inflow on ice formation amount is obvious and that on the distribution uniformity of current density is apparent over the cold start survival time. Additionally, the simulation predictions show that the non-uniform initial membrane water content distribution due to the purge procedure can significantly increase the rate of ice growth and deteriorate the uniformity of current density distribution in the membrane. It is found that high stoichiometry operating condition is favorable to cold startup, but may result in drying in the membrane at regions close to the channel inlet side. As non-uniform inflow rates issue is inevitable in actual PEMFC stack operation conditions, our results demonstrate that the initial membrane water content and cathode stoichiometry ratio need to be identified to moderate the effects of reactants/coolant inflow maldistribution and to maintain a stable cold start performance for the PEMFC stack.     

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.     

An overview: Current progress on hydrogen fuel cell vehicles

The harmful consequences of pollutants emitted by conventional fuel cars have prompted vehicle manufacturers to shift towards alternative energy sources. Currently, fuel cells (FCs) are commonly regarded as highly efficient and non-polluting power sources capable of delivering far greater energy densities and energy efficiency than conventional technologies. Proton exchange membrane fuel cells (PEMFC) are viewed as promising in transportation sectors because of their ability to start at cold temperatures and minimal emissions. PEMFC is an electrochemical device that converts hydrogen and oxidants into electricity, water, and heat at various temperatures. The pros and cons of the technology are discussed in this article. Various fuel cell types and their applications in the portable, automobile, and stationary sectors are discussed. Additionally, recent issues associated with existing fuel cell technology in the automobile sector are reviewed.     

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.     

Degradation behaviors of polymer electrolyte membrane fuel cell under freeze/thaw cycles

Degradation behaviors of polymer electrolyte membrane fuel cell (PEMFC) in high current density region were investigated under Freeze/Thaw cycles. Different dehumidification scenarios namely hot purge, cold purge and no purge were adopted for comparison. Micrographs from scanning electron microscopy proved little change in catalyst-coated membrane (CCM) integrity, no delamination or segregation occurred after many freeze/thaw cycles. Cyclic Voltammetry (CV) measurement revealed reduction in electrochemical active surface area of CCM. The observed performance decay in the high current density region was mainly attributed to the increased interface contact resistance and degraded electric and gas coupling characteristics at interfaces between CCM and GDL in this paper. Meanwhile, the performance degradation under low current densities (for example 400 mA cm⁻² or even lower) was mainly ascribed to the degraded characteristics of catalyst layers referring to CCM as cyclic voltammetry indicated. Proper dehumidification through gas purging is effective to maintain stable preference under subzero temperature.     

Effect of catalyst layer mesoscopic pore-morphology on cold start process of PEM fuel cells

Water transport is of paramount importance to the cold start of proton exchange membrane fuel cells (PEMFCs). Analysis of water transport in cathode catalyst layer (CCL) during cold start reveals the distinct characteristics from the normal temperature operation. This work studies the effect of CCL mesoscopic pore-morphology on PEMFC cold start. The CCL mesoscale morphology is characterized by two tortuosity factors of the ionomer network and pore structure, respectively. The simulation results demonstrate that the mesoscale morphology of CCL has a significant influence on the performance of PEMFC cold start. It was found that cold-starting of a cell with a CCL of less tortuous mesoscale morphology can succeed, whereas starting up a cell with a CCL of more tortuous mesoscale morphology may fail. The CCL of less tortuous pore structure reduces the water back diffusion resistance from the CCL to proton exchange membrane (PEM), thus enhancing the water storage in PEM, while reducing the tortuosity in ionomer network of CCL is found to enhance the water transport in and the water removal from CCL. For the sake of better cold start performance, novel preparation methods, which can create catalyst layers of larger size primary pores and less tortuous pore structure and ionomer network, are desirable.