Influence of operating temperature on cell performance and endurance of high temperature proton exchange membrane fuel cells

The relation between high temperature proton exchange membrane fuel cell (HT-PEMFC) operation temperature and cell durability was investigated in terms of the deterioration mechanism. Long-term durability tests were conducted at operational temperatures of 150, 170, and 190 °C for a HT-PEMFC with phosphoric acid-doped polybenzimidazole electrolyte membranes. Higher cell temperatures were found to result in a higher cell voltage, but decrease cell life. The reduction in cell voltage of approximately 20 mV during the long-term tests was considered to be caused both by aggregation of the electrode catalyst particles in the early stage of power generation, in addition to the effects of crossover due to the depletion of phosphoric acid in the terminal stage, which occurs regardless of cell temperature. It is expected that enhanced long-term durability for practical applications can be achieved through effective management of phosphoric acid transfer.     

Evaluation of HT-PEM MEAs: Load cycling versus start/stop cycling

With the help of consistent conditions for improved batch production and defined quality standards, the lifetime of fuel cell systems should be improved and cost-intensive losses should be minimized at an early state in the production process. Within this work, we concentrated on two accelerated stress tests: load cycling at high current densities and start/stop cycling to compare high temperature (HT) polymer electrolyte membrane (PEM) membrane electrode assemblies (MEAs) of three suppliers to evaluate performances and degradation rates under such conditions. These MEAs have been investigated in-situ via electrochemical characterization. MEAs of three providers differ significantly in their performance and power output for both operation strategies. It was also shown that load cyclization causes greater stress on the MEA than start/stop cycling. Next to the manufacturer comparison, a batch-to-batch evaluation of one provider has been performed including micro-computed tomography (μ-CT) investigations and the determination of the tortuosity of the cathode side gas diffusion layers.     

Study on the degradation of proton exchange membrane fuel cell under load cycling conditions

In order to study the changing regularity of proton exchange membrane fuel cell (PEMFC) performance in the aging process under load cycling condition and improve the durability of fuel cell, the orthogonal experiment method was introduced. In this paper, three-factor and three-level orthogonal experiments were set up to study the influence of upper potential limit (UPL), lower potential limit (LPL) and period of the load cycle on the degradation rate of fuel cell. The test results show that under variable load cycling conditions, the fuel cell performance decays first fast and then slowly. The degradation rate after hundreds of hours of load cycling experiment is usually less than 50% of that of the fresh fuel cell. The dominant factor which effect the degradation mostly significantly changes during the whole aging process. According to the influence degree of three factors on performance degradation rate, the degradation process can be divided into three stages: the UPL dominating stage, the LPL dominating stage and the slow decay stage. In order to mitigate the performance degradation, the UPL in the optimal combination should be as low as possible at all the three stages. The optimized parameters can reduce the degradation rate by more than 50%. The load cycling condition should be avoided at the initial stage after the fuel cell is put into use. And the lifespan of aged fuel cell because of loading cycling can be prolonged through work more under the conditions which will not lead to serious activation potential loss and ECSA loss.     

Development of a one-dimensional and semi-empirical model for a high temperature proton exchange membrane fuel cell

High temperature proton exchange membrane fuel cells (HT-PEMFC), which operate between 160 °C and 200 °C, can be generally used in portable and stationary power generation applications. In this study, a one-dimensional, semi-empirical, and steady-state model of a HT-PEMFC fed with a gas mixture consisting of hydrogen and carbon monoxide is developed. Some modeling parameters are adjusted using empirical data, which are obtained conducting experiments on a HT-PEMFC for different values of Pt loading and cell temperature. For adjusting these parameters, the total summation of the square of the difference between the cell voltages found using the experimental and theoretical methods is minimized using genetic algorithm. After finding the values of the adjusted parameters, the effects of different cell temperature, Pt loading, phosphoric acid (PA) percentage, and different binders (PBI and PVDF) on the performance of the fuel cell are examined. It was found that, the performance of the fuel cell using PVDF binder exhibited better performance as compared to that using PBI binder.     

Electrochemical carbon corrosion in high temperature proton exchange membrane fuel cells

Electrochemical carbon corrosion occurring in a high temperature proton exchange membrane fuel cell (HT-PEMFC) operating under non-humidification conditions was investigated by measuring CO₂ generation using on-line mass spectrometry and comparing the results with a low-temperature proton exchange membrane fuel cell (LT-PEMFC) operated under fully humidified conditions. The experimental results showed that more CO₂ was measured for the HT-PEMFC, indicating that more electrochemical carbon corrosion occurs in HT-PEMFCs. This observation is attributed to the enhanced kinetics of electrochemical carbon corrosion due to the elevated operating temperature in HT-PEMFCs. Additionally, electrochemical carbon corrosion in HT-PEMFCs showed a strong dependence on water content. Therefore, it is critical to remove the water content in the supply gases to reduce electrochemical carbon corrosion.     

Modeling of high temperature proton exchange membrane fuel cells with novel sulfonated polybenzimidazole membranes

In this study, a three-dimensional, steady-state, non-isothermal numerical model of high temperature proton exchange membrane fuel cells (HT-PEMFCs) operating with novel sulfonated polybenzimidazole (SPBI) membranes is developed. The proton conductivity of the phosphoric acid doped SPBI membranes with different degrees of sulfonation is correlated based on experimental data. The predicted conductivity of SPBI membranes and cell performance agree reasonably with published experimental data. It is shown that a better cell performance is obtained for the SPBI membrane with a higher level of phosphoric acid doping. Higher operating temperature or pressure is also beneficial for the cell performance. Electrochemical reaction rates under the ribs of the bipolar plates are larger than the values under the flow channels, indicating the importance and dominance of the charge transport over the mass transport.     

Polybenzimidazole containing ether units as electrolyte for high temperature proton exchange membrane fuel cells

A rapid method to synthesize poly[2,2′-(p-oxydiphenylene)-5,5′-benzimidazole] (OPBI) through a solution polycondensation under microwave irradiation is explored. Synthesis parameters affecting the molecular weight (M_w) of OPBI, including the mass ratio of solvent to P₂O₅, the monomer concentration, and reaction time, are optimized. The main characteristics of OPBI are studied, and the corresponding membrane is prepared through a solvent casting process. A series of sulfuric acid doped OPBI (H₂SO₄/OPBI) hybrid membranes with different acid doping levels (ADLs) are developed. The effects of H₂SO₄ on microstructure, ADL and electrochemical properties of these membranes are explored. Herein, the hybrid membrane shows high proton conductivity (190 mS cm⁻¹) at elevated temperature (160 °C) and anhydrous conditions, high ADL (18.73 mol of H₂SO₄ for OPBI per repeat unit, i.e., ADL = 18.73 mol PRU⁻¹) and excellent dimensional stability (40.3%). All these properties demonstrated that H₂SO₄/OPBI hybrid membrane can be used as an alternative membrane for high temperature proton exchange membrane fuel cells (HT-PEMFCs).     

In-situ diagnosis on performance degradation of high temperature polymer electrolyte membrane fuel cell by examining its electrochemical properties under operation

Ex-situ electrochemical characterization techniques could significantly alter or misrepresent the materials of high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) to the point where they are not reflective of their conditions during operation, resulting in difficulties in obtaining realistic fuel cell durability. To minimize this disturbance, we proposed an in-situ low-invasive technique of electrochemical impedance spectroscopy (EIS), combining with polarization curve and Tafel slope analysis, to investigate the performance degradation of HT-PEMFC. The membrane electrode assemblies (MEAs) used in the HT-PEMFC were lab-made but with commercial catalyst and poly(2,5-benzimidazole) (ABPBI) membrane. Two common test modes, i.e. steady-state operation and dynamic-state operation, were employed to mimic practical HT-PEMFC operation. By examining the changes of electrochemical properties of the HT-PEMFC under steady- or dynamic-state operation, the main mechanism for the performance degradation can be determined. The results from the study suggests that a high cell performance decay rate cannot be directly attributed to materials degradation, especially in a short-term steady-state operation. In contrast, the change of Tafel slope can be seen as a clear indicator to determine the extent of catalyst degradation of HT-PEMFC, no matter which test protocol was applied. Post-analysis of TEM on the catalysts before and after tests further confirmed the main mechanism for the performance losses of the HT-PEMFCs underwent two test protocols, while acid loss and membrane degradation were considered to be negligible during the short-term tests.     

Graphite oxide/functionalized graphene oxide and polybenzimidazole composite membranes for high temperature proton exchange membrane fuel cells

Graphite oxide/polybenzimidazole synthesized by 3, 3′-diaminobenzidine and 5-tert-butyl isophthalic acid (GO/BuIPBI) and isocyanate modified graphite oxide/BuIPBI (iGO/BuIPBI) composite membranes were prepared for high temperature polymer proton exchange membrane fuel cells (PEMFCs). All membranes were loaded with different content of phosphoric acid to provide proton conductivity. The GO/BuIPBI and iGO/BuIPBI membranes were characterized by SEM which showed that the filler GO or iGO were well dispersed in the polymer matrix and had a strong interaction with BuIPBI, which can improve the chemical stability of BuIPBI membrane and support a higher acid content. The proton conductivities of the GO/BuIPBI and iGO/BuIPBI with high acid loading were 0.016 and 0.027 S/cm, respectively, at 140 °C and without humidity.     

Analysis and optimization of high temperature proton exchange membrane (HT-PEM) fuel cell based on surrogate model

The stoichiometric ratio and flow channel geometry play a vital role in the performance of high temperature proton exchange membrane (HT-PEM) fuel cells. Because of the high cost of experiments or simulations, most analyses and optimization of the stoichiometric ratio and flow channel geometry are limited to several points in the entire design domain. In this study, an analysis and optimization method for HT-PEM fuel cells based on the surrogate model was proposed. Surrogate models were constructed using some of the available budgets of samples to analyze and optimize the entire design domain. With this method, it was indicated that the effect of the cathode stoichiometric ratio is more significant to the cell performance than the anode stoichiometric ratio and there are significant nonlinear interactions among the flow channel geometry parameters. At the fixed operating voltage, the flow channel geometry with the maximum current density and that with the maximum real power were obtained. Compared with the base design, the designs obtained by the surrogate model improve the current density and real power by 10.54% and 3.93%, respectively. Thus, this analysis and optimization method is demonstrated to be helpful and deserves attention in future research.     

Optimization of gas diffusion electrode for polybenzimidazole-based high temperature proton exchange membrane fuel cell: Evaluation of polymer binders in catalyst layer

Gas diffusion electrodes (GDEs) prepared with various polymer binders in their catalyst layers (CLs) were investigated to optimize the performance of phosphoric acid doped polybenzimidazole (PBI)-based high temperature proton exchange membrane fuel cells (HT-PEMFCs). The properties of these binders in the CLs were evaluated by structure characterization, electrochemical analysis, single cell polarization and durability test. The results showed that polytetrafluoroethylene (PTFE) and polyvinylidene difluoride (PVDF) are more attractive as CL binders than conventional PBI or Nafion binder. At ambient pressure and 160 °C, the maximum power density can reach ∼ 0.61 W cm⁻² (PTFE GDE), and the current density at 0.6 V is up to ca. 0.52 A cm⁻² (PVDF GDE), with H₂/air and a platinum loading of 0.5 mg cm⁻² on these electrodes. Also, both GDEs showed good stability for fuel cell operation in a short term durability test.     

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.     

Polybenzimidazole and benzyl-methyl-phosphoric acid grafted polybenzimidazole blend crosslinked membrane for proton exchange membrane fuel cells

We synthesize polybenzimidazole (PBI; M_w = 1.65 × 10⁵ g mol⁻¹) and benzyl-methyl-phosphoric acid grafted PBI (PBI-BP; 24 mol% degree of grafting). We demonstrate that blending 20 to −40 wt.% PBI-BP in the PBI membrane enhances the H₃PO₄ doping level, proton conductivity, and mechanical strength. However, the membrane is highly dissolved in an 85 wt.% H₃PO₄ aqueous solution as the PBI-BP content in the blend membrane is larger than 50 wt.%. To prevent PBI-BP from being dissolved out of the blend membrane by the H₃PO₄ aqueous solution, we fabricated a PBI/PBI-BP/epoxy (8/2/1.23 by wt.) crosslinked membrane. The crosslinked membrane demonstrated good fuel cell performance and excellent stability after a 23 on/off (12 h on at 160 °C with a current density of 200 mA cm⁻² and 12 h off at room temperature) fuel cell cycle test with an unhumidified H₂/O₂.     

质子交换膜燃料电池故障检测研究

针对质子交换膜燃料电池(PEMFC)发电系统的故障检测和系统稳定性问题,结合其多传感器特性,采用基于实时PCA的质子交换膜燃料电池故障检测方法,根据燃料电池反应信号数据建立PCA模型,通过窗口过滤方式和遗忘因子算法实时更新模型,并将降维后获得的数据用统计方法进行处理,从而检测出故障。有效地简化了燃料电池系统故障检测的过程,改善了故障检测的实时性,提高了燃料电池系统工作的稳定性和可靠性。     

Functionalized titania nanotube composite membranes for high temperature proton exchange membrane fuel cells

In this study, functionalized titania nanotubes (F-TiO₂-NT) were synthesized by using 3-mercaptopropyl-tri-methoxysilane (MPTMS) as a sulfonic acid functionalization agent. These F-TiO₂-NT were investigated for potential application in high temperature hydrogen polymer electrolyte membrane fuel cells (PEMFCs), specifically as an additive to the proton exchange membrane. Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) results confirmed that the sulfonic acid groups were successfully grafted onto the titania nanotubes (TiO₂-NT). F-TiO₂-NT showed a much higher conductivity than non-functionalized titania nanotubes. At 80 °C, the conductivity of F-TiO₂-NT was 0.08 S/cm, superior to that of 0.0011 S/cm for the non-functionalized TiO₂-NT. The F-TiO₂-NT/Nafion composite membrane shows good proton conductivity at high temperature and low humidity, where at 120 °C and 30% relative humidity, the proton conductivity of the composite membrane is 0.067 S/cm, a great improvement over 0.012 S/cm for a recast Nafion membrane. Based on the results of this study, F-TiO₂-NT has great potential for membrane applications in high temperature PEMFCs.     

Numerical modeling and investigation of gas crossover effects in high temperature proton exchange membrane (PEM) fuel cells

A gas crossover model is developed for a high temperature proton exchange membrane fuel cell (HT-PEMFC) with a phosphoric acid-doped polybenzimidazole membrane. The model considers dissolution of reactants into electrolyte phase in the catalyst layers and subsequent crossover of reactant gases through the membrane. Furthermore, the model accounts for a mixed potential on the cathode side resulting from hydrogen crossover and hydrogen/oxygen catalytic combustion on the anode side due to oxygen crossover, which were overlooked in the HT-PEMFC modeling works in the literature. Numerical simulations are carried out to investigate the effects of gas crossover on HT-PEMFC performance by varying three critical parameters, i.e. operating current density, operating temperature and gas crossover diffusivity to approximate the membrane degradation. The numerical results indicate that the effect of gas crossover on HT-PEMFC performance is insignificant in a fresh membrane. However, as the membrane is degraded and hence gas crossover diffusivities are raised, the model predicts non-uniform reactant and current density distributions as well as lower cell performance. In addition, the thermal analysis demonstrates that the amount of heat generated due to hydrogen/oxygen catalytic combustion is not appreciable compared to total waste heat released during HT-PEMFC operations.     

The development of PTFE/Nafion/TEOS membranes for application in moderate and high temperature proton exchange membrane fuel cells

PTFE/Nafion (PN) and PTFE/Nafion/TEOS (PNS) membranes were fabricated for the application of moderate and high temperature proton exchange membrane fuel cells (PEMFCs), respectively. Membrane electrode assemblies (MEAs) were fabricated by PTFE/Nafion (and PTFE/Nafion/TEOS) membranes with commercially available low and high temperature gas diffusion electrodes (GDEs). The effects of relative humidity, operation temperature, and back pressure on the performance and durability test of the as-prepared MEAs were investigated. Incorporating TEOS into a PNS membrane and adding another layer of carbon onto a GDE would result in low membrane conductivity and low fuel cell performance respectively. However, in this work it is shown that HT-PNS MEAs demonstrate a higher performance than LT-PN MEAs in severe conditions - high temperature (118 °C) and low humidity (25% RH). The TEOS and additional carbon layer function as water retaining agents which are especially important for high temperature and low humidity conditions. The HT-PNS MEA showed good stability in a 50 h fuel cell test at high temperature, moderate relative humidity (50% RH) and back pressure of 14.7 psi.     

Development and performance evaluation of a high temperature proton exchange membrane fuel cell with stamped 304 stainless steel bipolar plates

In this work, a high temperature proton exchange membrane fuel cell (HT-PEMFC) with stamped SS304 bipolar plates is successfully developed. Its performance was evaluated under two types of gaskets at different assembly torques and air stoichiometric ratios. The rates of pressure loss at a torque of 7 N-m with 50 Shore A hardness gaskets was 2.0 × 10^?3 MPa min^?1, which is acceptable. The best performance of the developed HT-PEMFC with stamped SS304 bipolar plates was 228.33 mW cm^?2, which approaches the performance of HT-PEMFCs with graphite bipolar plates. The optimal air stoichiometric ratio for the HT-PEMFC with stamped SS304 bipolar plates was 4.0, which is higher than that for proton exchange membrane fuel cells with CNC milled graphite bipolar plates. This is probably because of the deformation of the flow channels under the assembly compression force, which causes an elevated gas-diffusion drag in the flow channels. After the test, it was observed that some products of corrosion reaction formed on the surface of the SS304 bipolar plate. This phenomenon may lead to a decrease in the operating life of the HT-PEMFC.     

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.     

质子交换膜燃料电池双极板的设计与模拟分析

质子交换膜燃料电池是直接将化学能转换为电能的装置,双极板上的流道结构对燃料电池的工作性能具有较大的影响。根据应用要求设计了具有平行流道、蛇形流道及希尔伯特分形流道的双极板结构,模拟计算了氢气在不同类型的流道和气体扩散层中的分布状态,分析了燃料电池的输出电流密度和功率密度随电极间电压的变化特点,比较了不同的流道结构对燃料电池输出电流密度的影响,以及不同的工作温度及气体压强的情况下,燃料电池输出电流密度随温度及压强的变化规律。