Dynamic modeling of high temperature PEM fuel cell start-up process

High temperature proton exchange membrane fuel cells (HT-PEMFCs) are considered to be the next generation fuel cells. Compared with standard low temperature proton exchange membrane fuel cells (LT-PEMFCs) the electrochemical kinetics for electrode reactions are enhanced by using a polybenzimidazole based membrane at an operation temperature between 160 °C and 180 °C. However, starting HT-PEMFCs from room temperature to a proper operation temperature is a challenge in application where a fast start of the fuel cell is required such as in uninterruptible power supply systems. There are different methods to start-up HT-PEMFCs. Based on a 3D physical model of a single HT-PEMFC, the start-up process is analyzed by comparing the start-up duration of the different start-up concepts. Furthermore, the temperature distribution in the HT-PEMFC is also analyzed. Finally, an optimal start-up method is proposed for the given cell configuration.     

Effects of inlet relative humidity (RH) on the performance of a high temperature-proton exchange membrane fuel cell (HT-PEMFC)

A high temperature-proton exchange membrane fuel cells (HT-PEMFC) based on phosphoric acid (PA)-doped polybenzimidazole (PBI) membrane is able to operate at elevated temperature ranging from 100 to 200 °C. Therefore, it is evident that the relative humidity (RH) of gases within a HT-PEMFC must be minimal owing to its high operating temperature range. However, it has been continuously reported in the literature that a HT-PEMFC performs better under higher inlet RH conditions. In this study, inlet RH dependence on the performance of a HT-PEMFC is precisely studied by numerical HT-PEMFC simulations. Assuming phase equilibrium between membrane and gas phases, we newly develop a membrane water transport model for HT-PEMFCs and incorporate it into a three-dimensional (3-D) HT-PEMFC model developed in our previous study. The water diffusion coefficient in the membrane is considered as an adjustable parameter to fit the experimental water transport data. In addition, the expression of proton conductivity for PA-doped PBI membranes given in the literature is modified to be suitable for commercial PBI membranes with high PA doping levels such as those used in Celtec^® MEAs. Although the comparison between simulations and experiments shows a lack of agreement quantitatively, the model successfully captures the experimental trends, showing quantitative influence of inlet RH on membrane water flux, ohmic resistance, and cell performance during various HT-PEMFC operations.     

Acid doped polybenzimidazoles based membrane electrode assembly for high temperature proton exchange membrane fuel cell: A review

High temperature proton exchange membrane fuel cells (HT-PEMFCs) are proficient clean energy conversion devices for automotive and stationary applications. HT-PEMFC could mitigate the CO poisoning, humidity and heat management, and sluggish of oxygen reduction reaction (ORR). Acid doped polybenzimidazoles (PBIs)/functionalized PBIs polymer electrolyte membranes are familiar uses for HT-PEMFC because of high proton conductivity with thermo-mechanical stability. Proton conductivity of PBI membranes is greatly promising by acid doping dimension and cell operating temperature. PBI reactive sites (=NH) and acidic anions prominently contribute the proton transfer through the prolonged hydrogen bonding network. Coating and sprayed methods are prominent techniques for fabrication of gas diffusion electrodes (GDEs), although shrinkage and hairline surface cracks observed on GDEs. Multi walled carbon nanotubes (MWCNTs) has been compromising unique characteristics for steady carbon support materials. Moreover, PTFE and PVDF can be used as catalyst binder to reduce corrosion rate. In this review, it has been focused the PBIs membrane, acid doping, GDEs, MEA and durability of MEA.     

Hydrogen production from glycerol steam reforming for low- and high-temperature PEMFCs

This paper presents a thermodynamic study of a glycerol steam reforming process, with the aim of determining the optimal hydrogen production conditions for low- and high-temperature proton exchange membrane fuel cells (LT-PEMFCs and HT-PEMFCs). The results show that for LT-PEMFCs, the optimal temperature and steam to glycerol molar ratio of the glycerol reforming process (consisting of a steam reformer and a water gas shift reactor) are 1000 K and 6, respectively; under these conditions, the maximum hydrogen yield was obtained. Increasing the steam to glycerol ratio over its optimal value insignificantly enhanced the performance of the fuel processor. For HT-PEMFCs, to keep the CO content of the reformate gas within a desired range, the steam reformer can be operated at lower temperatures; however, a high steam to glycerol ratio is required. This requirement results in an increase in the energy consumption for steam generation. To determine the optimal conditions of glycerol steam reforming for HT-PEMFC, both the hydrogen yield and energy requirements were taken into consideration. The operational boundary of the glycerol steam reformer was also explored as a basic tool to design the reforming process for HT-PEMFC.     

Composite membrane by incorporating sulfonated graphene oxide in polybenzimidazole for high temperature proton exchange membrane fuel cells

The objective of this work is to examine the polybenzimidazole (PBI)/sulfonated graphene oxide (sGO) membranes as alternative materials for high-temperature proton exchange membrane fuel cell (HT-PEMFC). PBI/sGO composite membranes were characterized by TGA, FTIR, SEM analysis, acid doping&acid leaching tests, mechanical analysis, and proton conductivity measurements. The proton conductivity of composite membranes was considerably enhanced by the existence of sGO filler. The enhancement of these properties is related to the increased content of –SO₃H groups in the PBI/sGO composite membrane, increasing the channel availability required for the proton transport. The PBI/sGO membranes were tested in a single HT-PEMFC to evaluate high-temperature fuel cell performance. Amongst the PBI/sGO composite membranes, the membrane containing 5 wt. % GO (PBI/sGO-2) showed the highest HT-PEMFC performance. The maximum power density of 364 mW/cm² was yielded by PBI/sGO-2 membrane when operating the cell at 160 °C under non humidified conditions. In comparison, a maximum power density of 235 mW/cm² was determined by the PBI membrane under the same operating conditions. To investigate the HT-PEMFC stability, long-term stability tests were performed in comparison with the PBI membrane. After a long-term performance test for 200 h, the HT-PEMFC performance loss was obtained as 9% and 13% for PBI/sGO-2 and PBI membranes, respectively. The improved HT-PEMFC performance of PBI/sGO composite membranes suggests that PBI/sGO composites are feasible candidates for HT-PEMFC applications.     

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.     

Effect of operating conditions on carbon corrosion in polymer electrolyte membrane fuel cells

The influence of humidity, cell temperature and gas-phase O₂ on the electrochemical corrosion of carbon in polymer electrolyte membrane fuel cells is investigated by measuring CO₂ emission at a constant potential of 1.4 V for 30 min using on-line mass spectrometry. Carbon corrosion shows a strong positive correlation with humidity and cell temperature. The presence of water is indispensable for electrochemical carbon corrosion. By contrast, the presence of gas-phase O₂ has little effect on electrochemical carbon corrosion. With increased carbon corrosion, changes in fuel cell electrochemical characteristics become more prominent and thereby indicate that such corrosion significantly affects fuel cell durability.     

High temperature PEM fuel cells

There are several compelling technological and commercial reasons for operating H₂/air PEM fuel cells at temperatures above 100 °C. Rates of electrochemical kinetics are enhanced, water management and cooling is simplified, useful waste heat can be recovered, and lower quality reformed hydrogen may be used as the fuel. This review paper provides a concise review of high temperature PEM fuel cells (HT-PEMFCs) from the perspective of HT-specific materials, designs, and testing/diagnostics. The review describes the motivation for HT-PEMFC development, the technology gaps, and recent advances.

HT-membrane development accounts for 90% of the published research in the field of HT-PEMFCs. Despite this, the status of membrane development for high temperature/low humidity operation is less than satisfactory. A weakness in the development of HT-PEMFC technology is the deficiency in HT-specific fuel cell architectures, test station designs, and testing protocols, and an understanding of the underlying fundamental principles behind these areas. The development of HT-specific PEMFC designs is of key importance that may help mitigate issues of membrane dehydration and MEA degradation.     

Experimental and numerical investigation on effects of cathode flow field configurations in an air-breathing high-temperature PEMFC

Air-breathing high-temperature proton exchange membrane fuel cell (HT-PEMFC) gets rid of the cumbersome air supplying systems and avoids the water flooding problem by directly exposing the cathode to air and operating the fuel cell at elevated temperature. Performance of the air-breathing HT-PEMFC is dependent on many factors particularly the cathode flow field configurations. However, studies about air-breathing HT-PEMFCs are quite limited in the literature. In the present study, an experimental testing system was setup for the performance measurement of the air-breathing HT-PEMFC. A 3D numerical model was established and validated by the experimental data. Effects of the cathode flow field configurations including the opening shape, end plate thickness, open ratio and opening direction on performance of the air-breathing HT-PEMFC were experimentally and numerically investigated. It was found that the cathode end plate thickness and upward or sideways orientation have the least effect on the performance. The maximum power density of 160 mW/cm² at the current density of 394 mA/cm² can be achieved for the cathode flow field with slot holes and an open ratio of 75%.     

Parameter study of high-temperature proton exchange membrane fuel cell using data-driven models

In this paper, a numerical model of high-temperature proton exchange membrane fuel cell (HT-PEMFC) was developed, in which the thermal and electrical properties were treated as temperature dependent. Based on the numerical simulation, the needed training data was acquired and used for the development of data-driven model via the artificial neural network (ANN) algorithm. The developed data-driven model was then used to predict the performance of HT-PEMFC. The simulation results indicated that the deviation of ANN prediction was less than 2.48% compared with numerical simulation. The effects of various influential factors, such as the geometry size of the gas flow channel, the thickness of the membrane and the operating temperature, could be predicted easily by using the ANN model. The ANN model prediction results showed that the more compact fuel cell and the higher operating temperature improved the performance of HT-PEMFC. The proposed ANN model and the parameters study will contribute to the further design and operation of HT-PEMFC.     

3D non-isothermal dynamic simulation of high temperature proton exchange membrane fuel cell in the start-up process

High temperature proton exchange membrane fuel cell (HT-PEMFC) with phosphoric acid doped polybenzimidazole (PBI) electrolyte shows multiple advantages over conventional PEMFC working at below 373 K, such as faster electrochemical kinetics, simpler water management, higher carbon monoxide tolerance. However, starting HT-PEMFC from room temperature to the optimal operating temperature range (433.15 K–453.15 K) is still a serious challenge. In present work, the start-up strategy is proposed and evaluated and a three-dimensional non-isothermal dynamic model is developed to investigate start-up time and temperature distribution during the start-up process. The HT-PEMFC is preheated by gas to 393.15 K, followed by discharging a current from the cell for electrochemical heat generation. Firstly, different current loads are applied when the average temperature of membrane reaches 393.15 K. Then, the start-up time and temperature distribution of co-flow and counter-flow are compared at different current loads. Finally, the effect of inlet velocity and temperature on the start-up process are explored in the case of counter-flow. Numerical results clearly show that applied current load is necessary to reduce start-up time and just 0.1 A/cm² current load can reduce startup time by 45%. It is also found that co-flow takes 18.8% less time than counter-flow to heat membrane temperature to 393.15 K, but the maximum temperature difference of membrane is 39% higher than the counter-flow. Increasing the inlet gas flow velocity and temperature can shorten the start-up time but increases the temperature difference of the membrane.     

Degradation study of high temperature proton exchange membrane fuel cell under start/stop and load cycling conditions

The unreliable durability of high temperature proton exchange membrane fuel cells (HT-PEMFCs) is one of the restriction factors upon the commercialization process. In this paper, 600-h accelerated stress tests (ASTs) were performed on HT-PEMFCs to investigate the performance degradation under start/stop, load cycling (0.2–0.8 A cm^?2 and 0.04–0.2 A cm^?2) conditions. The activation, ohmic and mass transport polarization losses were determined in combination with the electrochemical impedance spectroscopy (EIS) and Tafel slope analysis, and the degradation modes such as carbon corrosion, catalyst degradation, acid loss and membrane degradation were analyzed by linear sweep voltammetry (LSV), cyclic voltammetry (CV) and transmission electron microscopy (TEM) characterization. The polarization curves of ASTs show that load cycling between 0.04 and 0.2 A cm^?2 extensively aggravates performance degradation, indicating that high-potential operation has the greatest detrimental impact on the durability. By comparing the changes of the activation, ohmic and mass transport polarization losses, it can be found that the activation polarization is the dominant factor leading to performance degradation in the 600-h test, and the ohmic polarization has little effect on the performance degradation. After the test at load cycling between 0.2 and 0.8 A cm^?2, the membrane is seriously degraded and the ohmic resistance increases significantly, and the severe acid loss becomes critical issue in the long-term durability of HT-PEMFC.     

Modeling and analysis of a 5 kWe HT-PEMFC system for residential heat and power generation

We present a high-temperature proton exchange membrane fuel cell (HT-PEMFC) system model that accounts for fuel reforming, HT-PEMFC stack, and heat-recovery modules along with heat exchangers and balance of plant (BOP) components. In the model developed for analysis, the reaction kinetics for the fuel reforming processes are considered to accurately capture exhaust gas compositions and reactor temperatures under various operating conditions. The HT-PEMFC stack model is simplified from the three-dimensional HT-PEMFC CFD models developed in our previous studies. In addition, the parasitic power consumption and waste heat release from the various BOP components are calculated based on their heat-capacity curves. An experimental fuel reforming reactor for a 5.0 kW_e HT-PEMFC system was tested to experimentally validate the fuel reforming sub model. The model predictions were found to be in good agreement with the experimental data in terms of exhaust gas compositions and bed temperatures. Additionally, the simulation revealed the impacts of the burner air-fuel ratio (AFR) and the steam reforming reactor steam-carbon ratio on the system performance and efficiency. In particular, the combined heat and power efficiency of the system increased up to 78% when the burner AFR was properly adjusted. This study clearly illustrates that an HT-PEMFC system requires a high degree of thermal integration and optimization of the system configuration and operating conditions.     

Coupled mechanical stress and multi-dimensional CFD analysis for high temperature proton exchange membrane fuel cells (HT-PEMFCs)

We use a combined finite element method (FEM)/computational fluid dynamics (CFD) methodology to numerically investigate the effects of gas diffusion layer (GDL) compression/intrusion on the performance of a phosphoric acid-doped polybenzimidazole (PBI) membrane-based high temperature proton exchange membrane fuel cell (HT-PEMFC). Three-dimensional (3-D) FEM simulations are conducted under various displacement clamping conditions to analyze cell deformation characteristics. Then, a multi-dimensional HT-PEMFC CFD model is applied to the deformed cell geometries to study transport and electrochemical processes during HT-PEMFC operations. Our numerical simulation results reveal that the maximum stresses in the deformed GDLs always occur near the edge of the ribs. The combined effects of GDL compression/intrusion considerably increase spatial non-uniformity in the species and current density distributions, and reduce cell performance.     

Comparative analysis of biomass and coal based co-gasification processes with and without CO2 capture for HT-PEMFCs

With the seasonal availability and low energy density of biomass and the high environmental impact of coal, the co-gasification of biomass and coal is an alternative approach facilitating a trade-off between renewable and non-renewable resources. The aim of this study was to investigate hydrogen production from the co-gasification of biomass and coal integrated by means of the sorption-enhanced water gas shift reactor (G-SEWGS) for a high temperature proton exchange membrane fuel cell (HT-PEMFC). The effects of the gasifier temperature, the steam to fuel ratio (S/F ratio), and the equivalence ratio (ER) on the hydrogen production performance and environmental impact of the G-SEWGS were theoretically analysed and compared with the conventional gasifier integrated with the water gas shift reactor (G-WGS) and the sorption-enhanced gasifier integrated with the water gas shift reactor (SEG-WGS). As compared to the conventional water gas shift reactor, the addition of a CaO sorbent in the modified water gas shift reactor not only reduces the amount of the CO₂ emission but also leads to an increase in the hydrogen concentration and hydrogen content. The G-SEWGS provides better performance in terms of its fuel processor efficiency and CO₂ emission than the G-WGS and the SEG-WGS. Also, the problem of sulphur compound in the hydrogen-rich gas can be reduced by using of the sorption-enhanced water gas shift reactor (SEWGS). The best system exergy efficiency, which was around 22% for the power generation, was determined from the HT-PEMFC integrated with the G-SEWGS. The main exergy destruction of around 70% of the total loss was caused by hydrogen production processes.     

Numerical study of thermal stresses in high-temperature proton exchange membrane fuel cell (HT-PEMFC)

The purpose of this work is to numerically examine the thermal stress distributions in a high-temperature proton exchange membrane fuel cell (HT-PEMFC) based on a phosphoric acid doped polybenzimidazole (PBI) membrane. A fluid structure interaction (FSI) method is adopted to simulate the expansion/compression that arises in various components of a membrane electrode assembly (MEA) during the HT-PEMFC assembly processes, as well as during cell operations. First, three-dimensional (3-D) finite element method (FEM) simulations are conducted to predict the cell deformation during cell clamping. Then, a nonisothermal computational fluid dynamic (CFD)-based HT-PEMFC model developed in a previous study [1] is applied to the deformed cell geometry to estimate the key species and temperature distributions inside the cell. Finally, the temperature distributions obtained from these CFD simulations are employed as the input load for 3-D FEM simulations. The present numerical study provides a fundamental understanding of the stress–temperature interaction during HT-PEMFC operations and demonstrates that the coupled FEM/CFD HT-PEMFC model presented in this paper can be used as a useful tool for optimizing HT-PEMFC clamping and operating conditions.     

Experimental investigation of CO tolerance in high temperature PEM fuel cells

In the present work, the effect of operating a high temperature proton exchange membrane fuel cell (HT-PEMFC) with different reactant gases has been investigated throughout performance tests. Also, the effects of temperature on the performance of a HT-PEMFC were analyzed at varying temperatures, ranging from 140 °C to 200 °C. Increasing the operating temperature of the cell increases the performance of the HT-PEMFC. The optimum operating temperature was determined to be 160 °C due to the deformations occurring in the cell components at high working temperatures. To investigate the effects of CO on the performance of HT-PEMFC, the CO concentration ranged from 1 to 5 vol %. The current density at 0.6 V decreases from 0.33 A/cm² for H₂ to 0.31 A/cm² for H₂ containing 1 vol % CO, to 0.29 A/cm² for 3 vol % CO, and 0.25 A/cm² for 5 vol % CO, respectively. The experimental results show that the presence of 25 vol % CO₂ or N₂ has only a dilution effect and therefore, there is a minor impact on the HT-PEMFC performance. However, the addition of CO to H₂/N₂ or H₂/CO₂ mixtures increased the performance loss. After long-term performance test for 500 h, the observed voltage drop at constant current density was obtained as ～14.8% for H₂/CO₂/CO (75/22/3) mixture. The overall results suggest that the anode side gas mixture with up to 5 vol % CO can be supplied to the HT-PEMFC stack directly from the reformer.     

Enhanced power generation,faster transient response and longer durability of HT-PEMFC using composite polybenzimidazole electrolyte membrane with optimum rGO loading

Here we report enhanced power generation, faster transient response and longer durability of HT-PEMFC by employing a composite membrane of PBI with reduced graphene oxide (rGO) at an optimum loading of 1%. Easy and low cost synthesis of the composite membranes at different loading of rGO is achieved using methane sulfonic acid (MSA) as solvent that resolves the long-standing issue of poor solubility of PBI in the conventional solvents. Property and performance mapping with respect to rGO loading not only leads to attain the optimum but also identifies the window of feasible operating zone. It is observed that with very low (1%) rGO content, composite PBI membrane (rGO-PBI-1) offers the maximum enhancement of all properties viz water uptake, acid uptake, proton conductivity, ion exchange capacity, acid retention capacity, chemical stability, yield strength, while beyond a threshold/critical loading (~4%) deterioration of electrochemical and mechanical properties occur. Steady state performance analysis reveals almost two times peak power enhancement of HT-PEMFC using rGO-PBI-1 electrolyte membrane at an operating temperature of 170 °C; insitu impedance analysis during fuel cell operation reveals sharp decay in charge transfer resistance. Multiple step response analysis confirms (~2 times) faster transient response of fuel cell using rGO-PBI-1 while compared to that with pristine PBI membrane. Fuel cell stability analysis ensures longer durability of operation with negligible decay in voltage.     

Graphene based catalyst supports for high temperature PEM fuel cell application

In this study, the effect of graphene nanoplatelet (GNP) and graphene oxide (GO) based carbon supports on polybenzimidazole (PBI) based high temperature proton exchange membrane fuel cells (HT-PEMFCs) performances were investigated. Pt/GNP and Pt/GO catalysts were synthesized by microwave assisted chemical reduction support. X-ray diffraction (XRD), Thermogravimetric analysis (TGA), Brauner, Emmet and Teller (BET) analysis and high resolution transmission electron microscopy (HRTEM) were used to investigate the microstructure and morphology of the as-prepared catalysts. The electrochemical surface area (ESA) was studied by cyclic voltammetry (CV). The results showed deposition of smaller Pt nanoparticles with uniform distribution and higher ECSA for Pt/GNP compared to Pt/GO. The Pt/GNP and Pt/GO catalysts were tested in 25 cm² active area single HT-PEMFC with H₂/air at 160 °C without humidification. Performance evaluation in HT-PEMFC shows current densities of 0.28, 0.17 and 0.22 A/cm² for the Pt/GNP, Pt/C and Pt/GO catalysts based MEAs at 160 °C, respectively. The maximum power density was obtained for MEA prepared by Pt/GNP catalyst with H₂/Air dry reactant gases as 0.34, 0.40 and 0.46 W/cm² at 160 °C, 175 °C and 190 °C, respectively. Graphene based catalyst supports exhibits an enhanced HT-PEMFC performance in both low and high current density regions. The results indicate the graphene catalyst support could be utilized as the catalyst support for HT-PEMFC application.     

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.