质子交换膜燃料电池堆的热力学分析

建立了质子交换膜燃料电池(PEMFC)堆的热力学分析模型,研究了运行温度、气体分压和阳极流量等工作参数对燃料电池堆能量效率和火用效率的影响。结果表明:对气体加压,能提高热力学能效率和火用效率;温度升高时,系统性能无明显变化;阳极流量增加时,系统的热力学能效率和火用效率有所降低。     

Experimental analysis of a degraded open-cathode PEM fuel cell stack

The well-known challenges to overcome in PEM fuel cell research are their relatively low durability and the high costs for the platinum catalysts. This work focuses on degradation mechanisms that are present in open-cathode PEM fuel cell systems and their links to the decaying fuel cell performance. Therefore a degraded, open-cathode, 20 cell, PEM fuel cell stack was analyzed by means of in-situ and ex-situ techniques. Voltage transients during external perturbations, such as changing temperature, humidity and stoichiometry show that degradation affects individual cells quite differently towards the end of life of the stack. Cells located close to the endplates of the stack show the biggest performance decay. Electrochemical impedance spectroscopy (EIS) data present non-reversible catalyst layer degradation but negligible membrane degradation of several cells. Post-mortem, ex-situ experiments, such as cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) show a significant active area loss of the first cells within the stack due to Pt dissolution, oxidation and agglomeration. Scanning electron microscope (SEM) images of the degraded cells in comparison with the normally working cells in the stack show severe carbon corrosion of the cathode catalyst layers.     

Constructal PEM fuel cell stack design

This paper describes a structured procedure to optimize the internal structure (relative sizes, spacings), single cells thickness, and external shape (aspect ratios) of a polymer electrolyte membrane fuel cell (PEMFC) stack so that net power is maximized. The constructal design starts from the smallest (elemental) level of a fuel cell stack (the single PEMFC), which is modeled as a unidirectional flow system, proceeding to the pressure drops experienced in the headers and gas channels of the single cells in the stack. The polarization curve, total and net power, and efficiencies are obtained as functions of temperature, pressure, geometry and operating parameters. The optimization is subjected to fixed stack total volume. There are two levels of optimization: (i) the internal structure, which accounts for the relative thicknesses of two reaction and diffusion layers and the membrane space, together with the single cells thickness, and (ii) the external shape, which accounts for the external aspect ratios of the PEMFC stack. The flow components are distributed optimally through the available volume so that the PEMFC stack net power is maximized. Numerical results show that the optimized single cells internal structure and stack external shape are “robust” with respect to changes in stoichiometric ratios, membrane water content, and total stack volume. The optimized internal structure and single cells thickness, and the stack external shape are results of an optimal balance between electrical power output and pumping power required to supply fuel and oxidant to the fuel cell through the stack headers and single-cell gas channels. It is shown that the twice maximized stack net power increases monotonically with total volume raised to the power 3/4, similarly to metabolic rate and body size in animal design.     

Performance optimisation of PEM fuel cell during MEA fabrication

We have analysed membrane electrode assemblies (MEAs) involving fabricated and commercially available electrodes using a scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) and developed simple mathematical models to simulate the best performance and design conditions. The analysis showed that a MEA surface with the catalyst layer consisting of 10 wt% Pt/C and 30 wt% Teflon^® (PTFE, designated E2) loaded with 0.38 mg Pt/cm² showed good localisation of the platinum particles. The SEM image of the E2 electrode showed the existence of a diffusion layer, while the cross-section of electrode E3 (without diffusion layer) showed only the backing layer of the carbon cloth. It was seen that good adhesion of the catalyst on the membrane was obtained as a result of the hot press used in fabrication. XPS analysis showed that the electrode surfaces consisted of C, O, F, Si and Pt, whose binding energies for the PTFE/C layer were C 1s, O 1s, F 1s and Si 2p states and were 285.0, 532.7, 689.5 and 103.0 eV, respectively. While for the catalyst layer, the binding energies for the elements, C 1s, O 1s, F 1s, Si 2p and Pt 4f states, were 284.3, 532.4, 689.3, 102.9 and 74.1 eV, respectively. Similar observations were made for a commercial E-TEK electrode. The mathematical and simulation investigations supported the hypothesis made in an earlier study in terms of optimum PEM fuel cell performance determination and design simulation. The calculated values of the voltage operational limit V_{opl cal.} agreed quite well with the experimental data V_{opl exp.} reported earlier. Other works from the open literature were also correlated using the mathematical model, and it was found that the V_opl values were comparable. Hydrogen usage thus calculated was best with the E2 electrode compared to E1, E3 and the commercially available E-TEK electrode.     

Dynamic behavior of a PEM fuel cell stack for stationary applications

We discuss the behavior and performance of a proton exchange membrane fuel cell stack under fast load commutations. We present experimental results for the polarization curves, energy balance sheet, and time response of the fuel cells. Although load transients are present both in the voltage and current generated, it is found that the fuel cell system response is faster than 0.15 s to load commutations. The experimental results were also compared to the Amphlett et al. and Kim et al. models, which were found to describe the data well.     

Data driven models for a PEM fuel cell stack performance prediction

The operating principles of polymer electrolyte membrane (PEM) fuel cells system involve electrochemistry, thermodynamics and hydrodynamics theory for which it is not always easy to establish a mathematical model. In this paper two different methods to model a commercial PEM fuel cell stack are discussed and compared. The models presented are nonlinear, derived from a black-box approach based on a set of measurable exogenous inputs and are able to predict the output voltage and cathode temperature of a 5 kW module working at the CNR-ITAE. A PEM fuel cell stack fed with H₂ rich gas is employed to experimentally investigate the dynamic behaviour and to reveal the most influential factors. The performance obtained using a classical Neural Networks (NNs) model are compared with a number of stacking strategies. The results show that both strategies are capable of simulating the effects of different stoichiometric ratio in the output variables under different working conditions.     

Diagnosis of PEM fuel cell stack dynamic behaviors

In this study, the steady-state performance and dynamic behavior of a commercial 10-cell Proton Exchange Membrane (PEM) fuel cell stack was experimentally investigated using a self-developed PEM fuel cell test stand. The start-up characteristics of the stack to different current loads and dynamic responses after current step-up to an elevated load were investigated. The stack voltage was observed to experience oscillation at air excess coefficient of 2 due to the flooding/recovery cycle of part of the cells. In order to correlate the stack voltage with the pressure drop across the cathode/anode, fast Fourier transform was performed. Dominant frequency of pressure drop signal was obtained to indicate the water behavior in cathode/anode, thereby predicting the stack voltage change. Such relationship between frequency of pressure drop and stack voltage was found and summarized. This provides an innovative approach to utilize frequency of pressure drop signal as a diagnostic tool for PEM fuel cell stack dynamic behaviors.     

Development and demonstration of a higher temperature PEM fuel cell stack

Research and development was conducted on a proton exchange membrane (PEM) fuel cell stack to demonstrate the capabilities of Ionomem Corporation's composite membrane to operate at 120 °C and ambient pressure for on-site electrical power generation with useful waste heat. The membrane was a composite of polytetrafluoroethylene (PTFE), Nafion^®, and phosphotungstic acid. Studies were first performed on the membrane, cathode catalyst layer, and gas diffusion layer to improve performance in 25 cm², subscale cells. This technology was then scaled-up to a commercial 300 cm² size and evaluated in multi-cell stacks. The resulting stack obtained a performance near that of the subscale cells, 0.60 V at 400 mA cm⁻² at near 120 °C and ambient pressure with hydrogen and air reactants containing water at 35% relative humidity. The water used for cooling the stack resulted in available waste heat at 116 °C. The performance of the stack was verified. This was the first successful test of a higher-temperature, PEM, fuel-cell stack that did not use phosphoric acid electrolyte.     

Modelling a PEM fuel cell stack with a nonlinear equivalent circuit

A nonlinear circuit model of a polymer electrolyte membrane (PEM) fuel cell stack is presented. The model allows the simulation of both steady-state and dynamic behaviour of the stack on condition that the values of some of its parameters are changed in the two operating conditions. The circuit parameters can be obtained by means of simple experimental tests and calculations. A commercial PEM fuel cell stack is modelled as seen from the power conditioning system side, without requiring parameters necessary for complex mathematical models and not easily obtainable by the majority of users. A procedure of parameter determination is developed and a comparison between the simulated and experimental results for both steady-state and dynamic behaviour of the PEM stack is shown.     

Exergy analysis of a regional-distributed PEM fuel cell system

In this paper, the exergy flow and exergy efficiency of a 3 kW proton-exchange-membrane fuel cell were investigated, and the regional characteristic of the distributed energy system was considered. In the environmental temperature range of 263–313 K, the difference in the total efficiency of the proposed system was 6%. On the other hand, the difference in the exergy total efficiency of the same temperature range was 30%. Moreover, as a result of examining how to improve the exergy efficiency of this system, certain improvement methods were proposed: (a) preheat the city-gas and air supplied to the system using exhaust heat and raise the combustion temperature; (b) preheat the water supplied to the system using exhaust heat; (c) change the catalyst material of each unit and reduce the amount of cooling of the reformed gas; and (d) examine the combined cycle power generation. The exergy efficiency, in the case of introducing the proposed system into individual homes in Sapporo, Tokyo, and Kagoshima, was evaluated. Consequently, when the system was introduced into a community with low outside air temperatures, exergy efficiency increased compared with communities with high outside air temperatures.     

Exergoeconomic analysis of a vehicular PEM fuel cell system

In this study, we deal with the exergoeconomic analysis of a proton exchange membrane (PEM) fuel cell power system for transportation applications. The PEM fuel cell performance model, that is the polarization curve, is previously developed by one of the authors by using the some derived and developed equations in literature. The exergoeconomic analysis includes the PEM fuel cell stack and system components as compressor, humidifiers, pressure regulator and the cooling system. A parametric study is also conducted to investigate the system performance and cost behaviour of the components, depending on the operating temperature, operating pressure, membrane thickness, anode stoichiometry and cathode stoichiometry. For the system performance, energy and exergy efficiencies and power output are investigated in detail. It is found that with an increase of temperature and pressure and a decrease of membrane thickness the system efficiency increases which leads to a decrease in the overall production cost. The minimization of the production costs is very crucial in commercialization of the fuel cells in transportation sector.     

Hydrogen pumping effect induced by fuel starvation in a single cell of a PEM fuel cell stack at galvanostatic operation

In a proton exchange membrane fuel cell stack, a single cell is potentially subjected to voltage reversal under fuel starvation conditions, which is extremely harmful to its durability. In this work, we develop a two-dimensional computational model to investigate the current and potential distributions in a single cell under these voltage reversal conditions. It is found that most of hydrogen under these conditions is oxidized in a narrow region close to the fuel-inlet, and the anode area before hydrogen depletion can be characterized into an activation limited region and a mass-transport limited region. Meanwhile, an unexpected hydrogen evolution phenomenon is discovered in the cathode catalyst layer (CCL) adjacent to the fuel inlet, owing to the imbalance between the localized ultrahigh hydrogen oxidation current density in the anode and the lower limiting current density of oxygen reduction reaction in the adjacent CCL. Furthermore, the evolved hydrogen gas is also found to be oxidized nearby due to the steep variation of electrolyte potential in the CCL, indicating the coexistence of hydrogen evolution, hydrogen oxidation and oxygen reduction within the micron-scale thickness of CCL, which significantly adds to the complexity of the coupled phenomena in the voltage-reversal single cell.     

Simulation and experimental analysis of the clamping pressure distribution in a PEM fuel cell stack

High performance and efficiency are often reported in single-cell polymer electrolyte membrane (PEM) fuel cell (FC) experiments. This however, can reduce substantially when moving from single-cell experiments to multiple cells. Fuel cell performance is degraded for many reasons when adding cells, but; possibly the most important, is contact resistance between the bipolar plate and gas diffusion layer (GDL). Contact resistance is in direct relation to the clamping configuration and clamping pressure applied to a FC stack. Simulation of a single cell and 16-cell FC was performed at various clamping pressures resulting in detailed 3D plots of stress and deformation. The stress on the GDL, for any value of clamping pressure simulated in this study, is around 1.5 MPa for the 16-cell stack and around 4 MPa in single cell simulations. Experimental testing of clamping pressure effects was performed on a 16-cell stack by placing a thin pressure-sensitive film between GDL and bipolar plate. Clamping pressure was applied using various loads, durations, and two types of GDLs. The results from experimental testing show that pressure on the GDL is in the range of 0–2.5 MPa. When using rectangular cells, experimental results show nearly zero pressure in the center of each cell and the center cells of the stack, regardless of clamping method.     

Modeling and simulation of a PEM fuel cell stack considering temperature effects

Management of the water and heat ejected as byproducts in an operating PEM fuel cell stack are crucial factors in their optimal design and safe operations. Models currently available for a PEM fuel cell are based on either empirical or 3-D computational fluid dynamics (CFD). Both models do not fully meet the need to represent physical behavior of a stack because of either their simplicity or complexity. We propose a highly dynamic PEM fuel cell stack model, taking into account the most influential property of temperature affecting performance and dynamics. Simulations have been conducted to analyze start-up behaviors and the performance of the stack in conjunction with the cells. Our analyses demonstrate static and dynamic behaviors of a stack. Major results presented are as follows: (1) operating dependent temperature gradient across through-plane direction of the fuel cell stack, (2) endplate effects on the temperature profile during start-up process, (3) temperature profile influences on the output voltage of individual cells and the stack, (4) temperature influence on the water content in membranes of different cells, and (5) cathode inlet relative humidity influence on the temperature profile of the stack.     

Unsteady 2D PEM fuel cell modeling for a stack emphasizing thermal effects

Models currently used for analyses of thermal and water behavior of a PEM fuel cell are based 3D computational fluid dynamics (CFD). However, the analyses are limited to a single cell with static behavior. Thus, these models cannot be used for analyses of dynamic behavior of a stack that continuously varies according to operating conditions. The model proposed describes dynamic behavior of a stack with two adjoining cells and endplate assembly, and work as a current controlled voltage source that can be used for optimization of BOPs and the associated controls. Simulations have been conducted to analyze start-up behaviors and the performance of the stack. Our analyses deliver following results: (1) dynamic temperature distribution in both the through-plane direction and the along channel direction of the fuel cell stack, (2) effects influencing the source terms of current density, and (3) dynamic oxygen concentration distribution. The temperature profile and its variation propensity are comparable to the previous results [Y. Shan, S.Y. Choe, J. Power Sources, 145 (1) (2005) 30–39; Y. Shan, S.Y. Choe, J. Power Sources, in press].     

Turbulent flow in the distribution header of a PEM fuel cell stack

A numerical investigation of the flowfield in a model distribution header manifold of a polymer electrolyte membrane fuel cell stack is conducted. The computational model simulates two segments of an experimental setup of a pair of model headers which replicate the headers of a fuel cell stack. The model headers consist of an inlet and outlet sections connected with a plate containing an array of holes that replicate the unit cells. The flow structures in the outlet header are rather complex and are the result of the superposition of a series of impinging jets in a confined space in the presence of crossflow. The flow from each hole, which represents an individual cell outlet, enters the outlet header as a jet stream and is subjected to a crossflow. Large Eddy Simulations (LES) are performed for a portion of the outlet header to investigate the complex turbulent flow and related structures under different crossflow conditions, and are complemented by Particle Image Velocimetry (PIV) measurements. The LES results show that two large vortical structures are formed in the header cross-section, with a high-speed round jet from the cell outlet holes forcing a diversion of the crossflow, dividing it into two separate branches. Investigation of the flow restructuring after a blockage of one of the jets is performed. Simulation results using a slot opening for the jet show flow instabilities. The results of this study highlight the unsteady and highly turbulent nature of the flow in the header and provide a characterization of the complex three-dimensional structure of the flow. The flowfield and flow structures may impact the overall pressure drop along the header and the effective cross-sectional area for the flow leaving the header. The observations and insights obtained from the LES simulation and PIV measurements point to the need to further investigate the impact on flow sharing in a stack of the flowfield development in the outlet header.     

Vibration tests on a PEM fuel cell stack usable in transportation application

A fuel cell stack for use in transportation or in applications which involves the positioning of such systems in a location of high vibration and shock, is subjected to accelerated stress screening to ascertain the reliability of the stack, mechanical integrity and also to assess the mounting requirements. Such studies have not been well documented in open literature. In this paper, we have done the vibration test analysis on a 500 W Proton Electrolyte Membrane (PEM) fuel cell stack developed at our centre by simulating some of the vibration, shock and resonance in the stack and the likelihood of the stack to undergo in any application and evaluated the robustness of the stack. An experimental setup was designed for this purpose consisting of subjecting the PEM fuel cell stack to random and swept-sine excitations on a vibrating platform in three axes and measuring the mechanical response using accelerometers fixed at various locations in the stack. The fuel cell performance (pre-vibration test and post-vibration test) as obtained from polarization studies and the power–amperage curves does not show any significant damage effects, and a post-testing stack inspection showed a minor torque release. Further tests are recommended to study the dynamic life test. This study opens up further investigation which the authors propose to carry out in due course.     

Flow distribution in the manifold of PEM fuel cell stack

In this study, the pressure variation and the flow distribution in the manifold of a fuel-cell stack are simulated by a computational fluid dynamics (CFD) approach. Two dimensional stack model composed of 72 cells filled with porous media is constructed to evaluate pressure drop caused by channel flow resistance. In order to simplify this model, electrochemical reactions, heat and mass transport phenomena are ignored and air is treated as working fluid to investigate flow distribution in stacks. Design parameters such as the permeability of the porous media, the manifold width and the air feeding rate were changed to estimate uniformity of the flow distribution in the manifold. A momentum-balance theory and a pressure-drop model are presented to explain the physical mechanism of flow distribution. Modeling results indicate that both the channel resistance and the manifold width can enhance the uniformity of the flow distribution. In addition, a lower air feeding rate can also enhance the uniformity of flow distribution. However, excessive pressure drop is not beneficial for realistic applications of a fuel-cell stack and hence enhanced manifold width is a better solution for flow distribution.     

PEM fuel-cell stack design for improved fuel utilization

We propose a new design for a polymer electrolyte membrane (PEM) fuel-cell stack that can achieve higher fuel utilization without using hydrogen recirculation devices such as hydrogen pumps or ejectors, which consume parasitic power and/or require additional control schemes. The basic concept of the proposed design is to divide the anodic cells of a stack into several blocks by inserting compartments between the cells, thereby constructing a multistage anode with a single-stage cathode in a single stack. In this design, a higher gaseous flow rate is maintained at the outlet of the anodic cells, even under dead-end conditions, and this results in a reduction of purge-gas emissions by hindering the accumulation of liquid water and nitrogen in the anodic cells. A 15 kW-class PEM fuel cell stack is designed, fabricated, and tested to investigate the effectiveness of the proposed design. The experimental results indicate that the amount of purge gas is significantly reduced, and consequently, a higher fuel utilization of more than 99.6% is achieved. Additionally, the output voltage of the stack fluctuates much less than that of conventional fuel cells owing to the multistage anode design.     

Dynamic modeling and analysis of a 20-cell PEM fuel cell stack considering temperature and two-phase effects

Dynamic characteristics and performance of a PEM fuel cell stack are crucial factors to ensure safe, effective and efficient operation. In particular, water and heat at varying loads are important factors that directly influence the stack performance and reliability. Herein, we present a new dynamic model that considers temperature and two-phase effects and analyze these effects on the characteristics of a stack.