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.     

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.     

Dodecylamine-modified carbon supports for cathode in proton exchange membrane fuel cells

In this investigation, hydrophobic dodecylamine-modified carbon supports are prepared for proton exchange membrane fuel cells by organic synthesis. Well-dispersed Pt-Ru nanoparticles, with a narrow size distribution, are then deposited on the dodecylamine-modified carbon supports by methanol reduction to serve as cathodic catalysts. These dodecylamine-modified catalysts are separately mixed with either a commercial catalyst or unmodified catalyst to provide hydrophobic channels to convey the reaction gas to the active sites in the catalyst layer. The best cathode composite catalyst, containing 20-40 wt% of modified-catalyst, gives approximate 30% increase in the maximum power density, comparing to E-TEK catalyst (125 mW cm⁻²). The increase in the maximum power density is attributed to higher activity and lower resistance. This result is discussed in the context of AC-impedance and proton conductivity analysis.     

Study of sulfur dioxide crossover in proton exchange membrane fuel cells

As one of the most deleterious impurities to proton exchange membrane fuel cells (PEMFCs), sulfur dioxide (SO₂) in air can pass through the membrane from the cathode to the anode and poison the catalyst of the two electrodes. The phenomenon of SO₂ crossover is investigated electrochemically in this paper. The influences of SO₂ concentration, relative humidity, gas pressure and current density on SO₂ crossover are discussed. Experimental results reveal that the anode tends to be poisoned heavily with the increasing concentration of SO₂ in the cathode. The coverage of the anode catalyst by SO₂ permeating from the cathode enlarges with the decreasing relative humidity in the anode. The rate of SO₂ crossover from the anode to the cathode is promoted at high current density when SO₂ is directly introduced into the anode side instead of the cathode side, which can be ascribed to the electro-osmotic drag effect. Gas pressures show no obvious effects on SO₂ crossover. A co-permeation mechanism of SO₂ with water is deduced based on the overall analysis.     

Behaviors of proton exchange membrane fuel cells under oxidant starvation

Durability is an important issue in proton exchange membrane fuel cells (PEMFCs) currently. Reactant starvation could be one of the reasons for PEMFC degradation. In this research, the oxidant starvation phenomena in a single cell are investigated. The local interfacial potential, current and temperature distribution are detected in situ with a specially constructed segmented cell. Experimental results show that during the cell reversal process due to oxidant starvation, the local interfacial potential in the oxidant inlet keeps positive while that of the middle and outlet regions become negative, which illustrates that oxygen and proton reduction reactions could occur simultaneously in different regions at the cathode. The current distribution would be more uneven with decreasing air stoichiometry before cell reversal. When cell reversal occurs, the current will redistribute and the current distribution tends more uniform. At the critical point of cell reversal, the most significant inhomogeneity in the current distribution can be observed. The temperature distribution in the cell is also monitored on-line. The local hot spot exists in the cell when cell reversal occurs. The study of the critical reversal air stoichiometry under different loads shows that the critical reversal air stoichiometry increases with the rising loads.     

Dynamic characteristics and mitigations of hydrogen starvations in proton exchange membrane fuel cells during start-ups

Hydrogen starvation during a start-up process in proton exchange membrane (PEM) fuel cells could result in drastic local current density variations, reverse cell voltage and irreversible cell damages. In this work, variations of local current densities and temperatures are measured in situ under both potentiostatic and galvanostatic modes. Experimental results show that when the cell starts up under potentiostatic mode with hydrogen starvation, current density undershoots occur in the downstream; while under the galvanostatic mode, local current density in the downstream almost drops to zero, but the current density near the outlet remains almost constant. The phenomenon of near constant current density near the outlet leads to a novel approach to alleviate hydrogen starvations - a hydrogen reservoir is added at the anode outlet. Experimental results show that the exit hydrogen reservoir can significantly reduce the zero current region and alleviate hydrogen starvations. A non-dimensional current-density variation coefficient is proposed to measure the magnitude of local current density changes during starvations. Experimental results show that the exit hydrogen reservoir can significantly reduce the current-density variations coefficient over the entire flow channel, indicating that adding an exit reservoir is an effective approach in mitigating hydrogen starvations.     

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.     

Ir-Pt/C composite with high metal loading as a high-performance anti-reversal anode catalyst for proton exchange membrane fuel cells

Voltage reversal induced by hydrogen starvation can severely corrode the anode catalyst support and deteriorate the performance of proton exchange membrane fuel cells. A material-based strategy is the inclusion of an oxygen evolution reaction catalyst (e.g., IrO₂) in the anode to promote water electrolysis over harmful carbon corrosion. In this work, an Ir-Pt/C composite catalyst with high metal loading is prepared. The membrane-electrode-assembly (MEA) with 80 wt% Ir-Pt(1:2)/C shows a first reversal time (FRT) of up to 20 hours, which is about ten times that of MEA with 50 wt% Ir-Pt(1:2)/C does. Furthermore, the MEA with 80 wt% Ir-Pt(1:2)/C exhibits a minimum cell voltage loss of 6 mV@1 A/cm² when the FRT is terminated in 2 hours, in which the MEA with 50 wt% Ir-Pt(1:2)/C exhibits a voltage loss of 105 mV@1 A/cm². Further physicochemical and electrochemical characterizations demonstrate that the destruction of anode catalyst layer caused by the voltage reversal process is alleviated by the use of the composite catalyst with high metal loading. Hence, our results reveal that the combination of OER catalyst on the Pt/C with high metal loading is a promising approach to alleviate the degradation of anode catalyst layer during the voltage reversal process for PEMFCs.     

Impedance study of membrane dehydration and compression in proton exchange membrane fuel cells

Electrochemical impedance spectroscopy (EIS) is used to measure drying and rehydration in proton exchange membrane fuel cells running under load. The hysteresis between forward and backward acquisition of polarization curves is shown to be largely due to changes in the membrane resistance. Drying tests are carried out with hydrogen and simulated reformate (hydrogen and carbon dioxide), and quasi-periodic drying and rehydration conditions are studied. The membrane hydration state is clearly linked to the high-frequency arc in the impedance spectrum, which increases in size for dry conditions indicating an increase in membrane resistance. Changes in impedance spectra as external compression is applied to the cell assembly show that EIS can separate membrane and interfacial effects, and that changes in membrane resistance dominate. Reasons for the presence of a capacitance in parallel with the membrane resistance are discussed.     

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.     

Model-based decoupling control for the thermal management system of proton exchange membrane fuel cells

As one of the most promising sustainable energy technologies available today, proton exchange membrane fuel cell (PEMFC) engines are becoming more and more popular in various applications, especially in transportation vehicles. However, the complexity and the severity of the vehicle operating conditions present challenges to control the temperature distribution in single cells and stack, which is an important factor influencing the performance and durability of PEMFC engines. It has been found that regulating the input and output coolant water temperature can improve the temperature distribution. Therefore, the control objective in this paper is regulating the input and output temperature of coolant water at the same time. Firstly, a coupled model of the thermal management system is established based on the physical structure of PEMFC engines. Then, in order to realize the simultaneous control of the inlet and outlet cooling water temperature of the PEMFC stack, a decoupling controller is proposed and its closed-loop stability is proved. Finally, based on the actual PEMFC engine platform, the effectiveness, accuracy and reliability of the proposed decoupling controller are tested. The experimental results show that with the proposed decoupling controller, the inlet and outlet temperatures of the PEMFC stack cooling water can be accurately controlled on-line. The temperature error range is less than 0.2 °C even under the dynamic current load conditions.     

Study of the cell reversal process of large area proton exchange membrane fuel cells under fuel starvation

In this research, the fuel starvation phenomena in a single proton exchange membrane fuel cell (PEMFC) are investigated experimentally. The response characteristics of a single cell under the different degrees of fuel starvation are explored. The key parameters (cell voltage, current distribution, cathode and anode potentials, and local interfacial potentials between anode and membrane, etc.) are measured in situ with a specially constructed segmented fuel cell. Experimental results show that during the cell reversal process due to the fuel starvation, the current distribution is extremely uneven, the local high interfacial potential is suffered near the anode outlet, hydrogen and water are oxidized simultaneously in the different regions at the anode, and the carbon corrosion is proved to occur at the anode by analyzing the anode exhaust gas. When the fuel starvation becomes severer, the water electrolysis current gets larger, the local interfacial potential turns higher, and the carbon corrosion near the anode outlet gets more significant. The local interfacial potential near the anode outlet increases from ca. 1.8 to 2.6 V when the hydrogen stoichiometry decreases from 0.91 to 0.55. The producing rate of the carbon dioxide also increases from 18 to 20 ml min⁻¹.     

Pore network modeling of cathode catalyst layer of proton exchange membrane fuel cell

In this paper, a pore network model is developed to investigate the coupled transport and reaction processes in the cathode catalyst layer (CCL) of proton exchange membrane fuel cell (PEMFC). The developed model is validated by comparing the predicted polarization curve with the experimental data, and the parametric studies are carried out to elucidate the effects of CCL design parameters. With the decrease of the CCL thickness and the Nafion content, the cell voltage reduces at the low current density but increases when the current density is higher. The cell performance is also improved by increasing the proton conductivity of the Nafion film in the CCL. As compared to the CCL of uniformly distributed Nafion, the CCL with the Nafion volume decreasing along the thickness direction exhibits better performance at the high current density.     

Carbon-supported Pd-Pt cathode electrocatalysts for proton exchange membrane fuel cells

A series of carbon-supported Pd-Pt alloy (Pd-Pt/C) catalysts for oxygen reduction reaction (ORR) with low-platinum content are synthesized via a modified sodium borohydride reduction method. The structure of as-prepared catalysts is characterized by powder X-ray diffraction (XRD) and transmission electron microscope (TEM) measurements. The prepared Pd-Pt/C catalysts with alloy form show face-centered-cubic (FCC) structure. The metal particles of Pd-Pt/C catalysts with mean size of around 4-5 nm are uniformly dispersed on the carbon support. The electrocatalytic activities for ORR of these catalysts are investigated by rotating disk electrode (RDE), cyclic voltammetry (CV), single cell measurements and electrochemical impedance spectra (EIS) measurements. The results suggest that the electrocatalytic activities of Pd-Pt/C catalysts with low platinum are comparable to that of the commercial Pt/C with the same metal loading. The maximum power density of MEA with a Pd-Pt/C catalyst, the Pd/Pt mass ratio of which is 7:3, is about 1040 mW cm⁻².     

Functionalizing carbon nanotubes for proton exchange membrane fuel cells electrode

In recent years, carbon nanotubes (CNTs) have been increasingly considered as an advanced metal catalyst support for proton exchange membrane fuel cells (PEMFCs), owing to their outstanding physical and mechanical characteristics. However, the effective attachment of metal catalysts, uniformly dispersed onto the CNT surface, remains a formidable challenge because of the inertness of the CNT walls. Therefore, the surface functionalization of CNTs seems necessary in most cases in order to enable a homogeneous metal deposition. This review presents the different surface functionalization approaches that provide efficient avenues for the deposition of metal nanoparticles on CNTs, for the application of catalyst supports in PEMFCs with improved reactivity.     

Dynamic modeling of a high-temperature proton exchange membrane fuel cell with a fuel processor

A dynamic model of a high-temperature proton exchange membrane fuel cell with a fuel processor is developed in this study. In the model, a fuel processing system, a fuel cell stack, and an exhaust gas burner are modeled and integrated. The model can predict the characteristics of the overall system and each component at the steady and transient states. Specifically, a unit fuel cell model is discretized in a simplified quasi-three-dimensional geometry; therefore, the model can rapidly predict the distribution of fuel cell characteristics. Various operating conditions such as the steam-to-carbon ratio, oxygen-to-carbon ratio, and autothermal reforming inlet temperature are varied and investigated in this study. In addition, the dynamic characteristics exhibited during the transient state are investigated, and an efficiency controller is developed and implemented in the model to maintain the electrical efficiency. The simulation results demonstrate that the steam-to-carbon ratio and the oxygen-to-carbon ratio affect the electrical and system efficiency and that controlling the fuel flow rate maintains the electrical efficiency in the transient state. The model may be a useful tool for investigating the characteristics of the overall system as well as for developing optimal control strategies for enhancing the system performance.     

The dew point temperature as a criterion for optimizing the operating conditions of proton exchange membrane fuel cells

In this article an analytical method to calculate the dew point temperatures of the anode and cathode exit gas streams of a proton exchange membrane fuel cell is developed. The results of these calculations are used to create diagrams that show the dew point temperatures as function of the operating pressure, the stoichiometric flow ratios and the net drag coefficient of water through the membrane. Then, computational modeling results obtained with a previously published model are analyzed and compared with the dew point charts, and it is demonstrated how cell flooding or membrane dry-out can be predicted a priori with the aid of these diagrams. Finally, guidelines for the desired cell operating temperature based on the expected dew point temperatures are developed. In the current work these guidelines are limited to the interdigitated flow field design, and they are likely to be different for conventional flow field plates. The diagrams presented here are created for completely dry inlet gases, but they can be easily corrected for a non-zero inlet relative humidity.     

Data-based short-term prognostics for proton exchange membrane fuel cells

Prognostics is an important tool in the life and cost management of the proton exchange membrane fuel cells (PEMFCs). In this paper, we propose a data-based short-term prognostics method based on the group method of data handling and the wavelet analysis. In particular, this method first decomposes the original voltage sequence of PEMFCs into multiple sub-waveforms. Then, prognostics are made for the sub-waveforms and are combined for the overall prognostics of PEMFCs. Moreover, the proposed method is validated by the experimental datasets from real aging tests. Simulation results demonstrate that, compared with the existing approaches, this proposed method not only can achieve accurate short-term prognostics for PEMFCs in different load conditions, but also can directly use the original experimental data with large disturbances.     

Dynamic performance for a kW-grade air-cooled proton exchange membrane fuel cell stack

In this study, a kW-grade air-cooled proton exchange membrane fuel cell (PEMFC) stack with a dead-end anode (DEA) operation is designed and manufactured. The gravity-assisted drainage principle is applied for the stack to design the wettability of gas diffusion layers (GDLs) and the anode channel geometry, which can help the liquid water that diffuses to the anode to drain out of the anode porous electrode and move down the anode channel outlets. As a result, the stack can stably operate in a long purge interval of 268 s and in a short purge time of 2 s. In addition, using this design, only four small-power fans are employed to pump air to the cathode to provide oxygen for the electrochemical reaction and cool the stack. With a constant load current of 30, 45, or 60 A, the stack output voltage is experimentally tested at various cathode air flow rates (CAFRs). The local temperatures (60 measurement points) inside the stack and the pressure differences across anode channels are also monitored to understand heat dissipation and the back diffusion of liquid water. In a wide range of operating conditions, the designed stack possesses superior and stable voltage output characteristics with relatively uniform temperature distributions. The measured maximum output power is 3.83 kW, and the parasitic powers of fans are only 80～112 W.     

Stack performance of phosphotungstic acid functionalized mesoporous silica (HPW-meso-silica) nanocomposite high temperature proton exchange membrane fuel cells

In this paper, a series of short stacks with 2-cell, 6-cell and 10-cell employing phosphotungstic acid functionalized mesoporous silica (HPW-meso-silica) nanocomposite proton exchange membranes (PEMs) have been successfully fabricated, assembled and tested from room temperature to 200 °C. The effective surface area of the membrane was 20 cm² and fabricated by a modified hot-pressing method. With the 2-cell stack, the open circuit voltage was 1.94 V and it was 5.01 V for the 6-cell stack, indicating a low gas permeability of the HPW-meso-silica membranes. With the 10-cell stack, a maximum power density of 74.4 W (equivalent to 372.1 mW cm⁻²) occurs at 150 °C in H₂/O₂, and the stack produces a near-constant power output of 31.6 W in H₂/air at 150 °C without external humidification for 50 h. The short stack also displays good performance and stability during startup and shutdown cycling testing for 8 days at 150 °C in H₂/air. Although the stack test period may be too short to extract definitive conclusions, the results are very promising, demonstrating the feasibility of the new inorganic HPW-meso-silica nanocomposites as PEMs for fuel cell stacks operating at elevated temperatures in the absence of external humidification.