High-Temperature Proton Exchange Membrane Fuel Research Articles

New Multiblock Copolymers Containing Quaternary Ammonium Groups with Ultramicroporous Structure for High-Temperature Proton Exchange Membrane Fuel Cells

New Multiblock Copolymers Containing Quaternary Ammonium Groups with Ultramicroporous Structure for High-Temperature Proton Exchange Membrane Fuel Cells

Effect of Coupled Microstructural Characteristics of Catalyst Layer on High Temperature: Proton Exchange Membrane Fuel Cell Performance

Abstract The widespread adoption of High Temperature-Proton Exchange Membrane Fuel Cells (HT-PEMFC) in commercial applications is limited by their performance and durability compared to conventional energy sources. A key factor affecting these cells is the sluggish oxygen reduction reaction (ORR) at the cathode catalyst layer (CL). Optimizing the structural parameters of the cathode CL can enhance cell performance and longevity. Current research on these parameters is mostly descriptive, lacking numerical evidence to quantify their impact. This study develops a three-dimensional, non-isothermal HT-PEMFC numerical model to investigate the sensitivities of coupled structural parameters of the cathode CL, including Pt loading, CL thickness, and Pt particle diameter, at three levels. The orthogonal/Taguchi approach quantitatively assesses the impact of these parameters. The study reveals that Pt loading significantly affects cell voltage and cathode overpotential, while Pt diameter influences the homogeneity of overpotential distribution. The dominant impact of a single parameter decreases at higher current densities, necessitating careful analysis of trade-offs between different structural characteristics to maximize performance. These findings offer valuable insights for future experimental studies to enhance cell performance through adjustments to cathode catalyst characteristics.

Post mortem Study of Catalyst Degradations Occurring in High-Temperature Proton Exchange Membrane Fuel Cells Upon Start-Stop Operation

High-temperature proton exchange membrane fuel cells (HT-PEMFCs) could replace fossil fuel-based technologies for applications which cannot involve bulky/heavy cooling systems, such as aeronautics. However, severe materials degradations upon operation prevent performance retention for acceptable lifetimes. While others have already reported degradations in HT-PEMFC, post mortem characterizations of used HT-PEMFC membrane electrode assemblies (MEAs) remain scarce. Herein, HT-PEMFC performance degradation is studied by applying a startup/shutdown protocol to a short-stack operated at 160 °C; one MEA is characterized using complementary physicochemical/electrochemical techniques to identify/understand the degradation mechanisms and their origin. This start/stop operation mode (co-flow gas reactants) leads to substantial degradation inhomogeneity. For the anode, migration, coalescence, and detachment of Pt nanoparticles are witnessed induced by high-surface-area carbon support functionalization and corrosion. The anode electrochemical surface area (ECSA) remains constant at the inlet and increases significantly at the outlet, following inhomogeneous degradation of the cathode catalyst: the Ptz+ ions formed at high potential/oxidizing conditions concentrate towards the outlet, where they redeposit locally or at the anode, after diffusion/migration across the PBI membrane. Hence, the cathode ECSA decreases significantly at the inlet. Furthermore, intense Ni-leaching from the initial PtNi alloy catalyst is reported as a result of O2 mass-transport and phosphoric acid dilution inhomogeneity.

The Corrosion Characteristics of Graphite Coatings on Nickel Foam and Their Applications in High-Temperature Proton Exchange Membrane Fuel Cells

This study investigates the effectiveness of graphite coatings on nickel foam for use in high-temperature proton exchange membrane fuel cells (HT-PEMFCs). Nickel foam, known for its high porosity and good conductivity, serves as an advantageous alternative to traditional flow channels but faces corrosion challenges in HT-PEMFCs, especially from phosphoric acid leakage. Graphite coatings are used as the protection layer and compared with nitride coatings. Chemical vapor deposition process parameters are first optimized for graphite growth. Corrosion polarization curves are then measured using a high-temperature phosphoric acid three-electrode system simulating HT-PEMFC conditions, followed by an analysis of the surface morphology of the samples. Subsequently, the performance and durability of the nickel foams with different coatings are evaluated after being assembled in single fuel cells. The results highlight the superior corrosion resistance of graphite coating under HT-PEMFC conditions, demonstrating its performance over other coatings. Graphite-coated foams showed a significant reduction in corrosion current, approximately 58% lower than uncoated foams and 21% lower than the TiN coated foams. In practical applications, an HT-PEMFC single cell with graphite-coated nickel foam demonstrated a current density of 763 mA/cm2 at 0.6 V under conditions of 180 oC and 2 atm H2/air. The current density is 40% higher than that of the uncoated nickel foam. The results show notable long-term durability under constant current holding tests at 160 oC. The voltage decay rate in the graphite-coated cell was 48% lower compared to the cell with uncoated nickel forms.

Strategies for Mitigating Phosphoric Acid Leaching in High-Temperature Proton Exchange Membrane Fuel Cells.

High-temperature proton exchange membrane fuel cells (HT-PEMFCs) have become one of the important development directions of PEMFCs because of their outstanding features, including fast reaction kinetics, high tolerance against impurities in fuel, and easy heat and water management. The proton exchange membrane (PEM), as the core component of HT-PEMFCs, plays the most critical role in the performance of fuel cells. Phosphoric acid (PA)-doped membranes have showed satisfied proton conductivity at high-temperature and anhydrous conditions, and significant advancements have been achieved in the design and development of HT-PEMFCs based on PA-doped membranes. However, the persistent issue of HT-PEMFCs caused by PA leaching remains a challenge that cannot be ignored. This paper provides a concise overview of the proton conduction mechanism in HT-PEMs and the underlying causes of PA leaching in HT-PEMFCs and highlights the strategies aimed at mitigating PA leaching, such as designing crosslinked structures, incorporation of hygroscopic nanoparticles, improving the alkalinity of polymers, covalently linking acidic groups, preparation of multilayer membranes, constructing microporous structures, and formation of micro-phase separation. This review will offer a guidance for further research and development of HT-PEMFCs with high performance and longevity.

Overcoming Challenges in Ion-Pair Membrane Technology: Advancements in Fuel Cells and Electrochemical Hydrogen Pumps

The Membrane Electrode Assembly (MEA) stands as the pivotal element in electrochemical devices such as fuel cells and electrochemical hydrogen pumps (EHP). Notably, ion-pair High-Temperature Proton Exchange Membrane Fuel Cells (HT-PEMFCs) with reduced phosphoric acid concentrations within the MEA have been innovatively designed, allowing for the integration of diverse ion-conducting binders, known as ionomers, into both the cathode and anode electrodes [1]. This study delineates initial distinctions in MEA configurations among different device types (HT-Fuel cell and EHP), conducting a comprehensive analysis of performance disparities between traditional polybenzimidazole-based systems and various ion-pair proton exchange membranes [2].Subsequently, a detailed exploration unfolds, focusing on the utilization of ion-pair membranes and different ionomer types for the three aforementioned devices. This comprehensive examination offers a unified comparative analysis encompassing ionomer type, membrane thickness, catalyst:ionomer ratio, and phosphoric acid doping levels, particularly in the context of performance at intermediate temperatures (160℃). Conclusions are drawn based on results derived from both half-cell and single-cell evaluations. Finally, overarching guidelines are presented to inform the formulation of high-performance MEA configurations tailored for ion-pair HT-PEMFCs and EHPs.

Simulation Examination of the Impact of Operating Parameters on a High-Temperature Proton Exchange Membrane Fuel Cell

Simulation Examination of the Impact of Operating Parameters on a High-Temperature Proton Exchange Membrane Fuel Cell

Design, modeling, and optimization of a novel 6 kWe hybrid solid oxide fuel cell high temperature-proton exchange membrane fuel cell system

This work investigates a novel approach in terms of design, configuration, heat integration and optimization of a 6 kWe total energy system fueled with natural gas. Specifically, a Solid Oxide Fuel Cell (SOFC) is used for both electricity generation and fuel reforming, since its exhaust stream fuels a polybenzimidazole (PBI)-based, High Temperature-Proton Exchange Membrane Fuel Cell (HT-PEMFC). The study investigates the possible advantages of such a system in both technical and economic terms. After modeling each component/subsystem, the total system model is optimized with the objective function aiming to maximize the net electrical efficiency of the total hybrid system. The system is optimized with a genetic algorithm-based optimization strategy, reaching a net electrical efficiency of 43.6 %. In comparison to standalone fuel cell systems with the same net electrical power output, the proposed hybrid system outperforms both an HT-PEMFC system and an SOFC system, which perform at net electrical efficiencies of 23.2 % and 40.7 %, respectively. Also, the lifecycle cost for the proposed system is $64,097, which is lower than both standalone HT-PEMFC and SOFC systems. Therefore, with the current high rising costs for natural gas, such highly efficient systems are likely to become important elements of the future energy infrastructure.

Influence of the Polymer Precursor Structure on the Porosity of Carbon Nanofibers: Application as Electrode in High-Temperature Proton Exchange Membrane Fuel Cells

Influence of the Polymer Precursor Structure on the Porosity of Carbon Nanofibers: Application as Electrode in High-Temperature Proton Exchange Membrane Fuel Cells

Grafting of Amine End-Functionalized Side-Chain Polybenzimidazole Acid-Base Membrane with Enhanced Phosphoric Acid Retention Ability for High-Temperature Proton Exchange Membrane Fuel Cells.

A high phosphoric acid uptake and retention capacity are crucial for the high performance and stable operation of phosphoric acid/polybenzimidazole (PA/PBI)-based high-temperature proton exchange membranes. In this work, amine end-functionalized side-chain grafted PBI (AGPBI) with different grafting degrees are synthesized to enhance both the phosphoric acid uptake and the acid retention ability of the accordingly formed membranes. The optimized acid-base membrane exhibits a PA uptake of 374.4% and an anhydrous proton conductivity of 0.067 S cm-1 at 160 °C, with the remaining proton conductivity percentages of 91.0% after a 100 h stability test. The accordingly fabricated membrane electrode assembly deliver peak power densities of 0.407 and 0.638 W cm-2 under backpressure of 0 and 200 kPa, which are significantly higher than 0.305 and 0.477 W cm-2 for the phosphoric acid-doped unmodified PBI membrane under the same conditions.

Impact of Nonuniform Platinum Loading Distribution Design in the Catalyst Layer on the High-Temperature Proton Exchange Membrane Fuel Cell Performance

Impact of Nonuniform Platinum Loading Distribution Design in the Catalyst Layer on the High-Temperature Proton Exchange Membrane Fuel Cell Performance

Multi-Objective Assessment and Optimization of a High-Temperature Proton Exchange Membrane Fuel Cell: Steady-State Analysis

The design and operational conditions of high-temperature proton exchange membrane fuel cells (HT-PEMFCs) substantially impact their performance. This model aims to investigate the influence of various parameters on the performance of HT-PEMFC. A comprehensive examination revealed that the performance of HT-PEMFC experienced a significant enhancement through modifications to the operating temperature, doping levels, and membrane thickness. Significantly, it can be observed that operating pressure showed a limited influence on performance. The HT-PEMFC was optimized using the non-dominated sorting genetic algorithm II (NSGA-II), specifically emphasizing three primary performance indicators: equivalent power density, energy efficiency, and exergy efficiency. The findings demonstrate promising outcomes, as they reveal a noteworthy enhancement in power density by 17.72% and improvements in energy efficiency and exergy efficiency by 21.11% and 10.37%, respectively, compared to the baseline case.

Guanidinium/Hydroxyl-Functionalized Polybenzimidazole for High-Temperature Proton Exchange Membrane Fuel Cell Applications

Guanidinium/Hydroxyl-Functionalized Polybenzimidazole for High-Temperature Proton Exchange Membrane Fuel Cell Applications

Insights into Oxygen Mass Transport Mechanisms in High-Temperature Proton Exchange Membrane Fuel Cells with Microelectrode

The mass transport of oxygen in the cathode catalyst layer of high-temperature proton exchange membrane fuel cells (HT-PEMFCs) has a great impact on cell performance. However, some bulk average methods are unable to study the permeation properties of oxygen near the triple phase boundary of HT-PEMFCs due to the size mismatch. Here, we develop a microelectrode integrated system to quantitatively study the O2 mass transport behavior at the Pt/binder interface under actual operating temperatures (100 °C–180 °C). The oxygen diffusion coefficients and solubility obtain from potential-step chronoamperometry and a modified Cottrell equation follow the diffusion “ball-cage” model and the dual-mode solubility model. Subsequently, molecular dynamics simulations are used to describe the key structural elements and diffusion behavior of oxygen molecules from the microscopic perspective. These results provide a scientific approach to study the mass transfer process of oxygen at the local environment, endowing with insightful strategies for future improvement and applications of HT-PEMFCs.

Experimental Analysis of Catalyst Layer Operation in a High-Temperature Proton Exchange Membrane Fuel Cell by Electrochemical Impedance Spectroscopy

High-temperature proton exchange membrane fuel cells (HT-PEMFC) directly convert hydrogen and oxygen to produce electric power at a temperature significantly higher than conventional low-temperature fuel cells. This achievement is due to the use of a phosphoric acid-doped polybenzimidazole membrane that can safely operate up to 200 °C. PBI-based HT-PEMFCs suffer severe performance limitations, despite the expectation that a higher operating temperature should positively impact both fuel cell efficiency and power density, e.g., improved ORR electrocatalyst activity or absence of liquid water flooding. These limitations must be overcome to comply with the requirements in mobility and stationary applications. In this work a systematic analysis of an HT-PEMFC is performed by means of electrochemical impedance spectroscopy (EIS), aiming to individuate the contributions of components, isolate physical phenomena, and understand the role of the operating conditions. The EIS analysis indicates that increases in both the charge transfer and mass transport impedances in the spectrum are negatively impacted by air humidification and consistently introduce a loss in performance. These findings suggest that water vapor reduces phosphoric acid density, which in turn leads to liquid flooding of the catalyst layers and increases the poisoning of the electrocatalyst by phosphoric acid anions, thus hindering performance.

Performance, Efficiency, and Flexibility Analysis of a High-Temperature Proton Exchange Membrane Fuel Cell-Based Micro-Combined Heat-and-Power System with Intensification of the Steam Methane Reforming Step by Using a Millistructured Reactor.

The complete simulation model of an existing 1 kW high-temperature proton exchange membrane (HT-PEM) fuel cell-based residential micro-combined heat-and-power process, including a compact intensified heat-exchanger-reactor, is developed in the simulation software ProSimPlus v3.6.16. Detailed simulation models of the heat-exchanger-reactor, a mathematical model of the HT-PEM fuel cell, and other components are presented. The results obtained by the simulation model and by the experimental micro-cogenerator are compared and discussed. To fully understand the behavior of the integrated system and assess its flexibility, a parametric study is performed considering fuel partialization and important operating parameters. The values of the air-to-fuel ratio = [30, 7.5] and steam-to-carbon ratio = 3.5 (corresponding to net electrical and thermal efficiencies of 21.5 and 71.4%) are chosen for the analysis of inlet/outlet component temperatures. Finally, the exchange network analysis of the full process proves that the process efficiencies can still be increased by further improving the process internal heat integration.

A Comparative Study of CCM and CCS Membrane Electrode Assemblies for High-Temperature Proton Exchange Membrane Fuel Cells with a CsH5(PO4)2-Doped Polybenzimidazole Membrane.

Membrane electrode assemblies (MEAs) are critical components in influencing the electrochemical performance of high-temperature proton exchange membrane fuel cells (HT-PEMFCs). MEA manufacturing processes are mainly divided into the catalyst-coated membrane (CCM) and the catalyst-coated substrate (CCS) methods. For conventional HT-PEMFCs based on phosphoric acid-doped polybenzimidazole (PBI) membranes, the wetting surface and extreme swelling of the PA-doped PBI membranes make the CCM method difficult to apply to the fabrication of MEAs. In this study, by taking advantage of the dry surface and low swelling of a CsH5(PO4)2-doped PBI membrane, an MEA fabricated by the CCM method was compared with an MEA made by the CCS method. Under each temperature condition, the peak power density of the CCM-MEA was higher than that of the CCS-MEA. Furthermore, under humidified gas conditions, an enhancement in the peak power densities was observed for both MEAs, which was attributed to the increase in the conductivity of the electrolyte membrane. The CCM-MEA exhibited a peak power density of 647 mW cm-2 at 200 °C, which was ~16% higher than that of the CCS-MEA. Electrochemical impedance spectroscopy results showed that the CCM-MEA had lower ohmic resistance, which implied that it had better contact between the membrane and catalyst layer.

Phosphonated Ionomers of Intrinsic Microporosity with Partially Ordered Structure for High-Temperature Proton Exchange Membrane Fuel Cells.

High mass transport resistance within the catalyst layer is one of the major factors restricting the performance and low Pt loadings of proton exchange membrane fuel cells (PEMFCs). To resolve the issue, a novel partially ordered phosphonated ionomer (PIM-P) with both an intrinsic microporous structure and proton-conductive functionality was designed as the catalyst binder to improve the mass transport of electrodes. The rigid and contorted structure of PIM-P limits the free movement of the conformation and the efficient packing of polymer chains, resulting in the formation of a robust gas transmission channel. The phosphonated groups provide sites for stable proton conduction. In particular, by incorporating fluorinated and phosphonated groups strategically on the local side chains, an orderly stacking of molecular chains based on group assembly contributes to the construction of efficient mass transport pathways. The peak power density of the membrane electrode assembly with the PIM-P ionomer is 18-379% greater than that of those with commercial or porous catalyst binders at 160 °C under an H2/O2 condition. This study emphasizes the crucial role of ordered structure in the rapid conduction of polymers with intrinsic microporosity and provides a new idea for increasing mass transport at electrodes from the perspective of structural design instead of complex processes.

Construction of Highly Conductive Cross-Linked Polybenzimidazole-Based Networks for High-Temperature Proton Exchange Membrane Fuel Cells

High-temperature proton exchange membrane fuel cells (HT-PEMFCs) are of great interest to researchers in industry and academia because of their wide range of applications. This review lists some creative cross-linked polybenzimidazole-based membranes that have been prepared in recent years. Based on the investigation into their chemical structure, the properties of cross-linked polybenzimidazole-based membranes and the prospect of their future applications are discussed. The focus is on the construction of cross-linked structure of various types of polybenzimidazole-based membranes and their effect on proton conductivity. This review expresses the outlook and good expectation of the future direction of cross-linked polybenzimidazole membranes.

Thermodynamic Modeling and Exergy Analysis of A Combined High-Temperature Proton Exchange Membrane Fuel Cell and ORC System for Automotive Applications

A combined system consisting of a high-temperature proton exchange membrane fuel cell (HT-PEMFC) and an organic Rankine cycle (ORC) is provided for automotive applications in this paper. The combined system uses HT-PEMFC stack cathode exhaust gas to preheat the inlet gas and the ORC to recover the waste heat from the stack. The model of the combined system was developed and the feasibility of the model was verified. In addition, the evaluation index of the proposed system was derived through an energy and exergy analysis. The numerical simulation results show that the HT-PEMFC stack, cathode heat exchanger, and evaporator contributed the most to the total exergy loss of the system. These components should be optimized as a focus of future research to improve system performance. The lower current density increased the ecological function and the system efficiency, but reduced the system's net out-power. A higher inlet temperature and higher hydrogen pressures of the stack and the lower oxygen pressure helped improve the system performance. Compared to the HT-PEFC system without an ORC subsystem, the output power of the combined system was increased by 12.95%.