Carbon nanotubes reinforced proton exchange membranes in fuel cells: An overview

The proton exchange membrane (PEM) is the core component in a fuel cell. In this review, recent progress and developments on per-fluorinated and non-fluorinated membranes with carbon nanotubes (CNTs) as reinforced fillers have been summarized on many key topics. Topics reviewed stem from correlating the mechanical stability, thermal stability, water retention capacity and proton conductivity of various membranes across different functionalized CNTs. In addition, topics such as the preparation strategies of membrane matrix and CNTs filler, the reinforced mechanism of CNTs in membrane are presented. Throughout, the impact of interactions between CNTs and various types of PEM is also discussed to present a deeper perspective. Finally, the strategy for improving the performance of PEM and the challenges of CNTs-based membranes are analyzed for prospects.     

Chemical durability of thin pore-filling membrane in open-circuit voltage hold test

Long-term chemical stability of proton exchange membranes in polymer electrolyte fuel cells (PEFCs) is an important issue for widespread commercialization. Here, we report on the chemical stability of a membrane-electrode assembly with a 7 μm thick pore-filling membrane (porous substrate filled with high ion exchange capacity perfluorosulfonic acid (PFSA) polymer) using an open-circuit voltage hold test. The very thin pore-filling membrane shows comparable chemical durability to Nafion 211. Interestingly, the pore-filling membrane shows a different degradation behavior from Nafion 211 due to the use of chemically and mechanically stable porous substrate, with no thickness change and little amounts of fluorine leakages are observed in the pore-filling membrane compared to membrane thinning and large amounts of fluorine leakage in Nafion 211. The thin pore-filling membrane shows promise for application in PEFCs, as it balances high fuel cell performance at high temperature and low relative humidity with high chemical durability.     

Performance deterioration and recovery in high-temperature polymer electrolyte membrane fuel cells: Effects of deliquescence of phosphoric acid

Phosphoric acid (PA)-doped polybenzimidazole (PBI) membranes used in high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) have high proton conductivity, and excellent mechanical and thermal stability. However, the deliquescence of PA leads to performance deterioration in humid atmosphere. The performance degradation upon exposure of the PA-doped membrane to humidity and the changes in the performance as a function of the PA loading in the electrodes are investigated. The performance of the HT-PEMFC employing the humidity-exposed membrane declines by 74.1% compared to that of the pristine membrane due to ineffective formation of the three-phase boundary. Loading a small amount of PA into the electrode induces drastic performance recovery with a decrease in the charge transfer resistance, especially at the anode. PA-dosing of both electrodes produces the best performance recovery, exceeding that of the pristine counterparts. This is a simple and effective method of recovering the performance of HT-PEMFCs after humidity-related deterioration.     

Enhanced proton conductivity from phosphoric acid-imbibed crosslinked 3D polyacrylamide frameworks for high-temperature proton exchange membranes

To enhance the proton conductivity of high-temperature proton exchange membranes (PEMs), one promising approach is to increase the proton conductor loading per unit membrane. The objectives of this research are to demonstrate the feasibility of the concept and realize H₃PO₄-imbibed polyacrylamide (PAM) frameworks as high-temperature PEMs using the unique absorption and retention of crosslinked PAM to H₃PO₄ aqueous solution. The 3D framework of PAM provides space to hold H₃PO₄ into the porous structure, which can be controlled by adjusting the polymerization process and crosslinking agent and initiator dosages. Results show that the H₃PO₄ loadings and therefore the conductivities of the membranes are significantly enhanced by expanding the size of pore structure. Proton conductivities as high as 0.0749 S cm⁻¹ at ambient-temperature and fully hydrated state and 0.0635 S cm⁻¹ at 183 °C under anhydrous atmosphere are recorded. The high conductivities at high temperatures in combination with the simple preparation, low cost, scalable hosts and proton conductors demonstrate the potential use of hydrogel materials in high-temperature PEMs.     

A review on current trends in potential use of metal-organic framework for hydrogen storage

Hydrogen can be a promising clean energy carrier for the replenishment of non-renewable fossil fuels. The set back of hydrogen as an alternative fuel is due to its difficulties in feasible storage and safety concerns. Current hydrogen adsorption technologies, such as cryo-compressed and liquefied storage, are costly for practical applications. Metal-organic frameworks (MOFs) are crystalline materials that have structural versatility, high porosity and surface area, which can adsorb hydrogen efficiently. Hydrogen is adsorbed by physisorption on the MOFs through weak van der Waals force of attraction which can be easily desorbed by applying suitable heat or pressure. The strategies to improve the MOFs surface area, hydrogen uptake capacities and parameters affecting them are studied. Hydrogen spill over mechanism is found to provide high-density storage when compared to other mechanisms. MOFs can be used as proton exchange membranes to convert the stored hydrogen into electricity and can be used as electrodes for the fuel cells. In this review, we addressed the key strategies that could improve hydrogen storage properties for utilizing hydrogen as fuel and opportunities for further growth to meet energy demands.     

Numerical study of cold start performance of proton exchange membrane fuel cell with coolant circulation

It has been well recognized that cold start is one of the key issues of proton exchange membrane fuel cell (PEMFC) used as the engine of vehicles. Coolant circulation is usually launched synchronously with the fuel cell during cold start to avoid sudden large temperature variation, which greatly increases the cell thermal mass, lowers the heating rate, and worsens the cell performance. Considering the flow and heat transfer of coolant circulation, a three-dimensional, transient, multi-disciplinary model for cold start is built up. The numerical results agree reasonably well with experimental data, indicating that the model can be used for the investigation of PEMFC cold start processes. The analysis of circulation parameter effects shows that increasing the coolant flow rate or coolant tank capacity has little influence on the cell voltage, but will increase the non-uniformity of temperature distribution along flow direction. At lower start-up temperature, this non-uniformity is more obvious. With higher coolant flow rate, although the distribution of current density becomes more evenly, the ice formation amount increases and its distribution and location are greatly affected.     

A comprehensive review on water management strategies and developments in anion exchange membrane fuel cells

In spite of significant achievements in alkaline exchange membrane fuel cells (AEMFCs) in recent years, they are still lagging behind proton exchange membrane fuel cells (PEMFCs) due to performance instability. Among the relevant operational parameters of AEMFC, the researchers have found that poor water management within the cell was the main reason for failure of the system. In the past five years, numerous modeling and experimental works were reported proposing different strategies to improve water management of AEMFC. With proper water management, the achievable power output in AEMFCs is comparable with that of PEMFCs or even more. Efforts have to be continued, but AEMFCs can become a strong competitor in the market place. This review paper discusses the strategies and developments impacting water management of AEMFCs providing knowledge source for upcoming studies.     

Optimization of the bipolar plate rib structure in proton exchange membrane fuel cells with an analytical method

In order to make proton exchange membrane fuel cell vehicles more marketable, not only should costs be reduced, but service life should also be further increased. Important factors determining the expected service life are the deformation and the stress distribution within the carbon paper gas diffusion layer (GDL), on which the rib structure of the bipolar plates (BPP) has a significant impact. Against this background, a new analytical method is firstly developed to predict the deformation and stress distribution within the GDL, due to compression by the ribs, with high accuracy and low computing resources. Based on the analytical method, a new parabolic rib geometry is then proposed, which can significantly reduce the maximum normal and shear stresses occurring within the GDL, thus reducing the possibility of its mechanical damage. The optimized rib design provides guidance for designing and processing commercial fuel cell BPPs.     

Additives in proton exchange membranes for low- and high-temperature fuel cell applications: A review

Polymer electrolyte membranes, also known as proton exchange membranes (PEMs), are a type of semipermeable membrane that exhibits the property of conducting ions while impeding the mixing of reactant materials across the membrane. Due to the large potential and substantial number of applications of these materials, the development of proton exchange membranes (PEMs) has been in progress for the last few decades to successfully replace the commercial Nafion^® membranes. In the course of this research, an alternate perspective of PEMs has been initiated with a desire to attain successful operations at higher working temperatures (120–200 °C) while retaining the physical properties, stability and high proton conductivity. Both low- and high-temperature PEMs have been fabricated by various processes, such as grafting, cross-linking, or combining polymer electrolytes with nanoparticles, additives and acid-base complexes by electrostatic interactions, or by employing layer-by-layer technologies. The current review suggests that the incorporation of additives such as plasticisers and fillers has proven potential to modify the physical and chemical properties of pristine and/or composite membranes. In many studies, additives have demonstrated a substantial role in ameliorating both the mechanical and electrical properties of PEMs to make them effective for fuel cell applications. It is notable that plasticiser additives are less desirable for the development of high-temperature PEMs, as their inherent highly hydrophilic properties may stiffen the membrane. Conversely, filler additives form an inorganic-organic composite with increased surface area to retain more bound water within the polymer matrices to overcome the drawbacks of ohmic losses at high operating temperatures.     

Proton exchange membrane from the blend of poly(vinylidene fluoride) and functional copolymer: Preparation,proton conductivity,methanol permeability,and stability

A polymer electrolyte membrane is considered as the heart of fuel cells. Here we report the preparation of proton exchange membranes (PEMs) of poly (vinylidene fluoride) (PVDF) blend poly (methyl methacrylate)-co-poly (sodium-4-styrene sulfonate) (PMMA-co-PSSNa) by solvent evaporation method. Three different types of PEMs have been prepared by using different ratios of PVDF and PMMA-co-PSSNa copolymer. We have investigated the effect of concentration of PVDF on water uptake, ion exchange capacity, mechanical, thermal, and oxidative stability, proton conductivity (K^m), and methanol permeability (P_M) of the blend membranes. These blend PEMs showed good physicochemical and electrochemical properties along with thermal and oxidative stability. The membrane prepared from PVDF (45% w/w) to PMMA-co-PSSNa (55% w/w) exhibited optimum P_M at room temperature (8.38 × 10^?7 cm²s^?1). This low fuel crossover and high relative selectivity can make our prepared blend membranes a potential candidate in polymer electrolyte membrane fuel cells (PEMFCs) or direct methanol fuel cells (DMFCs).     

Effects of branching structures on the properties of phosphoric acid-doped polybenzimidazole as a membrane material for high-temperature proton exchange membrane fuel cells

Highly branched copolymers have gained widespread attention due to their outstanding properties as proton exchange membranes (PEMs). However, the utilization of phosphoric acid-doped branched polybenzimidazole (PBI) as a PEM is rarely reported, and thus, the effects of branched structures on the properties of branched PBI membranes are not clear. In this work, three kinds of branched PBIs were prepared as high-temperature PEMs (HT-PEMs), and the branched polymer with the highest degree of branching was synthesized by introducing a branching agent with a large volume and rigid structure. In addition, the properties of the branched polymer membranes, such as the phosphoric acid doping content, proton conductivity, and oxidative stability, were characterized. The branched PBI membrane with the highest branching degree (9%) exhibited the highest proton conductivity (0.053 S cm^?1) and resistance to oxidation (only 6.9% reduction in weight following immersion in Fenton's reagent for 180 h). Furthermore, the proton conductivity and oxidative stability of the branched PBI membranes improved with increasing degree of branching. From these results, we infer that highly branched PBI is a promising material for application in the HT-PEMs of fuel cells.     

Incorporation of H3PO4 into three-dimensional polyacrylamide-graft-starch hydrogel frameworks for robust high-temperature proton exchange membrane fuel cells

To enhance the anhydrous proton conductivities of proton exchange membranes, we report here the incorporation of H₃PO₄ into three-dimensional (3D) framework of polyacrylamide-graft-starch (PAAm-g-starch) hydrogel materials using extraordinary absorption of hydrogels to H₃PO₄ aqueous solution. Intrinsic microporous structure can close to seal H₃PO₄ molecules in the interconnected 3D frameworks of PAAm-g-starch after suffering from dehydration. The hydrogel membranes are thoroughly characterized by morphology observation, thermal stability, swelling kinetics, proton-conducting performances as well as electrochemical behaviors. The results show that the H₃PO₄ loadings and therefore the proton conductivities of the hydrogel membranes are dramatically enhanced by employing PAAm-g-starch matrix. H₃PO₄ loading of 88.68 wt% and an anhydrous proton conductivity as high as 0.046 S cm⁻¹ at 180 °C are recorded. A fuel cell using a thick membrane shows a peak power density of 517 mW cm⁻² at 180 °C by feeding with H₂/O₂ streams. The high H₃PO₄ loading, reasonable proton conductivity in combination with simple preparation, low cost and scalable matrix demonstrates the potential use of PAAm-g-starch hydrogel membranes in high-temperature proton exchange membrane fuel cells.     

Enhancement of proton conductivity of polymer electrolyte membrane enabled by sulfonated nanotubes

Proton exchange membrane (PEM) with high proton conductivity is crucial to the commercial application of PEM fuel cell. Herein, sulfonated halloysite nanotubes (SHNTs) with tunable sulfonic acid group loading were synthesized and incorporated into sulfonated poly(ether ether ketone) (SPEEK) matrix to prepare nanocomposite membranes. Physicochemical characterization suggests that the well-dispersed SHNTs enhance the thermal and mechanical stabilities of nanocomposite membranes. The results of water uptake, ionic exchange capacity, and proton conductivity corroborate that the embedded SHNTs interconnect the ionic channels in SPEEK matrix and donate more continuous ionic networks. These networks then serve as proton pathways and allow efficient proton transfer with low resistance, affording enhanced proton conductivity. Particularly, incorporating 10% SHNTs affords the membrane a 61% increase in conductivity from 0.0152 to 0.0245 S cm⁻¹. This study may provide new insights into the structure-properties relationships of nanotube-embedded conducting membranes for PEM fuel cell.     

Increases in the proton conductivity and selectivity of proton exchange membranes for direct methanol fuel cells by formation of nanocomposites having proton conducting channels

We explore an approach to effectively enhance the properties of cost-effective hydrocarbon proton-exchange membranes for application in the direct methanol fuel cell (DMFC). This approach utilizes sulfonated silica nanoparticles (SA-SNP) as additives to modify sulfonated poly(arylene ether ether ketone ketone) (SPAEEKK). The interaction between the sulfonic acid groups of SA-SNP and those of SPAEEKK combined with hydrophilic-hydrophobic phase separation induce the formation of proton conducting channels, as evidenced by TEM images, which contribute to increases in the proton conductivity of the SPAEEKK/SA-SNP nanocomposite membrane. The presence of SA-SNP nanoparticles also reduces methanol crossover in the membrane. Therefore, the SPAEEKK/SA-SNP nanocomposite membrane shows a high selectivity, which is 2.79-fold the selectivity of Nafion^®117. The improved selectivity of the SPAEEKK/SNP nanocomposite membrane demonstrates potential of this approach in providing hydrocarbon-based PEMs as alternatives to Nafion in direct methanol fuel cells.     

An enhanced proton conductivity and reduced methanol permeability composite membrane prepared by sulfonated covalent organic nanosheets/Nafion

Sulfonated covalent organic nanosheets (SCONs) with a functional group (−SO₃H) are effective at reducing ion channels length and facilitating proton diffusion, indicating the potential advantage of SCONs in application for proton exchange membranes (PEMs). In this study, Nafion-SCONs composite membranes were prepared by introducing SCONs into a Nafion membrane. The incorporation of SCONs not only improved proton conductivity, but also suppressed methanol permeability. This was due to the even distribution of ion channels, formed by strong electrostatic interaction between the well dispersed SCONs and Nafion polymer molecules. Notably, Nafion-SCONs-0.6 was the best choice of composite membranes. It exhibited enhanced performance, such as high conductivity and low methanol permeability. The direct methanol fuel cell (DMFC) with Nafion-SCONs-0.6 membrane also showed higher power density (118.2 mW cm⁻²), which was 44% higher than the cell comprised of Nafion membrane (81.9 mW cm⁻²) in 2 M methanol at 60 °C. These results enabled us to work on building composite membranes with enhanced properties, made from nanomaterials and polymer molecules.     

Conductivity of aromatic-based proton exchange membranes at subzero temperatures

Stable proton exchange membrane (PEM) with good proton conductivity at subzero temperatures is important for the development of PEM fuel cell cold start. In this work, subfreezing conductivity was reported for several aromatic-based PEMs including sulfonated polyimides (SPIs) with three values of ion-exchange capacity (IEC), sulfonated poly(ether ether ketone) (SPEEK) and disulfonated poly(arylene ether sulfone) copolymer (SPSU) as well as Nafion^® 212. Measurements were performed using the electrochemical impedance spectroscopy (EIS) technique. The results showed that only fully hydrated SPEEK (IEC, 1.75) and SPSU (IEC, 2.08) had comparable conductivities with Nafion^® 212 at subzero temperatures. Considering implement of gas purge before subzero storage of PEM fuel cell, the conductivity for those PEMs humidified by water vapor at activity of 0.75 was also investigated. The state of water in aromatic-based PEMs was quantified by differential scanning calorimetry (DSC), and its correlation with conductivity of the membrane was also discussed.     

Cold-start icing characteristics of proton-exchange membrane fuel cells

Understanding the icing characteristics of proton-exchange membrane fuel cells (PEMFCs) is essential for optimizing their cold-start performance. This study examined the effects of start-up temperature, current density, and microporous layer (MPL) hydrophobicity on the cold-start performance and icing characteristics of PEMFCs. Further, the cold-start icing characteristics of PEMFCs were studied by testing the PEMFC output voltage, impedance, and temperature changes at different positions of the cathode gas diffusion layer. Observation of the MPL surface after cold-start failure allowed determination of the distribution of ice formation at the catalytic layer/MPL interface. At fuel cell temperatures below 0 °C, supercooled water in the cell was more likely to undergo concentrated instantaneous freezing at higher temperatures (−4 and −5 °C), whereas the cathode tended to freeze in sequence at lower temperatures (−8 °C). In addition, a more hydrophobic MPL resulted in two successive instantaneous icing phenomena in the fuel cell and improved the cold-start performance.     

Reinforcement learning based energy management systems and hydrogen refuelling stations for fuel cell electric vehicles: An overview

This paper examines the current state of the art of hydrogen refuelling stations-based production and storage systems for fuel cell hybrid electric vehicles (FCHEV). Nowadays, the emissions are increasing rapidly due to the usage of fossil fuels and the demand for hydrogen refuelling stations (HRS) is emerging to replace the conventional vehicles with FCHEVs. Hence, the availability of HRS and its economic aspects are discussed. In addition, a comprehensive study is presented on the energy storage systems such as batteries, supercapacitors and fuel cells which play a major role in the FCHEVs. An energy management system (EMS) is essential to meet the load requirement with effective utilisation of power sources with various optimizing techniques. A detailed comparative analysis is presented on the merits of Reinforcement learning (RL) for the FCHEVs. The significant challenges are discussed in depth with potential solutions for future work.     

3D multiphysics modeling aided APU development for vehicle applications: A thermo-structural investigation

Solid oxide fuel cells (SOFC) are suitable for on-board electricity generation as Auxiliary Power Unit (APU) to support the electric power supply in heavy-duty vehicles. In order to satisfy the requirements of a lightweight fuel cell stack for mobile applications, thin-walled components must be used for the stack structure. This necessity is associated with material, process and design difficulties that must be solved in order to achieve a successful utilization. In this work a novel lightweight SOFC stack design with metal-supported cell was studied both numerically and experimentally. The metallic components are made from the Intermediate Temperature Metal (ITM), a high performance, high chromium ferritic stainless steels alloy. The multiphysics modeling approach (fluid dynamics, heat transfer, structural mechanics) was utilized in this work to predict the temperature distribution and the thermo-structural behavior of the new developed design. Geometric details of the fuel cell stack components as well as appropriate nonlinear, temperature and time-dependent constitutive models were developed to describe the material behavior. Experimental data were used to determine the material model parameters and validated the simulation results. The three-dimensional stress and deformation distributions in the individual stack components were evaluated and their maximum values for elements at risk were identified. Thus, the developed model enables the investigation of sustainability and serviceability of the structural elements to ensure a reliable operation of the stack. The developed computational model can be used as a design tool for parametric studies and optimization analysis to investigate the effects of process boundary conditions, material properties as well as geometrical design parameters and their variation on the induced thermal stresses.