Perfluorosulfonic Acid Research Articles

Mechanism of Ionomer Degradation as a Consequence of Defective Anode PEMFC

Defects in the various components of the membrane-electrode assembly (MEA), initially present or created during aging, are known to be responsible for the short lifetime PEMFC. Catalytic layer degradation has been identified as one of them [1]. However, the possible propagation of these defects to other components within a cell or a stack is not clear in the literature. To shed light on these phenomena, customized MEAs with a localized lack of anode active layer at two different locations -near the hydrogen inlet or outlet- were manufactured and tested with specific accelerated aging tests, combining high and low current and humidity cycles; these were specifically tailored to observe a possible propagation of the defects [2]. Local performance monitoring using a segmented cell revealed variations within the catalytic layers upstream and downstream of the defect. In order to better understand the impact of anode active layer defects on MEA components, localized physicochemical analyses were performed post mortem along the gas flow, with the main objective to identify possible degradations of the reinforced perfluorosulfonic acid (PFSA) membranes. Microscopic thickness measurements showed significant membrane thinning in the defective segments. Difference of these localized degradations between the monopolar plates rib and channel zones will be highlighted depending on the defect location i.e. at the inlet and outlet of hydrogen flow (Figure below). In the defective area, decrease of the Ion Exchange Capacity estimated by Raman analyses is pointed out for the reinforced PFSA layer. The PFSA chain degradation mechanism will be discussed, and, thus, the degradation rate will be calculated based on Raman and FTIR microscope and 19F NMR. For longer ageing time, the ionomer degradation is extended to an non-defective area. A propagation mechanism of the degradation will be proposed.[1] L, Dubau, et al. WIREs Energy and Environ. 2014, 3, pp. 540-560.[2] S, Touhami, et al. J. Power Sources. 2021, 481, pp. 228908-228917. Figure 1

Deconvolution of Charge-Transfer, Mass Transfer, and Ohmic Resistances of Phosphonic Acid-Sulfonic Acid Ionomer Binders in Electrochemical Hydrogen Pumps

Ion-pair high-temperature polymer electrolyte membranes (HT-PEMs) paired with phosphonic acid ionomer electrode binders have substantially improved the performance of HT-PEM electrochemical hydrogen pumps (EHPs)1, 2 and fuel cells3. Recently, blending poly(pentafluorstyrene-co-tetrafluorostyrene phosphonic acid) (PTFSPA) with NafionTM improved ionomer conductivity under anhydrous conditions in the temperature range of 100 °C to 250 °C. Using the said polymer blend as an electrode binder resulted in a 2 W.cm-2 peak power density of fuel cells4 at 240 °C (a HT-PEM fuel cell record). However, much is still unknown about how phosphonic acid ionomers blended with perfluorosulfonic acid (PFSA) materials affect electrode kinetics and gas transport in porous electrodes. In this work, we studied the ionic conductivity, electrode kinetics, and gas transport resistance of 3 types of phosphonic acid ionomers, poly(vinyl phosphonic acid), poly(vinyl benzyl phosphonic acid) by themselves and when blended with Aquivion®. These studies were performed in the context of an EHP platform – both membrane electrode assemblies (MEAs) and interdigitated electrode arrays (IDAs) decorated with nanoscale platinum electrocatalysts with thin film ionomer electrolytes. For all phosphoric acid ionomer types, the addition of Aquivion® promoted ionic conductivity, hydrogen oxidation/evolution reaction kinetics (HOR/HER), and hydrogen gas permeability. Solid-state 31P NMR revealed that the addition of Aquivion® significantly reduced phosphate ester formation in phosphoric acid ionomers and this played a vital role in enhancing ionomer blend conductivity. Using the best blend variant, PTFSPA-Aquivion®, a remarkable EHP performance of 5.1 A.cm-2 at 0.4 V at T = 200 °C was attained. Density functional theory (DFT) simulations identified that phosphonic acids with electron-withdrawing moieties reduced the propensity of the phosphonic acid to adsorb to platinum electrocatalyst surfaces. All phosphonic acid ionomers are anticipated to have a greater affinity for adsorption on platinum when compared to sulphonic acid ionomers (PFSAs). The relative adsorption affiliation of the various phosphoric acid ionomers from DFT is consistent with an explanation that stronger anion-specific adsorption has a detrimental impact and is commensurate with experimentally obtained MEA charge-transfer kinetics. A machine learning-aided compositional model5 revealed that the addition of Aquivion® reduced activation and concentration overpotentials in EHP MEAs and improved exchange current density and diffusivity in EHP IDAs. Future work involves employing the EHPs in a real-world application for separating and compressing hydrogen from the natural gas mixture.References Venugopalan, G.; Bhattacharya, D.; Andrews, E.; Briceno-Mena, L.; Romagnoli, J.; Flake, J.; Arges, C. G., Electrochemical Pumping for Challenging Hydrogen Separations. ACS Energy Letters 2022, 7 (4), 1322-1329.Venugopalan, G.; Bhattacharya, D.; Kole, S.; Ysidron, C.; Angelopoulou, P. P.; Sakellariou, G.; Arges, C. G., Correlating high temperature thin film ionomer electrode binder properties to hydrogen pump polarization. Materials Advances 2021, 2 (13), 4228-4234.Atanasov, V.; Lee, A. S.; Park, E. J.; Maurya, S.; Baca, E. D.; Fujimoto, C.; Hibbs, M.; Matanovic, I.; Kerres, J.; Kim, Y. S., Synergistically integrated phosphonated poly(pentafluorostyrene) for fuel cells. Nat Mater 2021, 20 (3), 370-377.Lim, K. H.; Lee, A. S.; Atanasov, V.; Kerres, J.; Park, E. J.; Adhikari, S.; Maurya, S.; Manriquez, L. D.; Jung, J.; Fujimoto, C.; Matanovic, I.; Jankovic, J.; Hu, Z.; Jia, H.; Kim, Y. S., Protonated phosphonic acid electrodes for high power heavy-duty vehicle fuel cells. Nature Energy 2022, 7 (3), 248-259.Briceno-Mena, L. A.; Venugopalan, G.; Romagnoli, J. A.; Arges, C. G., Machine learning for guiding high-temperature PEM fuel cells with greater power density. Patterns 2021, 2 (2), 100187. Figure 1

(Keynote) Polyoxometallate Functionalized Membranes for Next Generation Fuel Cells, Electrolyzers and Other Devices

Using polyoxometalate moieties we are developing proton conducting membranes for proton exchange membrane fuel cells, electrolyzers and other devices that can solve the durability and environmental challenges and temperature limitations facing the state of the state-of-the-art perfluorinated sulfonic acid-based membranes. During recent work with perfluorinated membranes we have shown how to achieve stability enhancement that easily exceeds the Fuel Cell DOE accelerated stress tests (AST) for chemical stability and mechanical durability requirements for light duty vehicles. This indicates the potential of these For this perfluorinated polymer-HPA combination we obtained higher performance than the current state-of-the-art PFSAs under high humidity conditionsHPA moieties to give oxidative stability to hydrocarbon membranes as well. New membrane technology we are working on will utilize covalently bound heteropoly acids (HPA), inorganic super acids, that have both some of the highest proton conductivities when wet and have been proven to catalytically decompose oxygenated radicals that destroy existing membranes. We have already demonstrated similar membranes in fuel cells with high performance and some of the most stable long term durability ever demonstrated. In fuel cells, the materials always performed beyond state-of the-art when in humid conditions but struggled when the cells became dry, as electrolysis applications feeds water to the cell we have very high confidence that we will be able to easily exceed electrolyzer performance targets. We are improving upon this polymer chemistry and are now tailoring it specifically to electrolysis. When configured correctly within a hydrocarbon polymer membrane these HPA-hydrocarbon polymers will outperform perfluorosulfonic acid (PFSA) polymers. The correct HPA chemistry must be chosen, and we have shown that silicotungstic acid derivatives act as strong proton conducting moieties and also catalytically decompose oxygenated radicals. This will then enable hydrocarbon membranes with practical lifetimes and performance using the silicotungstic functionality. We are aiming to control the HPA channel morphology and allow for maximum proton conductivity with minimum water uptake. The engineered structures will facilitate proton conduction from ambient conditions to temperatures in excess of 120°C (the polymeric materials chosen are stable to 200°C when dry and potentially much higher when wet and pressurized), as well as achieving cost and durability targets for PEM membranes in electrolyzer applications. Our approach will also allow for development of an ionomer for optimal interfacing with the electrodes.

Present and Future Perspectives on Fuel Cell Membrane Chemical Stability

Durability is key to the value proposition of proton exchange membrane (PEM) fuel cells for transportation applications. Ultimately, fuel cell vehicles need to match the lifetimes of diesel powered trucks, and last longer than lithium batteries, for widespread adoption[1]. The burden of reaching these aggressive targets falls on all components of the system, stack, and membrane electrode assembly. Of these, membrane durability remains an important area of research, in particular the chemical stability of the ionomer. The recognition of the ‘simple unzipping’ of the perfluorosulfonic acid (PFSA) backbone by hydroxyl radicals (HO·)[2],[3] and the subsequent introduction of cerium radical scavengers[4],[5] mark significant advancements in fuel cell lifetimes. Yet, even with this technology, it is unclear if this class of membranes can meet the 25,000+ hours required for heavy duty applications without additional improvements. Furthermore, recent proposals to restrict usage of fluorochemicals in many applications[6] presents a risk to the rapidly growing PEM fuel cell and water electrolysis markets. This talk will outline recent work that looks beyond simple peroxide degradation of PFSA ionomers and highlight the role of other reaction mechanisms suspected in accelerated fuel cell durability testing. Analysis of effluent water for ionomer fragments during these tests provides a greater understanding of the degradation mechanisms and suggests additional pathways beyond back-bone unzipping. Not only are these fragments useful in inferring reaction mechanisms, but there is also evidence they adsorb to the platinum surface, ultimately adding to performance decay. In other words, increased membrane durability may also result in increased catalyst stability. Finally, chemical stability of hydrocarbon membranes will be considered in light of the advances over the last two decades in understanding PFSA stability. Similarities and differences will be discussed between these two classes of PEM membrane with suggestions on how the techniques used to understand PFSA stability could be applied to hydrocarbon ionomers and advance the understanding of chemical stability in these systems.[1] Cullen, D. A.; Neyerlin, K. C.; Ahluwalia, R. K.; Mukundan, R.; More, K. L.; Borup, R. L.; Weber, A. Z.; Myers, D. J.; Kusoglu, A. New Roads and Challenges for Fuel Cells in Heavy-Duty Transportation. Nat Energy 2021, 6 (5), 462–474. .[2] Curtin, D. E.; Lousenberg, R. D.; Henry, T. J.; Tangeman, P. C.; Tisack, M. E. Advanced Materials for Improved PEMFC Performance and Life. Journal of Power Sources 2004, 131 (1), 41–48.[3] Coms, F. D. The Chemistry of Fuel Cell Membrane Chemical Degradation. ECS Trans. 2008, 16 (2), 235.[4] Frey, M. H., Pierpont, D. M., Hamrock, S. J., US 8,367,267 and US 9,431,670[5] Coms, F. D.; Liu, H.; Owejan, J. E. Mitigation of Perfluorosulfonic Acid Membrane Chemical Degradation Using Cerium and Manganese Ions. ECS Trans. 2008, 16 (2), 1735.[6] European Chemicals Agency (ECHA) proposal submitted 7th February 2023

Influence of Sidechain Length in Perfluoro-Sulfonic Acid Ionomer on Electrode Slurry Interactions and Finalized Microstructure in the Polymer Electrolyte Fuel Cells

Polymer electrolyte fuel cells (PEFCs) have emerged as one of the most promising next-generation energy devices for both passenger-owned and heavy-duty vehicles due to their high energy efficiency, low emissions, and quiet operation. However, the performance of the fuel cell electrode is often limited by the strong specific adsorption of long sidechain (LSC) perfluoro-sulfonic acid (PFSA) ionomer onto the platinum (Pt) catalyst2, which results in a decrease in the electrocatalytic activity1 as well as increase oxygen mass transport resistenace at the MEA level. To address this issue, a short sidechain (SSC) ionomer has been developed, which has been found to exhibit excellent efficiency over LSC ionomer3 The reduced specific adsorption of SSC ionomer onto the Pt catalyst results in a higher available surface area for the electrochemical reaction, which improves the overall fuel cell performance. The sidechain length of ionomers plays a crucial role in determining the overall cell performance4 however, due to the differences between them, the interactions among slurry components are not yet fully understood.Unlike the previous literatures, we investigates the details of ionomer sidechain length and its impact on the interaction among slurry components and resulting electrode microstructure, through a comparative analysis of LSC and SSC ionomers.5 Our hypothesis propose that the physical interactions between components are considerably impacted by the sidechains with a specific emphasis on the mobility and ion-pair association in the slurry. To probe the influence of ionomer sidechains, we conducted a thorough investigation wherein incrementally varied its concentration from 0 to 1.5 mmolSO3-gC -1, at intervals of 0.3 mmolSO3-gC -1. The main purpose of this evaluation was to observe the evolution of particle aggregation according to the correlation between adsorbed ionomer and free ionomer in electrode slurry. Drawing from the U-shaped viscosity profile obtained through rheological measurements, we propose an optimized ionomer concentration of 0.6 mmolSO3-gC -1 for the SSC ionomer-based slurry and 0.9 mmolSO3-gC -1 for the LSC ionomer-based slurry. To characterize the microstructure of the as-prepared electrode, we employed scanning electron microscopy (SEM) and confocal microscopy, with a focus on particle agglomeration and the homogeneous ionomer distribution. Finally, the electrochemical analysis was performed on the fabricated membrane electrode assembly (MEA) in a 25 cm² single cell for a cathode Pt loading of 0.1 mgPtcm⁻². As a result, the optimized SSC ionomer-based electrode exhibited low local O₂ transport resistance and high Pt utilization, leading to over a 40 % enhancement in fuel cell performance at 0.6 V with a high proton accessibility value above 0.85 when compared to the optimized LSC ionomer-based electrode. This study highlights the crucial importance of understanding the effects of ionomer sidechain length on electrode slurry interactions and microstructure and establishes a significant correlation between them. Our findings contribute to the ongoing development of high-performance PEFCs, offering valuable insights into optimizing electrode composition and structure for enhanced fuel cell performance.(1) Ahn, C.-Y.; Park, J. E.; Kim, S.; Kim, O.-H.; Hwang, W.; Her, M.; Kang, S. Y.; Park, S.; Kwon, O. J.; Park, H. S. Differences in the electrochemical performance of Pt-based catalysts used for polymer electrolyte membrane fuel cells in liquid half-and full-cells. Chemical Reviews 2021, 121 (24), 15075-15140.(2)Kodama, K.; Motobayashi, K.; Shinohara, A.; Hasegawa, N.; Kudo, K.; Jinnouchi, R.; Osawa, M.; Morimoto, Y. Effect of the side-chain structure of perfluoro-sulfonic acid ionomers on the oxygen reduction reaction on the surface of Pt. ACS Catalysis 2018, 8 (1), 694-700. (2) Garsany, Y.; Atkinson, R. W.; Sassin, M. B.; Hjelm, R. M.; (3) Gould, B. D.; Swider-Lyons, K. E. Improving PEMFC Performance Using Short-Side-Chain Low-Equivalent-Weight PFSA Ionomer in the Cathode Catalyst Layer. Journal of The Electrochemical Society 2018, 165 (5), F381-F391.(4) Ramaswamy, N.; Kumaraguru, S.; Koestner, R.; Fuller, T.; Gu, W.; Kariuki, N.; Myers, D.; Dudenas, P. J.; Kusoglu, A. Editors’ Choice—Ionomer Side Chain Length and Equivalent Weight Impact on High Current Density Transport Resistances in PEMFC Cathodes. Journal of The Electrochemical Society 2021, 168 (2), 024518.(5) Mauritz, K. A.; Moore, R. B. State of Understanding of Nafion. Chemical Reviews 2004, 104 (10), 4535-4586. DOI: 10.1021/cr0207123.

Embrittlement of PFSA Reinforced Membrane Interfaces after Ex-Situ Chemical-Mechanical Aging

Perfluorosulfonic acid (PFSA) membrane degradation has been identified as one of the main factors responsible for the short lifetime of PEMFCs [1,2]. The aging mechanisms of these membranes are complex due to mechanical fatigue combined to chemical aggressions. Mechanical fatigue results from the wetting/drying cycles while the chemical aggressions are induced by radicals formed during fuel cell operation. Although it is commonly accepted that chemical and mechanical stresses can interact to accelerate membrane degradation [3], coupled studies are rarely conducted. Thus, an original experimental set-up to perform ex-situ aging tests combining membrane exposure to cyclic mechanical stresses to a free radical environment under conditions close to those observed during cell operation has been developed [4]. Ex-situ aging was performed on PFSA membranes reinforced (Nafion™ XL) with a cyclic compression oscillating between 0 - 10 MPa (0.1 Hz frequency) and a Fenton solution containing 1 ppm Fe2+ and 3 %vol H2O2. Such stresses revealed a significant morphological alteration with the appearance of “bubbles” close to the surface membrane (Figure 1, left). No chemical structure modification was detected within the three different layers. Nevertheless, SEM-EDX, FTIR and Raman microscopic analyses highlight delamination close to the reinforcement/PFSA interface (Figure 1, rigth). Additional peeling tests argued this failure point in the Nafion™ XL membrane. Figure 1

Impact of Reinforced Polymer Electrolyte Membrane Scratch on Fuel Cell Durability Using 4D X-Ray Computed Tomography Technique

PEMFCs, or Polymer Electrolyte Membrane Fuel Cells, can be used in both stationary power and transportation applications and are promising for use in heavy duty electric vehicles due to their high energy density, ability to be refueled quickly, and extended range, which are key challenges for battery-powered vehicles [1]. Despite these advantages, there are still obstacles preventing the widespread commercialization of PEMFCs, one of which is production cost [2]. To reduce manufacturing costs, it is imperative to ensure that quality control rejects and scraps are minimized. Moreover, enhancing component integration defect detection would ensure the durability of the fuel cell and enhance its operational lifetime. However, robust quality control requires a thorough understanding of potential non-uniformities and their effects on fuel cell performance and operational degradation.Non-uniformities of the membrane electrolyte assembly (MEA) can result in durability issues by damaging the membrane and making it more vulnerable to mechanical and chemical stress during the operation [3]. Several studies have been done on cation contamination and membrane pinholes and their effect on fuel cell performance and durability [4,5] but little attention has been paid to other types of non-uniformities such as membrane scratches and foreign particles, which may also conceivably affect durability [6]. By implementing 4D in-situ X-ray computed tomography (XCT) [7,8], the current work aims to track the evolution of scratches that appear on a reinforced membrane surface during fabrication and its specific objective is to determine the impacts of membrane scratches on membrane durability in fuel cells.The study was conducted by using small-scale fuel cells with GORE-SELECT® membranes that were intentionally scratched with a razor blade, subjecting them to combined chemomechanical membrane accelerated stress test (AST), and monitoring the membrane degradation and evolution of the scratches using 4D-XCT throughout the AST. During the fabrication step, the depth of scratches was regulated by a weak bond between the reinforcement layer and the perfluorosulfonic acid (PFSA) layer, i.e., the scratches did not tear through the reinforcement. Furthermore, the scratches did not adversely impact the initial cell performance. However, during AST operation the evolution of the scratched region was affected by several factors, including the friction between the layers of the membrane electrode assembly, the width of the scratch (Figure 1), the presence of membrane debris, and the extent of membrane strain. Additionally, it was observed that changes in the quality of catalyst layer transfer onto the scratched region can alter the degradation pattern and potentially create a self-mitigating mechanism. These findings may be used to develop more optimized quality control measures for membrane scratches in fuel cell production. Acknowledgements This research was supported by the Natural Sciences and Engineering Research Council of Canada, Canada Foundation for Innovation, British Columbia Knowledge Development Fund, Western Economic Diversification Canada, Ballard Power Systems, and W.L. Gore & Associates. This research was undertaken, in part, thanks to funding from the Canada Research Chairs program. Keywords: fuel cell; membrane durability; X-ray computed tomography; membrane scratch; manufacturing References [1] Cullen DA, Neyerlin KC, Ahluwalia RK, Mukundan R, More KL, Borup RL, et al. New roads and challenges for fuel cells in heavy-duty transportation. Nat Energy 2021;6:462–74. https://doi.org/10.1038/s41560-021-00775-z.[2] Whiston MM, Azevedo IL, Litster S, Whitefoot KS, Samaras C, Whitacre JF. Expert assessments of the cost and expected future performance of proton exchange membrane fuel cells for vehicles. Proc Natl Acad Sci U S A 2019;116:4899–904.[3] De Bruijn FA, Dam VAT, Janssen GJM. Review: Durability and degradation issues of PEM fuel cell components. Fuel Cells 2008;8:3–22.[4] Tavassoli A, Lim C, Kolodziej J, Lauritzen M, Knights S, Wang GG, et al. Effect of catalyst layer defects on local membrane degradation in polymer electrolyte fuel cells. J Power Sources 2016;322:17–25.[5] Lü W, Liu Z, Wang C, Mao Z, Zhang M. The effects of pinholes on proton exchange membrane fuel cell performance. Int J Energy Res 2011;35:24–30.[6] Kundu S, Fowler MW, Simon LC, Grot S. Morphological features (defects) in fuel cell membrane electrode assemblies. J Power Sources 2006;157:650–6.[7] Ramani D, Singh Y, White RT, Wegener M, Orfino FP, Dutta M, et al. 4D in situ visualization of mechanical degradation evolution in reinforced fuel cell membranes. Int J Hydrogen Energy 2020;45:10089–103.[8] White RT, Eberhardt SH, Singh Y, Haddow T, Dutta M, Orfino FP, et al. Four-dimensional joint visualization of electrode degradation and liquid water distribution inside operating polymer electrolyte fuel cells. Sci Rep 2019;9:1–12. Figure 1

Reinforced Membranes with PTFE Matrix and Sulfonated Hydrocarbon Electrolyte for PEM Fuel Cells

Proton exchange membrane fuel cells (PEMFCs) have emerged as a promising technology for clean energy conversion with various potential applications. Due to its cost-effectiveness, sulfonated hydrocarbon has been researched as an alternative to Nafion, a commercial proton exchange membrane. However, sulfonated hydrocarbon's mechanical and chemical stability remains a critical challenge that needs to be addressed, as the membrane must withstand harsh operating conditions, such as wet-dry mechanisms in high-temperature operations. To compete with perfluorosulfonic acid (PFSA), sulfonated hydrocarbon should be reinforced with a polytetrafluoroethylene (PTFE) substrate. However, there are significant issues with incompatibility between sulfonated hydrocarbon and PTFE substrate.To improve the impregnation, simple and reproducible chemical treatment has been developed to enhance the hydrophilicity of PTFE using a mixture of acids and oxidizing agents. Moreover, surfactant was added to increase compatibility and improve impregnation. After the reinforced membrane was fabricated, the membranes were characterized, including their water uptake and dimensional stability. The reinforced membrane also showed superior mechanical properties, including gas permeability, tensile strength, and dynamic mechanical analysis. To evaluate the degree of impregnation, the transparency of the reinforced membrane was checked for haziness and further analyzed with scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) mapping to quantify the impregnation degree. Finally, the performance and durability of the reinforced membrane were measured by single-cell and wet-dry cycling tests.

Cross-Aligned PTFE Nanofiber Reinforced Composite Membrane for PEM Fuel Cells

Polymer electrolyte membrane fuel cells (PEMFCs) have widely been considered environmental friendly alternative energy technologies due to their high energy conversion efficiency and zero emission. In the recent, the importance of performance and durability of electrolyte membrane, interfacial layer separating two electrodes, prohibiting fuel cross-over, while transporting only protons, has become much crucial for utilizing PEMFCs to the automobile applications such as fuel cell electric vehicles (FCEVs) and drones.Unfortunately, the current state membranes, mainly composed of perfluorosulfonic acid (PFSA) ionomers, have suffered from the high cost and low proton conductivity, and low dimensional stability during dynamic humidity changes during fuel cell operation. In order to deal with these issues, recently, a reinforced composite membranes (RCMs) have been developed in which a PFSA ionomer is impregnated into a porous support matrix consisted with nanofibrous polymer materials such as polytetrafluoroethylene (PTFE) due to their thermal/mechanical robustness. The PTFE based RCMs could provide enhanced mechanical stability and electrochemical performance with a reduced use of PFSA ionomer, but low impregnation of ionomers into nanosized hydrophobic PTFE networks, resulting in phase separation and irreversible creep deformation.Herein, we report a novel preparation of vertically alined PTFE aggregated fibers (PTFE AFs) as a reinforcement by using facile electrospinning hetero-polymer solutions containing PTFE nanoparticles and PEO (Polyethylene oxide) carrier polymer and subsequent thermal removal of PEO. Developed PTFE AF were effectively soaked by PFSA ionomers, and PTFE AF based RCMs delivered outstanding dimensional stability and proton conductivity compared to commercial RCMs. Furthermore, PTFE AF based RCMs used MEA exhibited exceptional single-cell performance and long-term stability. The enhanced performance was attributed to the facile proton conduction through the one dimensional channels between aligned fibers without fiber scattering, and effective suppression of volume expansion of hydrated PFSA ionomer by rectangular shaped PTFE fiber network. We believe the widespread use of novel PTFE fiber based membranes with an unique pattern in a variety of membrane applications where porous supports are used. Figure 1

Non-destructively incorporating ceria in Nafion membrane as hydroxyl radical scavenging agent for long-term PEMFC application

Aiming at enhancing the long-term operation of proton exchange membrane fuel cell (PEMFC), Nafion as a typical example of perfluorosulfonic acid proton exchange membrane is non-destructively modified by sulfonated ceria (CeO2-DS) nanoparticles via a swelling-filling strategy. CeO2-DS nanoparticles in Nafion matrix can not only act as radical scavenging agent to improve the durability of Nafion, but also assist the re-construction of the efficient proton conduction channel in the composite Nafion membrane. Both oxidative stability and proton conductivity of the Nafion membrane are therefore remarkably improved with the great mechanical and thermal stability of Nafion maintained. PEMFC equipped with the modified Nafion membrane therefore outperforms that with the pristine Nafion membrane in terms of both power output and durability. Specifically, the maximum power density of the PEMFC equipped with modified Nafion after Fenton accelerated degradation test was significantly improved by ca. 25 % compared with that of the pristine Nafion membrane. This work hence provides a facile way to improve the durability of the PEMFC for practical applications.

Structure, Ionomer and Water Distribution in Catalyst Layer of Proton Exchange Membrane Fuel Cell

Catalyst layer’s (CL) ionomer plays a crucial role in the operation of Proton Exchange Membrane Fuel Cell (PEMFC), not simply because it binds the catalyst nanopowder but mostly because it allows proton transport and affects both gas diffusivity and water management [1]. In the CL, the ionomer is a perfluorosulfonic acid polymer similar to that use in the membrane as electrolyte. It is in the form of a few nanometer thick film dispersed around the carbon support or as aggregates larger than 150 nm within the pores of the carbon network [2,3]. In contrast with bulk ionomer membrane or model thin films that have been extensively studied, still little is known on the distributions of ionomer, and especially of water, within the catalyst layer upon hydration [4]. However, this information is crucial to understand the operation and degradation of PEMFC.In the frame of the project FURTHER-FC [5], we perform extensive analysis of the water sorption properties, and in a more unusual way, of the structure of the catalyst layer as a function of relative humidity for different types of carbon support, using Small Angle Neutron Scattering (SANS). It allows us to estimate qualitatively the distribution of the ionomer, and to quantify the average thickness of the ionomer film coating the catalyst, as well as the location of water within the CL upon hydration. The project FURTHER-FC [2] has received funding from the Fuel Cells and Hydrogen 2 Joint Undertaking (now Clean Hydrogen Partnership) under Grant Agreement No 875025. This Joint Undertaking receives support from the European Union’s Horizon 2020 Research and Innovation program, Hydrogen Europe and Hydrogen Europe Research. Jinnouchi, R. et al. Nat. Commun. 12, (2021)Ueda, S. et al., Phys B Condens Matter 551, 309–314 (2018)Morawietz, T. et al., Fuel Cells 18, 239–250 (2018)Kusoglu et al., Chem. Rev. 117, 987−1104 (2017)https://further-fc.eu/

(Energy Technology Division Walter van Schalkwijk Award in Sustainable Energy Technology Address) Exploring New Electrode Designs with Nanofibers

In recent years, electrospinning has been gaining popularity as a robust and scalable technique for the fabrication of non-woven mats of sub-micron diameter polymer fibers. Although not as well studied, the technique can also be used to prepare particle/polymer fiber networks with high intra- and inter-fiber porosity. Such fibrous mats can be used as porous electrodes in fuel cells and batteries, where a high electrode/electrolyte interfacial area is needed. In this talk, particle/polymer electrospinning will be presented as a platform technique to fabricate a variety of electrode and membrane-electrode-assembly (MEA) products with unique and desirable compositions, architectures, and performance characteristics. Laboratory results will be presented for: (1) hydrogen/air fuel cell cathodes with Pt/C and PGM-free catalysts, (2) Pt/C hydrogen electrodes in a H2/Br2 redox flow battery, and (3) Si anodes for lithium-ion batteries.High particle content fibers containing Pt/C or Pt-alloy catalyst powder and a Nafion®perfluorosulfonic acid binder have shown great promise as electrodes in H2/air fuel cells. During electrospinning, Nafion ionomer migrates to the outer edges of the fiber, effectively creating a core-shell fiber morphology, with a low I/C ratio in the fiber interior. Additionally, the interior of the fiber contains nm-size pores and the outer surface of the Nafion shell exhibits enhanced hydrophobicity, due presumably to an accumulation of the polytetrafluoroethylene backbone chains (-CF2-CF2-) of Nafion. The resulting structure is advantageous in that the majority of catalyst particles are in a low I/C environment, nanopores in the fiber interior trap electro-generated water via capillary condensation, and the hydrophobic surface of the fibers facilitates electrogenerated water removal from the mat during fuel cell operation. The fuel cell power output using fiber mat anodes and cathodes is very high for a low Pt loading (0.10 -0.20 mg/cm2), near or above 1.0 W/cm2 for H2/air feeds in the range of 60-100% relative humidity.1,2 Additionally, the fiber mat cathodes exhibit excellent durability, with minimal power loss after accelerated voltage cycling tests. The hydrophobicity of fibers can be enhanced by adding polyvinylidene fluoride (PVDF) directly to the Nafion binder. Such blended binders in fiber/particle hybrid electrodes extend the operational lifetime of fuel cells with iron-based PGM-free cathode MEAs.As an extension of the fuel cell electrode work, electrospun Pt/C-Nafion nanofiber mat hydrogen electrodes have been made and tested for a H2-Br2 redox flow battery.3 The hydrophobic surface coating of core-shell fibers effectively blocks bromine species from poisoning the hydrogen electrode. In a 6.6 M HBr electrolyte lab-scale redox flow battery, the fiber mat electrodes worked extraordinarily well, with: (i) high power at low Pt loading, e.g., 650 mW/cm2 at 0.70 Vfor a loading of 0.11 mgPt/cm2 (6.4 kW/gPt) and 550 mW/cm2 at 0.65 V for a loading of 0.048 mgPt/cm2 (11.5 kW/gPt), (ii) no loss in power for more than 170 charge/discharge cycles, and (iii) a roundtrip current efficiency of 95%at both 0.2 and 0.3 A/cm2.For Li-ion battery applications, single and dual fiber anode mats have been prepared and evaluated, where the fibers contain a polymer binder (e.g., polyacrylic acid, polyamidimide, or polyvinylidene fluoride), Si nanoparticles as the electrochemically active material, and carbon powder as an electron conductor.4 Here, the gravimetric and areal capacities of the fiber anode are considerably higher than those of a conventional carbon particle anode. Inter-fiber voids allow for volume changes in Si during lithiation/delithiation, thus minimizing capacity fade during charge/discharge cycling (up to 600 cycles).AcknowledgmentsThis work was funded by the U.S. Department of Energy, Contract No. DE-EE0007653 from the Fuel Cell Technologies Office, through the Fuel Cell Performance and Durability Consortium (Fuel Cells Program Manager: Dimitrios Papageoropoulos) and Contract No. DE-EE0007215 from the Vehicle Technology Office.

Synthesis of Calamitic Fluorinated Mesogens with Complex Crystallization Behavior.

This work presents the synthesis and self-organization of the calamitic fluorinated mesogen, 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-4-iodobutoxy)ethanesulfonic acid, a potential model for perfluorosulfonic acid membranes (PFSA). The compound is derived in three steps from 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-2-iodoethoxy)ethanesulfonyl fluoride, achieving a 78% overall yield. The resulting compound exhibits intricate thermal behavior. At 150 °C, a crystal-to-crystal transition is observed due to the partial disordering of calamitic molecules, which is followed by isotropization at 218 °C. Upon cooling, sample ordering occurs through the formation of large smectic liquid crystalline phase domains. This thermotropic state transforms into a layered crystal phase at lower temperatures, characterized by alternating hydrophilic and hydrophobic layers. Using X-ray diffraction, crystalline unit cell models at both room temperature and 170 °C were proposed. Computer simulations of the molecule across varying temperatures support the idea that thermal transitions correlate with a loss of molecular orientation. Importantly, the study underscores the pivotal role of precursor self-organization in aligning channels during membrane fabrication, ensuring controlled and oriented positioning.

An asymmetric membrane electrode assembly for high-performance proton exchange membrane fuel cells

The membrane electrode assembly (MEA) is a critical part of proton exchange membrane fuel cells (PEMFCs) and has a significant impact on their performance. A novel preparation method of MEA is proposed in this work to inhibit the swelling and deformation of the proton exchange membrane (PEM) during MEA preparation and improve the interface between the PEM and cathode catalyst layer (CL). Using this novel fabrication method, an asymmetric MEA is prepared, where the anode and cathode parts are fabricated separately and then integrated by a hot-pressing process. The cathode part is prepared by covering the gas diffusion electrode (GDE) onto a layer of a perfluorosulfonic acid dispersion to form a membrane-coated electrode according to a wet-contact interface design, thereby ensuring a tight and concave-convex PEM/CL interface on the cathode. The anode part is prepared by spraying the CL onto a commercial PEM with a substrate to form a CL-coated PEM. An MEA was also prepared according to the traditional catalyst-coated membrane (CCM) method for comparison. The asymmetric MEA based on the new manufacturing process performs better than the traditional CCM-type MEA under the same PEM thickness prerequisite. The peak power densities of the asymmetric MEA are verified to be 18% (H2/air) and 31% (H2/O2) higher than conventional CCM-type MEA. In addition, the asymmetric MEA shows less cell performance degradation after 3000 dry/wet test cycles than the CCM-type MEA.

Effect of Boiling Pretreatment on Physicochemical and Transport Properties of Perfluorosulfonic Acid Membrane

Effect of Boiling Pretreatment on Physicochemical and Transport Properties of Perfluorosulfonic Acid Membrane

Short-side-chain perfluorosulfonic acid incorporated with functionalized silane-based hybrid membrane for the application of energy devices

A unique functionalized organosilane (FOSi) is synthesized and prepared as a hybrid organic-inorganic composite membrane (OICM) using short-side-chain perfluorosulfonic acid (SSC-PFSA) at a large scale for vanadium redox flow battery (VRFB). The OICM solution is fabricated by using 75 wt % of SSC-PFSA and 25 wt % of FOSi and cast with the help of Roll to Roll (R2R) film casting equipment. The OICM's proton conductivity and performance are comparable to the Nafion membrane, owing to additional hydrophilic fields in the hybrid membrane. The OICM possesses proton conductivity of 0.13 S/cm and an ion exchange capacity of 1.44 meq/g, even though the water uptake has been lowered than the PFSA owing to better dispersion of FOSi. OICM has a low vanadium permeability (1.52 × 10−6 cm2/min) and remarkable selectivity, which is a significant benefit. Consequently, over 45th cycles, the OICM performs comparably to Nafion in energy efficiency combined with coulombic and voltage efficiency. The unit cell-test with OICM shows a normalized coulombic efficiency due to low permeability than PFSA and high voltage efficiency due to high proton conductivity. Hence OICM divulges a promising path to developing an alternative membrane for energy devices.

Incorporating amphiphilic modifier into PVDF membrane through in-situ electrostatic crosslinking for efficient oil-water separation

Constructing stable amphiphilic membrane surfaces in a facile and controlled way is highly desired for fabrication of antifouling water purification membranes. Herein, inspired by adhesives of sandcastle worms, we proposed an in-situ electrostatic crosslinking method to incorporate amphiphilic modifiers into poly (vinylidene fluoride) membranes. Pluronic F127 grafted with positively charged quaternary ammonium groups are added into the casting solution, while perfluorosulfonic acid bearing negatively charged sulfonic acid groups and perfluorocarbon chains are dissolved in the coagulation bath. During non-solvent induced phase separation process, electrostatic crosslinking between quaternary ammonium and sulfonic acid led to the in-situ formation of amphiphilic modifiers on membrane surfaces and pore walls. The resulting membrane exhibits high water permeance up to 625 Lm−2h−1 bar−1 and superior antifouling performance with total flux decline ratio of 2 % and flux recovery ratio of 99.3 % for oil-water separation. Besides, the membrane displays excellent structural stability and self-cleaning properties against highly viscous crude oils.

Perfluorosulfonic Acid Polymer Membranes: Microstructure and Basic Functional Properties

The development of modern technologies and the requirements that are imposed on the ecology of production require the producing of new polymeric ion-exchange membrane materials with a set of given properties. Such materials are used in systems of separation and purification of liquids and gases, chemical and electrochemical synthesis, in alternative energy. Membranes based on perfluorosulfonic acid (PFSA) polymers have a set of characteristics necessary for their practical application: good transport properties, strength, elasticity and chemical stability. In this review, the microstructure of PFSA membranes, its change upon sorption of water and solvents, the features of ion and gas transport, mechanical properties as well as the dependence of a number of parameters on the chain length and ionic form of the polymer are discussed.

High-performance and durable membrane electrode assemblies based on CeO2 and ePTFE double-reinforcement strategy for proton exchange membrane fuel cells operating at elevated temperatures

The membrane electrode assemblies (MEAs) play a decisive role in operating conditions and lifetime of fuel cell. In this study, MEAs that could work stably at elevated temperatures were prepared. With this method, a short-side chain perfluorosulfonic acid ionomer coating with CeO2 nanoparticles and two layers of expanded polytetrafluoroethylene reinforcement, to be used as a proton exchange membrane, was directly deposited between the cathode and anode gas diffusion electrodes, forming a double-reinforced integrated MEA. The effects of CeO2 doping amount on performance and other electrochemical properties of MEAs were systematically studied. Under the coupling effect of the water-retention and non-proton-conducting properties of CeO2, the 0.5 wt% CeO2-doped MEA (MEA-S0.5) had optimal performance above 100 °C and under low relative humidity (RH) conditions. At 120 °C and 30% RH, MEA-S0.5 exhibited peak power density of 0.460 W cm−2 (H2/air operation, 100 kPa), which was about 1.28 times that of MEA without CeO2 doping (MEA-S0). Furthermore, CeO2 effectively enhanced the durability of the MEA. Compared with MEA-S0, MEA-S0.5 did not exhibit significant degradation in output power, H2 crossover, or proton conductivity in the 100-h open-circuit voltage-holding test. This work paves the way for developing high-performance, durable MEAs that are suitable for elevated temperatures.

Sub-20 nm ultrathin perfluorosulfonic acid-grafted graphene oxide composite membranes for vanadium redox flow batteries

Perfluorosulfonic acid (PFSA) membranes, such as Nafion, are widely used in vanadium redox flow batteries (VRFBs) because of their high proton conduction through the ion channels and excellent chemical stability. However, the high vanadium permeability of PFSA membranes induced by the randomly interconnected channels limits efficient cell operation. In this work, we demonstrate a sub-20 nm ultrathin PFSA-grafted graphene oxide/PFSA (PFSA-g-GO/PFSA) composite membrane with highly aligned ion channel morphology, which results in a 100-fold improvement in proton/vanadium ion selectivity compared to 25 μm-thick Nafion 211. In addition, the PFSA-g-GO nanosheets physically reinforce the ultrathin membrane while enabling the proton transport through the grafted PFSA ionomers, leading to stable cell operation at overall current densities from 40 to 200 mA cm−2. Especially, at a high current density of 200 mA cm−2, the PFSA-g-GO/PFSA composite membrane shows an energy efficiency (EE) of 78%, which is higher than that of Nafion 211, indicating its potential as an ion-selective membrane for VRFB.