Performance Of Polymer Electrolyte Fuel Cells Research Articles

Polymer electrolyte fuel cell operating with nickel foam-based gas diffusion layers: A numerical investigation

Due to their outstanding structural, transport and electrical characteristics, nickel foams serve as excellent candidate materials for gas diffusion layers (GDLs) in polymer electrolyte fuel cells (PEFCs). In this work, a new three-dimensional PEFC model was developed to explore the local and global fuel cell performance with nickel foam-based GDLs. The fuel cell operating with nickel foam GDLs was shown to have, due to its superior mass and charge transport properties, higher oxygen and water concentration and current density compared to that operating with the conventional carbon fibre-based GDLs. The results show that the pumping power should be taken into account when optimising the dimensions of the flow channels and as such the net power density must be the criterion for optimisation. The optimal dimensions of the flow channels for the fuel cell operating with nickel foam based GDLs were found to be 0.25 mm for the channel height and 1 mm for the channel width; the maximum net power density with these dimensions was around 0.95 W/cm2 which is two times higher than that operating with carbon fibre based GDLs. All the results have been presented and critically discussed.

Performance uniformity analysis in polymer electrolyte fuel cell using long-term dynamic simulation

The temporal stability and spatial homogeneity of current density are key factors in Polymer Electrolyte Fuel Cell (PEFC) performance and durability. Temporal and spatial variations of relative humidity, fuel concentration, and water droplets in the channels are the principal causes of non-homogeneous current density. A dynamic pseudo-3D model was previously proposed by the authors and has been extended and improved to perform the long-term and intensive simulations of PEFC with low computational cost, which allows to study of the performances homogeneity with different experimental configurations and flow field topologies. The model considers important phenomena in the homogeneity analysis, such as gases and liquid water movement in diffusion layers and flow field, electrochemical reactions, and others. Model validation has been performed using experimental data obtained from a 25 cm2 cell with a single serpentine, which has allowed studying the model transient response and spatial representation. The simulations have been used to study the homogeneity and stability of 36 setups of PEFC, varying the rib/channel width ratio, the stoichiometric ratio, and the number of parallel serpentine channels. The results show the importance of a properly flow field design to control gas flow, remove the channels’ liquid water, and keep a homogeneous feeding. The study evaluated a set of channel configurations that show the improved temporal voltage stability and current density spatial homogeneity. The results show the impact of channel gas speed and ratio channel/rib width in liquid droplets removal and the proper fuel spatial distribution; and how configurations with a lesser number of channels in serpentine design require a lower stoichiometric ratio to perform better temporal and spatial uniformity. In the case of the cell configurations simulated, the optimum design was achieved using between 5 and 7 parallel serpentine channels and a channel/rib ratio 3/5.

Pt nanorods supported on Nb-doped ceria: A promising anode catalyst for polymer electrolyte fuel cells

For polymer electrolyte fuel cells (PEFCs), platinum nanoparticles supported on carbon black (Pt/C) serve as the commonly used hydrogen anode catalyst, exhibiting high activity for the hydrogen oxidation reaction (HOR), while the carbon support is susceptible to corrosion under PEFC operation. Here, a highly active HOR anode catalyst of Pt nanorod supported on niobium (Nb)-doped ceria without using corrosive carbon support was developed, which exhibits high durability at high potentials associated with hydrogen starvation. The production of hydrogen peroxide (H2O2), which can degrade the polymer electrolyte membrane, was also found to be significantly suppressed on the Pt nanorod/doped ceria catalyst. Density functional theory (DFT) calculations suggests that the Pt nanorod geometry and interaction with Nb and Ce favor HOR activity and stability while suppressing H2O2 production by modulating the adsorption of key reaction intermediates. This new catalyst has the potential to be used as an anode for high-performance and high-durability PEFCs.

Adaptability of Heteropolytungstate Anions as Efficient Anode Redox Mediators in Redox Flow Polymer Electrolyte Fuel Cells.

Heteropolyanions (HPAs) are known as the candidate for an anode redox mediator for redox flow polymer electrolyte fuel cells (PEFCs). The electrochemical properties of HPAs differ depending on the transition elements and heteroatoms in HPAs. For example, heteropolytungstate anions (W-HPAs), in which the transition element is tungsten, have a lower one-electron reduction potential than other HPAs. Therefore, it has been reported that redox flow PEFCs adapted with W-HPAs exhibit high power generation performance. On the other hand, studies on the heteroatoms of HPAs are limited only to electrochemical properties, and statistical and comprehensive studies on the power generation performance of redox flow PEFCs are lacking. Thus, it is beneficial to clarify the optimal heteroatom in order to design anolytes suitable for redox flow PEFCs. In this study, heteropolytungstate anions with different heteroatoms were adapted as anodic redox mediators in a redox flow PEFC. In power generation tests, the redox flow PEFC with an anolyte of zinctungstate anion showed the highest performance. Zinctungstate anion exhibited the fastest reduction and oxidation rates among the W-HPAs investigated in this study.

Fuel Cells with Proton Exchange Membrane Modeling and Control Techniques

Comprehensive mathematical models with three distinct controllers (PID, FOPID, and fuzzy + PID) for polymer electrolyte fuel cells (PEFCs) are constructed in this work. The models are made to indirectly control the input hydrogen mass flow rate in order to set the output voltage of the PEMFCs at a predetermined value. The simulation results demonstrate how effectively the es-tablished model fits the task of characterizing a PEFC's performance. While the developed control-lers are capable of stabilizing voltage, the fuzzy + PID controller performs better, exhibiting a re-duced overshoot and a faster response time.

Three-dimensional nanostructure analysis of non-stained Nafion in fuel cell electrode by combined ADF-STEM tomography.

The polymer electrolyte fuel cell (PEFC) is one of the strongest candidates for a next-generation power source for vehicles which do not emit carbon dioxide gas (CO2) as exhaust gas. The key factor in PEFCs is the nano-scaled electrochemical reactions that take place on the catalyst material and an ionomer supported by a carbon support. However, because the nano-scaled morphological features of the key materials in the catalyst compound cannot be observed clearly by transmission electron microscopy, improvement of PEFC performance had been approached by an imaginal schematic diagram based on an electrochemical analysis. In this study, we revealed the nano-scaled morphological features of the PEFC electrode in three dimensions and performed a quantitative analysis of the nanostructure by the newly-developed "Combined ADF-STEM tomography technique." This method combines information from plural ADF detectors with different electron collection angles and can emphasize the difference of the electron scattering intensity between the ionomer and carbon in the cross-sectional image of the reconstructed three-dimensional data. Therefore, this segmentation method utilizing image contrast does not require a high electron beam current like that used in EDX analysis, and thus is suitable for electron beam damage-sensitive materials. By eliminating the process of manually determining the thresholds for obtaining classified component data from grayscale data, the obtained 3D structures have sufficient accuracy to allow quantitative analysis and specify the nano-scaled structural parameters directly related to power generation characteristics.

Effect of Hydrophilic and Hydrophobic Composite Microporous Layer Coated Gas Diffusion Layers on PEFC Performance

In order to widen the market application of the polymer electrolyte fuel cell (PEFC), the output power of the PEFC system must be increased. One of the barriers is the cell voltage loss under high current density conditions. This is mainly caused by the deteriorated reactant mass transport, which is blocked by the water flooding at the catalyst layer (CL), microporous layer (MPL), and gas diffusion layer (GDL). Modifying the MPL coated on the GDL is an accessible way to provide better water management for PEFCs to elongate the operating range of the cell, so a novel MPL-coated GDL should be developed to realize the goal. Previously, we evaluated double MPL-coated GDLs, which coated a thin hydrophilic layer on the hydrophobic MPL-coated GDL in the through-plane direction. The extra hydrophilic layer was influential in promoting the introduction of water into the small pores of the hydrophobic MPL, enhancing the ability to reduce flooding, and the oxygen transport resistance under high humidity conditions can be declined.The present study evaluates a novel composite MPL that the hydrophobic and hydrophilic pores are randomly allocated in the same layer. Excess water is expelled from the hydrophilic pores while maintaining gas transport by the hydrophobic pores. To determine the appropriate hydrophobic and hydrophilic compositions, we first evaluated the most commonly used hydrophobic polytetrafluoroethylene (PTFE) binder, and the contact angle of PTFE-MPL was 136°. Polyvinyl alcohol (PVA) was chosen as the hydrophilic binder, and the contact angle of PVA-MPL was 105°. The slurry containing PTFE, PVA, carbon black, and distilled water was mixed using a mixer and then spread on the carbon paper substrate by a bar coating machine. The temperature was heated at 350°C to sinter the MPL on the substrate. However, the sintering temperature of PVA should be lower than 150°C, so the PVA in the composite MPL was burned and led to a similar contact angle as the PTFE-MPL. Meanwhile, the performance enhancement could not be obtained compared with a PTFE-MPL-coated GDL. Oppositely, when decreasing the sintering temperature to 150C°, the PTFE-PVA composite MPL demonstrated strong hydrophilicity with a small contact angle value, and the performance was exacerbated than the PTFE-MPL. Therefore, to coordinate the lower sintering temperature of PVA, polyvinylidene difluoride (PVDF) was selected as the hydrophobic binder. The contact angle of PVDF-MPL was 143°. After the PVA was preserved, the unexpectedly strong hydrophilicity was exhibited in PVDF-PVA composite MPL, aggravating the liquid water accumulation in the MPL and without performance improvement. Finally, the Nafion ionomer with relatively weak hydrophobicity was used for the composite MPL. As a hydrophilicity complement, titanium dioxide (TiO2) particles were added to the slurry to control hydrophilicity. The contact angle of Nafion/TiO2-MPL was 113°. Similarly, the Nafion/TiO2-PVDF composite MPL indicated a contact angle of 114°, and the water permeability test proved that separate hydrophobic and hydrophilic pores were generated.The oxygen transport resistances were measured based on the limiting current density values of polarization curves to evaluate the ability of the MPL-coated GDL to reduce flooding under high humidity conditions. The active area of the MEA was 1.0 cm2, and the cell temperature was kept at 35°C. Pure hydrogen and diluted oxygen (2 vol% O2 and 98 vol% N2) gases were supplied at the anode and cathode, respectively, and the flow rates were set at 1000 cm3 min-1. The relative humidity of gases supplied to the anode and cathode was 200%RH, and the gas backpressure was set at zero. The oxygen transport resistance of the Nafion/TiO2-PVDF composite MPL-coated GDL was lower than that obtained with a commercial SGL-22BB GDL. Thus, an appropriate composite MPL-coated GDL effectively enhanced PEFC performance under high humidity conditions.

Investigating Nano-Sized Dispersity and High Crystallinity of Perfluoro-Sulfonic Acidionomer in Polymer Electrolyte Fuel Cell Electrodes Via Electrospray Deposition

Polymer electrolyte fuel cells (PEFCs) hold great promise for mitigating the worldwide climate crisis by tapping into the potential of producing clean energy from renewable sources. However, widespread commercial adoption of PEFCs requires addressing the challenges associated with PEFC performance and durability, particularly concerning electrode materials and design. The PEFC electrode is a crucial component of PEFC performance, with the ionomer playing a vital role as both an electrode binder and proton conductor. Nano-sized dispersity and high crystallinity of the ionomer are vital properties that are crucial for achieving enhanced performance and durability. However, existing methods for fabricating PEFC electrodes have been unable to attain these desirable ionomer characteristics. In this work, we propose a novel approach to fabricating PEFC electrode architectures with ionomers possessing nano-sized dispersity and high crystallinity using the electrospray deposition (ESD) technique. In the ESD process, a precursor solution is atomized into charged droplets, while evaporating the solvent, and results in the formation of advanced electrode with vertical architecture that exhibits high crystallinity of ionomer, in contrast to much lower crystallinity of those fabricated by conventional decal methods. The ionomer characteristics significantly impact the overall fuel cell performance and durability. Therefore, controlling the residual solvent content during the ESD process is a crucial aspect that is vital for achieving the desired ionomer characteristics. The residual solvent content is tuned by investigating the initial mixed solvent ratio, substrate temperature, and distance between the nozzle to substrate. By fine-tuning the residual solvent content and optimizing the deposition parameters, the ESD technique can overcome the limitations of traditional fabrication methods, resulting in PEFC electrodes that offer enhanced performance, increased durability, and improved energy efficiency. The electrospray deposition (ESD) technique provides precise control over the amount of residual solvent required for deposition, making it a scalable technique. This work shows that the residual solvent content of PEFC electrodes significantly impacts the ionomer crystallinity and the electrode architecture using a well-controlled and optimized electrospray technique, without the use of any additives or special ionomer. In summary, this work demonstrates a novel approach to fabricating PEFC electrode architectures with ionomers possessing nano-sized dispersity and high crystallinity using the electrospray deposition technique. This approach provides precise control over the residual solvent content, allowing for enhanced performance and increased durability of PEFC electrodes due to the high-crystallinity of the ionomer. These findings have important implications for the development of sustainable energy technologies and contribute to the ongoing efforts towards mitigating the worldwide climate crisis.

CO Oxidation Behavior of Pt/RuO2-Sphere Catalyst in Acidic Electrolyte

Polymer electrolyte fuel cells (PEFCs) are one of the candidates for the next-generation power source. PtRu alloy catalyst is used as an anode catalyst because it has high CO poisoning tolerance. It is well known that PtRu alloy has high CO poisoning tolerance because of the bifunctional mechanism and the ligand effects of the Ru atom working as the co-catalyst. However, the Ru atom dissolves during the operation of PEFCs, such as start-up/shut-down, and then the CO poisoning tolerance becomes low. The author reported using ruthenium oxide nanosheet (RuO2ns) acted as high stable co-catalyst [1]. The composition catalyst of traditional Pt/C and RuO2ns (RuO2-Pt/C) showed high CO poisoning tolerance and long life. But the high CO poisoning tolerance site in the RuO2ns-Pt/C catalyst was limited to the very close position of Pt nanoparticles and RuO2ns. Thus, the CO poisoning tolerance was uneven, even within the same catalyst. On the other hand, we reported that new catalyst support with the sphere shape composited by the reduced graphene oxide wall provided high substance diffusion and Pt utilization rate [2]. It is expected that the spherical catalyst support composed from the RuO2ns wall provides complete contact with Pt nanoparticles and not only exquisite CO poisoning tolerance but also high Pt utilization. In this study, the new spherical catalyst support with the RuO2ns wall was synthesized and supported Pt nanoparticles, and its CO oxidation ability was evaluated by CO stripping voltammetry. The spherical catalyst support (RuO2-sphere) was composed of a SiO2 bead as a core and the RuO2ns wall, and its synthesis method was similar to the previous work [2]. Concretely, this study changed the wall material from graphene oxide to RuO2ns. And the Pt complex adsorbing on a RuO2-sphere was reduced by heating reflux with hydrazine at 100°C and 24 hours in ethanol solvent. After water washing, Pt-supported RuO2-sphere (Pt/RuO2-sphere) was obtained. The morphology, crystal structure, and electron state of the Pt/RuO2-sphere were evaluated by SEM, XRD, and XPS, respectively.A three-electrode cell, which is composed of a working electrode, Pt counter, Ag/AgCl reference electrode, and 0.1 M HClO4 electrolyte, was used for the electrochemical measurements, and the measurement temperature was 60°C. This study converted the potentials from Ag/AgCl reference to RHE reference. The CO stripping voltammetry was conducted in the following steps. CO gas was introduced had flowed into the electrolyte for two minutes to adsorb on the metal surface while its potential was kept at 0.05 V. The inert gas purged out excess CO gas in the electrolyte for 30 minutes. And then, the potential was swept to 1.2 V at 10 mV s-1. SEM images of the Pt/RuO2-sphere showed about 500 nm sphere of RuO2-sphere and a few nanometer sizes of Pt particles. Results of XRD and XPS suggested that Pt particles were mainly metallic state and not alloying with Ru. In addition, Ru valence in Pt/RuO2-sphere was predicted at quadrivalent. The cyclic voltammogram of the Pt/RuO2-sphere had characteristic peaks attributed to both Pt and RuO2ns. Specifically, the redox peaks below 0.4 V and at 0.8V-1.2V could be assigned the hydrogen adsorption/desorption and redox of the Pt surface, respectively. In addition, the unique redox peaks of RuO2ns were also observed around 0.6 V. The estimated on-set potential of the CO oxidation peak in the Pt/RuO2-sphere was at 0.36 V, and this value was superior to that of traditional Pt/C and near that of PtRu/C. The CO oxidation peak of the Pt/RuO2-sphere was sharply compared to the composite catalyst of Pt/C and RuO2ns in previous work. This change in peak shape was thought to be attributed to the expansion of the contact sites between the Pt nanoparticles and the RuO2ns surface.Developed Pt/RuO2-sphere catalyst, which had the RuO2ns wall and spherical shape, showed high CO poisoning catalyst as well as PtRu/C.[1] T. Saida, et al., Electrochim. Acta, 55, 857–864 (2010).[2] T. Saida, et al., Energy & Fuels, 36, 1027-1033 (2022).

(Digital Presentation) Operando x-Ray Fluorescence Spectroscopic Study of in-Plane Cerium-Ion Radical Quencher Distribution in Polymer Electrolyte Membranes

One of the challenges for the widespread use of polymer electrolyte fuel cells (PEFCs) is the suppression of chemical degradation in polymer electrolyte membrane (PEM). This degradation is caused by radical species generated due to the reaction of hydrogen peroxide with impurities in the PEM during PEFC operation. One way to suppress the chemical degradation is to add cerium ions to the PEM as radical quencher, 1) which absorbs the radicals through a redox reaction, thereby suppressing PEM degradation caused by radicals. However, it is known that cerium ions move in the in-plane direction due to the humidity and potential distribution, where the depletion of cerium ions causes PEM degradation.2) Therefore, it is required to elucidate the mechanism of cerium ion transport phenomena in the in-plane direction under PEFC operating conditions. High-energy X-ray fluorescence spectroscopy enables operando measurements of cerium distribution by taking advantage of penetration into the fuel cell inside.3) In this study, we have developed operando measurement cells that can observe the distribution phenomenon of cerium ions by using X-ray fluorescence spectroscopy while controlling the humidity gradient in the in-plane direction. Using the developed method, we analyze the cerium ion transport phenomena under the humidity gradient in the membrane electrode assembly (MEA). For the operando X-ray fluorescence measurements, end-plates with an X-ray transmission window and two gas inlets were used to control two different humidity conditions in the PEM. X-ray was incident at 90 degrees from the MEA plane, and a germanium solid-state detector was positioned perpendicular to the incident X-rays to acquire Ce-Ka fluorescence X-ray from the MEA. The catalyst coated membranes composed of a perfluorosulfonic acid-based cation exchange membrane with cerium-ion substitution, coated with a platinum catalyst layer were used. Operando X-ray fluorescence measurements were performed at BL37XU at SPring-8 (Japan). X-rays with incident energy ranging from 40 to 65 keV were used to scan the cell position and detect Ce-Ka fluorescence X-ray. The cell temperature was set at 60°C. Cerium ions in the MEA were found to migrate from the high humidity side to the low humidity side within a range of millimeters in approximately one hour. The migrated cerium ions tended to diffuse into homogeneous state within in a few hours under the uniform humidity condition. Acknowledgments The authors would like to thank M. Toida (Toyota Motor Corporation) for providing samples and for in-depth discussions. References 1) Endoh, ECS Trans., 16, 1229 (2008).2) Y-H. Lai, K. Rahmoeller, J. Hurst, R. Kukreja, M. Atwan, A. Maslyn and C. Gittleman, Electrochem. Soc., 165, F3217 (2018).3) Y. Orikasa, A. Takezawa, K. Amemiya, Y. Tsuji, T. Asaoka, M. Ohki, O. Sekizawa, and K. Nitta, ECS Trans., 109, 109 (2022).

Deuterium Isotope Separation By Polymer Electrolyte Fuel Cell with Gas Circulation System

IntroductionHydrogen isotopes such as deuterium (D) and tritium (T) are in increasing demand in the fields of materials, energy, and medicine. A international fusion reactor in France will be equipped with water electrolysis for T separation. New methods are required, since the conventional processes perform low separation and consume large amount of energy. We have been studying D separation by polymer electrolyte fuel cell (PEFC) [1-3]. Here, the relationship between the gas consumption rate and separation efficiency is investigated. Therefore, the present PEFC can recirculate the unreacted hydrogen gas discharged from the anode, which proceeds high gas utilization. In our poster presentation, we will show the separation factor, D concentration and production volume depending on the gas circulation ratio.ExperimentalA JARI cell (electrode area: 25 cm2) was used for PEFC, and platinum was used as catalyst for both electrodes. For the anode, protium (H) concentration was set to 90 at% as a mixed gas. Oxygen gas was supplied to the cathode. Power generation was performed at room temperature, and a constant output current was obtained using a variable resistor. The H concentration in the anode gas was analyzed with a quadrupole mass spectrometer, and the gas volume discharged from the PEFC circulation system was calculated.Results and discussionThe ratio of the hydrogen gas circulation rate to the supply rate is defined as λ. The relationship with the H concentration is shown (Fig. 1). The H concentration was enriched during PEFC operation, while D was condensed in produced water. The gas circulation improved the separation efficiency because the outlet gas was repeatedly processed in PEFC. Figure 2 shows the relationship between λ and the volume rate of exhaust gas from anode. As λ increased, the gas rate decreased linearly from 8 mL min-1 to 2 mL min-1. That is, the circulation system let the gas residential time in PEFC be longer. When the gas was circulated more, the gas could react for long time. This was attributed to the high H concentration seen in Fig. 1. The present results demonstrated the importance of circulation parameter, λ, for the enrichment production.

Highly Durable and Active Electrocatalysts Using Pt Nanorod Catalysts Supported on Nb Doped SnO2 for Polymer Electrolyte Fuel Cells Operating at Wide Temperature Range

The improvement of the durability and activity in cathode catalyst is required toward the wide spread use of polymer electrolyte fuel cells. One of the interesting catalysts is the Pt catalysts supported on SnO2 (Pt/M-SnO2, M = Nb, Ta) without carbon additives [1,2]. The durability (startup/shutdown, load cycling) and oxygen reduction reaction (ORR) activity of the Pt/M-SnO2 is superior to those of commercial Pt catalysts supported on carbon black (Pt/CB) etc. [3-8]. The non-carbon support of M-SnO2 nanoparticles has a unique carbon-like microstructure of a fused-aggregate network structure, which supply the essential function of the electronically constructing pathways via necking of each support particles and the gas diffusion pathways via the open pores surrounded by particles. The Pt nanorod catalyst on M-SnO2 also improves the ORR activity as shown in the catalyst design concept (Fig. 1)[9]. The IV performance of the single cell using the Pt nanorod/Nb-SnO2 cathode catalyst layers at operating temperatures from 80oC to 120oC is quite high to approach the NEDO target performance (Fig. 2) with keeping high durability. The catalyst is considered to have possibilities for application of the heavy-duty vehicles operating at wide-temperature range (< 120oC)[10]. Acknowledgments This work was partially supported by funds for the project “Electrolytes, Catalysts and Catalyst layers with Extraordinary Efficiency, power and Durability for PEFCs-2030 (ECCEED’30) from the New Energy and Industrial Technology Development Organization (NEDO) of Japan, and JSPS KAKENHI Grant Number (23H02059) from the Ministry of Education, Culture, Sports, Science and Technology. References A. Masao, S. Noda, F. Takasaki, K. Ito, K. Sasaki, Electrochem. Solid-State Lett.,12, B119 (2009).E. Fabbri, A. Rabis, R. Kötz, T.J. Schmidt, Phys. Chem. Chem. Phys., 16, 13672 (2014).K. Kakinuma, M. Uchida, T. Kamino, H. Uchida, M. Watanabe, Electrochim. Acta, 56, 2881 (2011).Y. Senoo, K. Kakinuma, M. Uchida, H. Uchida, S. Deki, M. Watanabe, RSC Adv., 6, 321800 (2014).Y. Chino, K. Taniguchi, Y. Senoo, K. Kakinuma, M. Watanabe, M. Uchida, J. Electrochem. Soc., 162, F736 (2015).K. Kakinuma, R. Kobayashi, A. Iiyama, M. Uchida, J. Electrochem. Soc., 165, J3083 (2018).K. Kakinuma, K. Suda, R. Kobayashi, T. Tano, C. Arata, I. Amemiya, S. Watanabe, M. Matsumoto, H. Imai, A. Iiyama, M. Uchida, ACS Appl. Mater. Interfaces 11, 34957 (2019).K. Kakinuma, M. Hayashi, T. Hashimoto, A. Iiyama, M. Uchida, ACS Appl. Energy Mater., 3, 6922 (2020).G. Shi, T. Tano, D.A. Tryk, A. Iiyama, M. Uchida, K.Kakinuma, ACS Catal., 11, 5222 (2021).K. Kakinuma, H. Taniguchi, T. Asakawa, T. Miyao, M. Uchida, Y. Aoki, T. Akiyama, A. Masuda, N. Sato, A. Iiyama J. Electrochem. Soc. 169 (2022) 044522. Figure 1

Development of Hydrophilic Oxide/Polymer Composite Membranes for Polymer Electrolyte Fuel Cells Operating at Wide Temperature Range

Toward the wide-spread use of heavy-duty vehicles (HDVs) operated by polymer electrolyte fuel cells (PEFCs) should approach the higher temperature around 120oC besides normal temperature (60-80oC). Commercial perfluorosulfonic acid-based electrolyte (PFSA, e.g. NafionⓇ) shows better proton conductivity with chemical stability in wide temperatures range, though decreases under low back pressure at 100~120 oC. In order to improve the proton conductivity at the higher temperature range, composite membrane of NafionⓇ with a hydrophilic filler of Ta doped TiO2 (Ta-TiO2) was synthesized. The Ta-TiO2 nanoparticles fillers with fused-aggregate network microstructure were synthesized by the flame method, and were crushed by wet mill(Star Burst, :Sugino Machine Limited CO.). The fillers were mixed with NafionⓇsolution (20 wt.%：D2020 Chemours Co.) by use of a rotary ultrasonic dispersing processor (500 rpm, 60 min. PR-1 :Thnky Co.), a planetary ball mill (500 rpm、30 min.：PULVERISETTE 6：FRITSCH Co.), and a defoaming processor (500 rpm、5 min.：HM-400W: Kyouritu Seiki). The dispersion solution was coated in hot air by use of a die coating system (die coater: Taku-Dai Mini-50: Daimon Co., Ltd.), and were hot-pressed (140 ℃ 3 min. TCMD-2.5:TOHO KOGYO co.) to form composite membranes (9 cm×9 cm ×25 µmt).The cross-sectional backscattered electron image BSE) of the composite membrane observed by scanning electron microscope (SEM, acceleration voltage 2 kV, SU9000: Hitachi High-Tech Co.) and transmission electron microscope (TEM, H-9500: Hitachi High-Tech Co.). The proton conductivity of the composite membrane was measured by the AC four-probe method. The current-voltage (IV) polarization curves of Single cells using the prepared composite membrane (membrane thickness: 25 µm) were measured at 80 ℃ 100% RH and 120 ℃ 20% RH, back pressure 50 kPaG.The obtained composite membranes were well flexibility with softness. The BSE images indicated that the high contrast images of Ta-TiO2 parties were uniformly dispersed in composite membrane. The higher magnified of the cross-sectional TEM images also showed that the hydrophilic surface of Ta-TiO2 adhered to the Nafion® without any air pores. The proton conductivity of the composite membrane at 80% RH increased with increasing Ta-TiO2 content and showed maximum value of 0.13 S cm-1at 3 wt%, and then decreased. The maximum proton conductivity was 1.3 times higher than that of Nafion®. The IV performance of the single cell using composite membrane kept same performance to that using Nafion® membrane at 80 oC 100% RH, and then improved at 120 oC 20% RH. The water content at 120 oC 20% RH kept higher value by the effect of hydrophilicity of the Ta-TiO2, which would be one of the reasons to enhance the cell performance at 120 oC 20% RH. Figure 1

Nanoscale Investigations of the Electric Double Layer in Protic Ionic Liquids

A hydrogen-based energy storage system will be the backbone of a future energy grid using renewable energies. Polymer electrolyte membrane fuel cells (PEMFCs) are a key element in this energy system as they convert chemical energy stored as hydrogen into electrical energy on demand. PEMFC systems, especially for automotive application, could be significantly improved by increasing the operation temperature above 100 °C. Protic ionic liquids are promising candidates as non-aqueous protic electrolytes for next-generation high-temperature polymer electrolyte membrane fuel cells. These fuel cells have a target operation temperature of 160 °C and allowing for a more efficient water and heat management compared to conventional Nafion®-based PEMFCs, which operate at temperatures below 80 °C [1].In order to ensure a reliable and efficient operation an electrolyte with a high electrochemical performance and stability has to be selected. For this purpose, protic ionic liquids have been proposed and first fuel cell tests have shown promising results [2]. Hence, we aim on understanding the properties of this class of novel electrolytes on an atomistic level, which would allow designing suitable material combinations and predicting their properties for an efficient fuel cell operation. As ionic liquids are molten salts, which are liquid below 100 °C, their electrochemical properties differ significantly from those of aqueous solutions. Instead of a classical electric double layer, which can be described by the models provided by Helmholtz, Gouy-Chapman and Stern, the interface structure formed between the electrolyte and a charged electrode is governed by the interplay between coulomb interaction and steric effects between the (large) molecular ions [3]. In order to understand the formation of this double layer on a metallic electrode, we employ atomic force microscopy and infrared spectroscopy in combination with molecular dynamics simulations. Our results show that in the interface region between the prototype protic ionic liquid diethylmethylammonium triflate ([Dema][TfO]) and a Pt electrode, a dense layered structure consisting of alternating anion and cation layers is present, that extends several nanometres into the bulk of the electrolyte [4]. The composition and structure changes with applied potential due to a preferential attraction of anions or cations depending on the electrode charge. When water is added to the ionic liquid, the layered structure becomes distorted and water molecules appear near the electrode. Since the presence of water will also influence the relevant electrochemical processes such as the oxygen reduction reaction (ORR), the analysis of the double layer structure on an atomistic scale is necessary in order to understand the subtle interactions between the molecules in the electrolyte and to propose design routes for novel more efficient ionic liquid-based electrolytes. Wippermann, K.; Suo, Y.; Korte, C. Oxygen Reduction Reaction Kinetics on Pt in Mixtures of Proton-Conducting Ionic Liquids and Water: The Influence of Cation Acidity. J. Phys. Chem. C 2021, 125, 4423–4435, doi:10.1021/acs.jpcc.0c11374.Skorikova, G.; Rauber, D.; Aili, D.; Martin, S.; Li, Q.; Henkensmeier, D.; Hempelmann, R. Protic Ionic Liquids Immobilized in Phosphoric Acid-Doped Polybenzimidazole Matrix Enable Polymer Electrolyte Fuel Cell Operation at 200 °C. Journal of Membrane Science 2020, 608, 118188, doi:10.1016/j.memsci.2020.118188.Rodenbücher, C.; Wippermann, K.; Korte, C. Atomic Force Spectroscopy on Ionic Liquids. Applied Sciences 2019, 9, 2207, doi:10.3390/app9112207.Rodenbücher, C.; Chen, Y.; Wippermann, K.; Kowalski, P.M.; Giesen, M.; Mayer, D.; Hausen, F.; Korte, C. The Structure of the Electric Double Layer of the Protic Ionic Liquid [Dema][TfO] Analyzed by Atomic Force Spectroscopy. International Journal of Molecular Sciences 2021, 22, 12653, doi:10.3390/ijms222312653. Figure 1

On the Importance of MPL Structural Characteristics for PEM Fuel Cell Performance

Gas diffusions layers (GDLs) constitute vital subcomponents of proton exchange membrane fuel cells (PEMFCs) since they participate in all relevant transport processes (gases, vapor, liquid water, electricity and heat).Meanwhile, state-of-the-art GDLs are produced on commercial scale using high volume reel-to-reel (R2R) processes. In almost any case, GDLs are designed as dual-layer structures with a macro-porous carbon fiber-based substrate (backing) and a micro-porous layer (MPL) consisting of carbon particulates bonded with polytetrafluoroethylene (PTFE) binder. A body of scientific work has verified that different aspects of the MPL microstructure and the MPL/macroporous substrate interface play a substantial role in the water management of PEMFCs [1-6].A systematic study was performed based on a singular backing using different MPL types and penetration levels.A simple method to estimate the micro-porous layer penetration in gas diffusion layers based on data obtained from force-deflection behavior of backings and MPL-coated GDLs is proposed. Comparison with SEM and previously published tomographic studies shows that a good estimate for the extent of MPL intrusion into the backing is obtained.MPL loading and penetration is shown to affect different ex-situ GDL properties (in-plane gas permeability, electrical and thermal conductivity) as well as the GDL single cell performance characteristics with respect to humification and high current density operation.Keywords: Gas diffusion layers, Microporous Layer, PEMFC fuel cells Weber, and J. Newman, “Effects of microporous layers in polymer electrolyte fuel cells”, J. Electrochem. Soc. 152, A677-A688 (2005).Lee, R. Yip, P. Antonacci, N. Ge, T. Kotaka, Y. Tabuchi, and A. Bazylak, Synchrotron investigation of microporous layer thickness on liquid water distribution in a PEM fuel cell, J. Electrochem. Soc. 162, F669-F676 (2015).Zhou, S. Shukla, A. Putz, and M. Secanell, “Analysis of the role of the microporous layer in improving polymer electrolyte fuel cell performance”, Electrochim. Acta. 268, 366-382 (2018).Cho, J. Park, H. Oh, K. Min, E. Lee, and J.Y. Jyoung, “Analysis of the transient response and durability characteristics of a proton exchange membrane fuel cell with different micro-porous layer penetration thicknesses”, Appl. Energy 111, 300-309 (2013).T. Gostick, M. A. Ioannidis, M. W. Fowler, and M. D. Pritzker, “On the role of the microporous layer in PEMFC operation.”, Electrochem. Comm. 11, 576-579 (2009).P. Ramasamy, E. C. Kumbur, M. M. Mench, W. Liu, D. Moore, and M. Murthy, “Investigation of macro- and micro-porous layer interaction in polymer electrolyte fuel cells”, Int. J. Hydrogen Energy 33, 3351-3367 (2008).

Nonuniform Compensation of the Current Density Distribution in the Polymer Electrolyte Fuel Cell Using Local Heating

It is well known that reasonable current density distribution can improve fuel cells' output performance and prolong their service life. Which can be achieved by elaborately designed structures and compression, and the reaction occurs evenly in the entire activation area. However, duo the coupling relationships between electrical, thermal and water, the effect of operation conditions (such as the local heating) on the current density mapping is still blank. This paper studies the effect of local heating on polymer electrolyte fuel cell performance and analyses the causes of the output voltage differences through the mapping of the current density distribution. Compared with the inlet and central heating, the heating at the outlet area exhibits the best performance. This is due to the concentration of reactants along the flow field decreases continuously, and the accumulation of liquid water leads to the low current density distribution at the outlet. Here, we show that local heating can compensate for the lowest current density and achieve the more homogeneous current distribution; on the contrary, inlet heating will increase the unevenness of the current density distribution. This study provides practical guidance for the optimal design of the thermal management system.The design of the cooling channel should be locally optimised for more uniform distribution of current density, in addition to the overall temperature balance,

Suppression of PEFC Membrane Degradation By Using SnO2 As Electrocatalyst Support

Introduction Long-term durability of polymer electrolyte fuel cells (PEFCs) is required for various applications such as automobiles. It has been suggested that certain ions dissolved from electrocatalyst materials accelerate radical formation and subsequent chemical degradation of polymer electrolyte membrane (PEM) by the Fenton reaction [1]. Membrane degradation increases hydrogen and oxygen permeability and decreases proton conductivity and mechanical strength [2]. These phenomena significantly affect the electrochemical performance and durability of PEFCs. Therefore, in case metal oxides are used as catalyst support, it is necessary to check the dissolution of metal ions and to evaluate their effects on membranes. Our research group has been studying Nb-doped SnO2 (Sn(Nb)O2), showing improved durability of the electrocatalysts [3]. Here in this study, we evaluate the effects of Sn(Nb)O2 on the chemical degradation of PEMs. Experimental A commercial Pt/C catalyst (TEC10E50E, Tanaka Kikinzoku Kogyo, Japan) was used as the anode catalyst, while three types of cathode catalysts were applied and compared: 1) the commercial Pt/C; 2) Pt/MC where Pt was directly deposited on mesoporous carbon (MC); and 3) Pt/Sn(Nb)O2/MC where Pt was deposited on the Sn(Nb)O2 decorated on the MC. The durability test at open circuit voltage (OCV) was performed for 100 h. Before and after the durability test, cell performance, hydrogen crossover current density, and electrochemical surface area (ECSA) were characterized. The degree of membrane degradation was evaluated by measuring fluorine emission rate (FER) by ion chromatography, and membrane thickness and elemental distribution by energy-dispersive x-ray spectroscopy (EDS) coupled with field-emission scanning electron microscopy (FESEM). Results and discussion It was found that the use of Pt/Sn(Nb)O2/MC led to better durability in the OCV durability test. The decrease in OCV using Pt/Sn(Nb)O2/MC was smaller than that using Pt/C and Pt/MC, less than half of that Pt/C, as shown in Figure 1. The membrane thickness with Pt/Sn(Nb)O2/MC after the durability test was the same as that before the durability test, indicating that SnO2 actually suppressed the membrane degradation as shown in Figure 2. EDS elemental analysis confirmed no Sn ion dissolution from the cathode side as shown in Figure 3, also suggesting that SnO2 at the cathode suppressed the membrane degradation. In this presentation, we will quantitatively analyze the membrane degradation in using SnO2 and discuss possible mechanisms. Acknowledgment This paper is based on results obtained from a project, JPNP20003, commissioned by the New Energy and Industrial Technology Development Organization (NEDO).

The Role of Thermal Conductivity on Liquid Water Distribution in GDLs

Operating polymer electrolyte fuel cells (PEFCs) at increasingly higher current density and efficiency necessitates overall improvements in fuel cell water management [1]. A crucial role facilitating these improvements is played by the gas diffusion layer (GDL) within the membrane electrode assembly (MEA) [2]. The GDL is responsible for distributing the reactant gases from the flow field towards the catalyst layer as well as removing reaction products from the catalyst layer to the flow fields. For example, at the cathode, the electrochemical reaction of oxygen ions with protons and excess electrons yields water and heat, which must be removed through the GDL to the flow field. The removal of water through the GDL can lead to blocked pores in the GDL [2], thereby restricting the reactants’ gas flow towards the catalyst layer causing mass transport losses. GDL design is crucial towards improving the performance of PEFCs, especially at high current densities, such that it minimizes these transport losses. Additionally, removal of the excess heat generated at the cathode catalyst layer through the GDL indicates that the GDL thermal conductivity (k) plays a crucial role affecting the temperature distribution within the MEA [3].In this work, two GDLs varying in thermal conductivity were selected and assembled in MEAs which were then imaged in-operando using X-ray tomographic microscopy [4]. In-Operando imaging allowed the evaluation of the liquid water distribution at steady state over a range of operational conditions such as temperature and current density. Water distribution results for a range of current densities will be presented for selected cell temperatures between 40 and 70 °C. For GDL I with the lower thermal conductivity, the channels are completely dry at 40 °C. For GDL II with the higher thermal conductivity, a wet-dry transition was observed in between 50 and 70°C. High saturations were observed in both the channel and the land regions at 50 °C, while at 70 °C the channels appear to be dry with liquid water only being present under the lands (see Figure 1). These results provide experimental evidence of a major influence of GDL thermal conductivity on liquid water distribution and overall water management in fuel cells. Keywords – operando, X-ray tomographic microscopy, GDL, water visualization Acknowledgement Funding for this research was provided by the Natural Sciences and Engineering Research Council of Canada, Ballard Power Systems, Canada Foundation for Innovation, British Columbia Knowledge Development Fund, and Canada Research Chairs.

Carbon-Free, Connected Core-Shell Nanoparticle Catalysts with Advanced Oxygen-Reduction Performances for PEFCs

As the world faces diminishing non-renewable energy sources and a surge in global pollution, establishing a hydrogen and low-carbon economy has become crucial. Polymer electrolyte fuel cells (PEFCs) hold great promise as a sustainable energy source with the potential for high efficiency, and clean power generation in both stationary and mobile applications. However, the conventional platinum nanoparticle catalysts on carbon support (Pt/C) used for the oxygen reduction reaction (ORR) at the cathode shows sluggish ORR activity, leading to high cost and inferior PEFC performance. Moreover, the carbon-supports used for the Pt catalysts are susceptible to degradation caused by carbon-corrosion during start-stop operations, which can severely compromise the overall performance of the PEFCs. Hence, in order to significantly enhance the commercial viability of PEFCs, considerable progress must be made in terms of cost, performance, and durability.Previously our group has reported carbon-free, connected Pt-alloy catalysts to address the above issues. This catalyst is composed of connected Pt-alloy nanonetworks with high electronic conductivity and exhibits enhanced ORR activity, high start-stop durability, and thin catalyst layers. Specifically, this catalyst exhibited 9 times higher specific activity than that of the commercial Pt/C, making it an excellent candidate for cathode catalyst applications.[1,2] However, high-temperature annealing process is required to develop connected networks between the Pt-alloy nanoparticles, resulting in larger crystallite sizes and reduced surface areas. This limitation has prevented connected Pt-alloy catalysts from achieving significant improvement in mass activity.In this work, we have proposed a novel synthesis method that enables the development of connected core-shell nanoparticle catalysts without any high-temperature treatment. This method eliminates the particle growth and exhibit a high surface area, making it highly effective for ORR applications. Here, a carbon-free catalyst with a core-shell nanonetwork structure having a non-Pt (Pd) core and Pt shell was developed. Additionally, the relationship between the thickness of the Pt-shell layer and ORR activity was investigated.Connected core-shell catalysts with Pd nanoparticles as core and Pt as atomic shell (Pd@Pt) were synthesized in a one-pot polyol process that does not require high-temperature annealing as shown in Fig. 1. The formation of connected Pd@Pt core-shell nanonetworks (< 10 nm) was confirmed by TEM and STEM-EDX analysis. Also, the structure of Pt shell on core metals was successfully tuned by controlling the reaction temperature and time, precursor ratio, etc. Here, the number of the Pt layers on the surface of the connected Pd@Pt core-shell catalysts were varied from 1–6 atomic layers and the results show that the ORR mass activity was notably enhanced in the catalyst with a moderate shell thickness ranging from 2.5 to 3.5 Pt atomic layers. This suggests that connected Pd@Pt catalyst with a moderate Pt layer achieves both high surface area and ORR specific activity. The high surface area of the developed catalysts is attributed to a new synthesis method that does not use high temperature annealing and a low Pt core-shell structure. The improvement in ORR specific activity can be attributed to the more suitable d-band center position of the Pt shell, which is influenced by strain and ligand effects resulting from the Pd core. The ORR performance of the carbon-free connected Pd@Pt catalyst showed 2–4 times enhancement in electrochemical surface area (ECSA) and 1.5–3 times improvement in ORR mass activity compared to the connected Pt-alloy catalysts prepared using high-temperature annealing. Further, high durability of the connected core-shell catalyst against load cycles (0.6 ↔1.0 V) at 60 °C in acidic electrolyte solution was also demonstrated, indicating that a high stability nanonetwork connected by Pt atomic shell.In summary, we have successfully demonstrated a new synthesis method for the formation of connected core-shell nanoparticles by Pt atomic shell without high-temperature annealing and prepared a carbon-free, connected Pd@Pt core-shell catalyst with advanced ORR performance, highlighting its great potential as a cathode catalyst. Acknowledgement The part of this presentation is based on results obtained from a project, JPNP20003, commissioned by the New Energy and Industrial Technology Development Organization (NEDO).

Capillary Pressure Controlled Water Pathways in Gas Diffusion Layers for Polymer Electrolyte Fuel Cells Designed By Additive Manufacturing

Polymer electrolyte fuel cells (PEFC) are considered to make a significant contribution to the transition towards carbon free energy conversion, as they produce electric power from hydrogen and oxygen with water as the only by-product [1]. On its way to widespread commercialization, in particular the water management in PEFC is challenging. On one hand, the electrolyte membrane needs to be humidified to be highly conductive for the hydrogen protons. On the other hand, accumulation of the product water in the gas diffusion layer (GDL) on the cathode side mitigates the oxygen transport towards the catalytic surface, which leads to severe performance limitations [2-3]. Previous work has shown that structured GDLs can enhance PEFC performance [5] and additive manufacturing (AM) has been identified as a viable method to fabricate just such [4,6].Currently available AM technologies are struggling to fulfill the needs in terms of minimal feature size (~8 um fiber diameter) and sample size (at least some cm2). Initial AM prepared GDLs were coarse with finest structures of about 120 um [6] which is in the range of typical GDL thickness. Here, we present AM prepared GDL like structures with 20 um printed features that can reach sizes of some tens of mm2.The 3D printed structures are designed to guide the product water through the GDL by adjusting the throat size [7] and therefore the capillary pressure, which is required in the water phase to percolate through the throats to the neighboring pore as described by Young-Laplace law. Figure 1 shows tomographic data of a test lattice structure manufactured by high-resolution projection micro stereolithography (PµSL). The concept is validated by measuring the pressure in the water phase as a function of the throat size under ex-situ conditions. The desired percolation path of the water is monitored by 2D as well as 3D image data acquired by X-ray radiography and X-ray tomographic microscopy (XTM), respectively. Figure caption: XTM scan of a lattice structure manufactured by P µ SL: a) 3D rendering, b) x-z-plane cross section, c) x-y-plane cross section. Slight deformation in the base layers of the lattice structure is observed.