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At least 199 records · Page 11

Experimental and computational study of the microporous layer and hydrophobic treatment in the gas diffusion layer of a proton exchange membrane fuel cell

Enabling fuel cell operation at high current density is critical for developing competitive alternative power system to replace internal combustion engine. However, liquid water management continues to be a challenge for high humidity or high current density operation. Water condensation in the porous media hinders efficient oxygen transport to the catalyst layer, which in turns, reduces fuel cell performance. To improve water management capability, the gas diffusion layer is often impregnated with Polytetrafluoroethylene (PTFE) and coated with a thin microporous layer, which have shown to improve fuel cell performance, especially under wet conditions. However, the fundamental mechanism that drives the performance enhancement is still not well understood. In this work, the effects of PTFE impregnation and MPL were studied using both experimental and computational techniques. Both limiting current and polarization tests under dry and wet operating condition are conducted to study the oxygen transport resistance and fuel cell performance. In addition, a 2-D, two-phase, multi-physics PEMFC model is developed to simulate performance and gain a fundamental understanding of local water saturation and oxygen concentration. The combined results show that 5 wt% PTFE impregnation with MPL significantly enhances liquid water management, which enables higher current density operation of a fuel cell.

25 ENERGY STORAGE↗

Local ionic transport enables selective PGM-free bipolar membrane electrode assembly

Bipolar membranes in electrochemical CO 2 conversion cells enable different reaction environments in the CO 2 -reduction and O 2 -evolution compartments. Under ideal conditions, water-splitting in the bipolar membrane allows for platinum-group-metal-free anode materials and high CO 2 utilizations. In practice, however, even minor unwanted ion crossover limits stability to short time periods. Here we report the vital role of managing ionic species to improve CO 2 conversion efficiency while preventing acidification of the anodic compartment. Through transport modelling, we identify that an anion-exchange ionomer in the catalyst layer improves local bicarbonate availability and increasing the proton transference number in the bipolar membranes increases CO 2 regeneration and limits K + concentration in the cathode region. Through experiments, we show that a uniform local distribution of bicarbonate ions increases the accessibility of reverted CO 2 to the catalyst surface, improving Faradaic efficiency and limiting current densities by twofold. Using these insights, we demonstrate a fully platinum-group-metal-free bipolar membrane electrode assembly CO 2 conversion system exhibiting <1% CO 2 /cation crossover rates and 80-90% CO 2 -to-CO utilization efficiency over 150 h operation at 100 mA cm -2 without anolyte replenishment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low temperature hydrogen superpermeation in vanadium composite metal foil pumps

Palladium-based foil membranes are an effective option for hydrogen isotope recovery from the plasma exhaust of future fusion plants, but cost and availability are concerns. Vanadium (V) is a relatively low cost, neutron tolerant material with high hydrogen permeability. It has been well-studied as a superpermeable membrane at high temperature (>500 °C), but V displays negligible superpermeation at low temperature (75–200 °C) due to catalytic limitations. Composite membranes were fabricated by depositing thin layers (~100 nm) of either Pd or BCC PdCu on sputter-cleaned vanadium foils (100 μm). Symmetric membranes elevated superpermeation to levels approaching bulk Pd or PdCu foils, with ~5X higher flux in the latter reflecting the superior properties of PdCu. Asymmetric membranes revealed that the Pd-based catalyst layer was critical for both efficient absorption of superthermal hydrogen upstream as well as catalyzing re-combinative desorption downstream. At T ≥ 150 °C composite membrane superpermeation was equivalent to the Pd-based foils, but the flux was attenuated by a factor of 2-3X as the temperature was reduced. This deviation from pure foil performance coincided with the formation of vanadium hydride (β-V 2 H), which also impacted the transient response. Nevertheless, no embrittlement was observed under the conditions examined and elevating the temperature >150 °C removed the hydride and restored full performance. The achievement of palladium-level performance with a >99% reduction in Pd inventory makes these V composite metal foils pumps an attractive option for low temperature hydrogen isotope recovery in future fusion plants.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Catalyst-Specific Accelerated Stress Tests in Proton Exchange Membrane Low-Temperature Electrolysis for Intermittent Operation

Device-level stress tests are developed that focus on anode catalyst layer degradation and future anticipated operating conditions, including intermittent load and reduced platinum group metal content. Square-wave cycles with an upper load limit of 2.5 A cm -2 are utilized to screen commercial iridium (Ir) materials. Performance losses are primarily due to decreasing kinetics and are accompanied by catalyst migration into the membrane, worsening catalyst/ionomer integration, and weakening of the catalyst/membrane interface. For ruthenium-containing catalysts, the in situ performances are higher but durabilities lower than Ir baselines, and any performance advantage is lost within the test. Increased loss is likely due to the higher dissolution rate; microscopy confirmed greater degrees of ruthenium migration. For Ir metal or mixed oxides, ex situ activity improvements generally did not translate to in situ performance. The durability, however, is significantly lower and the loss rate increased from 3 (oxide) to 9 (metal) μ V cycle -1 . These results are consistent with historical findings in literature, rationalize the continued use of iridium oxide as a baseline catalyst, and demonstrate that traditional catalyst development approaches may not improve device-level durability when focused on low-cost applications. A shift in focus may therefore be more effective at improving catalyst utilization and lessening load requirements.

08 HYDROGEN↗

Catalytic Activity and Stability of Non-Platinum Group Metal Oxides for the Oxygen Evolution Reaction in Anion Exchange Membrane Electrolyzers

The activities and stabilities of non-platinum group metals (PGMs) in the forms of monometallic (Mn 2 O 3 , Fe 2 O 3 , Co 3 O 4 , NiO) and bimetallic (NiFe 2 O 4 , CoNiO 2 ) oxides were assessed for the oxygen evolution reaction (OER) in alkaline media and compared with IrO 2 . Both half-cell, rotating disc electrode (RDE) apparatus and single-cell, membrane electrode assemblies (MEA) were used to study kinetic and device-level performance in parallel and to provide insights into the use of these materials in anion exchange membrane (AEM) electrolyzers. Normalization of RDE results by geometric and physical surface areas, double layer capacitance, and metal content probed differences in physically vs electrochemically accessible surface areas and ensured reported trends were independent of the normalization method. The results showed that: (i) Ni- and Co- containing materials met or exceeded IrO 2 performance in both RDE and MEA testing, (ii) Co 3 O 4 deactivated over time-on-stream (1.8 V for 13.5 h) due to oxide and, relatedly, particle growth, (iii) NiFe 2 O 4 increased in activity over time-on-stream due to dissolution of Fe and an increased Ni/Fe ratio, and (iv) reduction of catalyst layer resistance is an avenue to further increase device-level performance. These results demonstrated the clear viability for non-PGMs to be used as anode catalysts in AEM devices.

25 ENERGY STORAGE↗

Effect of porous transport layer properties on the anode electrode in anion exchange membrane electrolyzers

Anion exchange membrane water electrolyzers (AEMELs) have recently received significant attention due to their potential advantages over existing commercial water electrolysis technologies. However, AEM electrolyzers have not yet met performance and durability targets. One of the critical components in achieving high AEMEL performance is the porous transport layer (PTL) which serves many critical functions in the oxygen evolution reaction (OER) electrode. In this study, several OER PTL attributes were investigated, including: material of construction, fabrication method, feature size, porosity/density, and thickness. It was found that higher porosity helped facilitate multiphase (O 2 , H 2 O, etc.) transport; however, as the porosity increased, the catalyst layer adhesion to the PTL decreased, the contact resistance with the bipolar plate increased and the cell operating voltage increased. It was found that nickel-based PTLs allowed for lower operating voltages than similarly-structured stainless steel PTLs. Improved operating voltages were achieved with both fiber felts and sintered structures by porosity optimization. Furthermore, an increase in thickness did not affect transient voltage response, however, it had a negative effect on performance stability. As a result, the experimental findings presented here provide important insights for development of PTL materials and structures for efficient and low-cost water electrolysis.

08 HYDROGEN↗

Impact of Porous Transport Layer In-Plane Conduction on Spatially Resolved Current and EIS Measurements in a Proton Exchange Membrane Water Electrolyzer

An XY segmented cell was developed for low temperature PEM water electrolysis (PEMWE). The system can assess the local performance by enabling in situ measurements of spatial currents and impedances. In this work, we show through experiments, as well as through modelling work, that the porous transport layer (PTL) must be segmented to eliminate crosstalk. Accurate measurements are only possible when crosstalk is fully eliminated. The XY segmented cell is applied to a case study characterizing the impact of a PTL platinum coating void on spatial performance. The localized performance impact of the coating void is found to be orientation specific: coating voids facing the catalyst layer reduce performance significantly more than coating voids facing the flow field. The results suggest that the tolerances for PTL coating uniformity can be lower at the side facing the flow field. The work showcases the feasibility of the XY segmented cell for impact assessment studies. The presented XY segmented cell enables the characterization of spatial phenomena in PEMWE devices and is envisioned to support modeling efforts and the investigation of manufacturing related tolerances for mass produced PEMWE devices.

08 HYDROGEN↗

All-in-one bipolar electrode: A new concept for compact and efficient water electrolyzers

Highly compact and efficient proton exchange membrane electrolyzer cells (PEMECs) are strongly desired for commercializing hydrogen production. Here, a novel concept of all-in-one bipolar electrode (AIOBE) is proposed for high-efficiency and compact PEMECs with the help of 3D printing and sputtering coating. AIOBE ideally integrated catalyst layer (CL)/gas diffusion layer/bipolar plate/current distributor/gasket, which significantly reduced component quantity on the cathode side of PEMECs from 5 to 1, cut down on part weight and volume, and drastically accelerated the fabrication and maintenance processes. Moreover, AIOBE with the micro-scale flat surface and nano-scale rough CL provided an ultralow ohmic resistance (~100 mOhm cm 2 ) and a high catalyst utilization. Finally, AIOBE delivered a practical voltage of 1.62 V and a high energy efficiency of 91% at 1000 mA/cm 2 , and its mass activity (4.48 A/mg Pt ) was 14 times higher than conventional PEMECs. In conclusion, this work provides a new route for developing highly compact electrochemical devices, such as fuel cells, electrolyzers for N 2 reduction and CO 2 conversion, and many more.

3D printing↗

Transport–Friendly Microstructure in SSC–MEA: Unveiling the SSC Ionomer–Based Membrane Electrode Assemblies for Enhanced Fuel Cell Performance

The significant role of the cathodic binder in modulating mass transport within the catalyst layer (CL) of fuel cells is essential for optimizing cell performance. This investigation focuses on enhancing the membrane electrode assembly (MEA) through the utilization of a short-side-chain perfluoro-sulfonic acid (SSC-PFSA) ionomer as the cathode binder, referred to as SSC-MEA. This study meticulously visualizes the distinctive interpenetrating networks of ionomers and catalysts, and explicitly clarifies the triple-phase interface, unveiling the transport-friendly microstructure and transport mechanisms inherent in SSC-MEA. The SSC-MEA exhibits advantageous microstructural features, including a better-connected ionomer network and well-organized hierarchical porous structure, culminating in superior mass transfer properties. Relative to the MEA bonded by long-side-chain perfluoro-sulfonic acid (LSC-PFSA) ionomer, noted as LSC-MEA, SSC-MEA exhibits a notable peak power density (1.23 W cm –2 ), efficient O 2 transport, and remarkable proton conductivity (65% improvement) at 65 °C and 70% relativity humidity (RH). These findings establish crucial insights into the intricate morphology-transport-performance relationship in the CL, thereby providing strategic guidance for developing highly efficient MEA.

25 ENERGY STORAGE↗

Exploring the Interface of Skin-Layered Titanium Fibers for Electrochemical Water Splitting

Water electrolysis is the key to a decarbonized energy system, as it enables the conversion and storage of renewably generated intermittent electricity in the form of hydrogen. However, reliability challenges arising from titanium-based porous transport layers (PTLs) have hitherto restricted the deployment of next-generation water-splitting devices. Here, it is shown for the first time how PTLs can be adapted so that their interface remains well protected and resistant to corrosion across ˜4000 h under real electrolysis conditions. It is also demonstrated that the malfunctioning of unprotected PTLs is a result triggered by additional fatal degradation mechanisms over the anodic catalyst layer beyond the impacts expected from iridium oxide stability. Now, superior durability and efficiency in water electrolyzers can be achieved over extended periods of operation with less-expensive PTLs with proper protection, which can be explained by the detailed reconstruction of the interface between the different elements, materials, layers, and components presented in this work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Combining Distributed Electrochemical Measurements with a Semi-Empirical Model to Identify Local Variations in Overpotentials for PEM Water Electrolyzers

Abstract A segmented cell and PCB approach was used to demonstrate an advanced technique for measuring and understanding the electrochemical behavior of PEM water electrolyzers. By employing a semi-empirical model, discrete modes of overpotential and their spatial distributions were identified in an operating cell. Distributed area-specific resistance (DASR measurements indicate that local dehydration of the polymer electrolyte membrane is the primary driver of increased polarization, behaving similarly to mass transport-limited currents at low flow rates due to ineffective gas-phase bubble removal. To improve quantification, the overall ohmic overpotential is divided into background (η Ohm,b ) and mass transport-coupled (η Ohm,mt ) components. Two types of anode diffusion media, a baseline PTL and a thin foil liquid/gas diffusion layer (LGDL), were examined. The results show significant variations in η Ohm,b and highlight that ineffective bubble removal leads to pronounced local dehydration. The effect of cell temperature on various overpotentials was also examined. Negligible differences in diffusion overpotential were observed when comparing PEWE performance using the PTL and LGDL, despite major differences in two-phase fluid transport within each diffusion media. This underscores the critical role of the catalyst layer's micro-porous structure in diffusion processes. The study highlights the complex nature and intricacies of mass transport limitations within PEWEs.

Roy, Anirban (ORCID:0000000163803386)↗

Study of Cathode Gas Diffusion Architecture for Improved Oxygen Transport in Hydroxide Exchange Membrane Fuel Cells

The high pH environment in hydroxide exchange membrane fuel cells (HEMFCs) has the potential to reach lower costs than the current proton exchange membrane fuel cells (PEMFCs), the incumbent technology. A significant difference between HEMFCs and PEMFCs is the location of water production within the cell. In PEMFCs, the water is produced on the cathode, limiting oxygen transport. In HEMFCs, the water is produced on the anode where the fuel is pure hydrogen. This allows the cathode to be optimized for oxygen transport without the presence of excess liquid water. Limiting current analysis, a technique previously used in PEMFCs, is adopted in HEMFCs to evaluate the oxygen mass transport resistances for different sections of the cathode. Through elimination of the microporous layer (MPL), gas diffusion layer (GDL), and traditional flow field and using porous nickel foam for gas distribution, the transport resistance at an operating condition of 150 kPa(g) and with the cell temperature at 80 °C was decreased from 112 s m −1 to 48 s m −1 , effectively halved. The optimal configuration for performance was found with Ni foam and a GDL, eliminating the MPL and traditional flow field, which vastly improved oxygen transport while maintaining adequate electrical contact with the cathode catalyst layer.

25 ENERGY STORAGE↗

Linking structure to performance: Characterization of porous transport layers for high-pressure water electrolysis

Proton exchange membrane (PEM) water electrolysis is a promising technology to produce cost-efficient hydrogen. PEM electrolyzers offer a large current density range and the ability to operate at differential pressure which can be used to minimize both capital and operational expenditures. However, directly producing pressurized hydrogen at the cathode results in pushing the membrane against the anode porous transport layer (PTL). This can lead to detrimental effects, such as membrane deformation or ruptures, which depend on membrane properties as well as PTL material properties such as pore size, structure, and morphology. In this work, a range of sinter and felt-based commercial PTLs are evaluated for their contributions to the cell's electrochemical and H 2 crossover performance at cathode pressures up to 30 bar. X-ray tomography and post-operando optical microscopy are used to assess the morphology of the PTLs, and the PTL induced deformation experienced by the catalyst coated membrane (CCM), respectively. PTL samples with lower porosity were found to reduce both the cell voltage and the amount of H 2 permeating from the cathode to the anode exhaust, which was ascribed to improved catalyst layer contact and reduced membrane deformation, respectively. The best performing PTLs improved electrolyzer efficiency by ~1.5 kWh/kg H2 . Specifically, 1 kWh/kg H2 was gained due to reducing membrane deformation and decreasing H 2 crossover. The remainder 0.5 kWh/kg H2 were achieved by improving the electrical contact at the electrode/PTL interface which decreased cell voltage.

08 HYDROGEN↗

Titanium porous-transport layers for PEM water electrolysis prepared by tape casting

While the porous-transport layer (PTL) is a key component in PEM electrolyzers, it is one of the most underexplored due to limited available structures. In this work, we present a novel PTL design for PEM water electrolyzers enabled by a cost-effective, scalable tape-casting technique. Here, a precise control of the PTL pore structure is achieved by incorporating poreformers of various sizes, and by varying the titanium and poreformer ratio. The structures are characterized with SEM and synchrotron X-ray computed tomography imaging techniques. Comprehensive electrochemical performance analysis demonstrates that higher titanium loading provides improved contact at the catalyst-layer/PTL interface but suffers from severe mass-transport losses due to gas bubbles. We solve this mass-transport problem by mixing in large poreformer beads that produce a highly porous structure with excellent gas removal properties yet still maintaining mechanical integrity. The PTL fabricated with 60:40 Ti:PMMA ratio and 60 μm PMMA bead size outperformed the standard commercial Ti powder-based PTL by 62 mV at 4 A/cm 2 .

25 ENERGY STORAGE↗

A review of functions, attributes, properties and measurements for the quality control of proton exchange membrane fuel cell components

Quality control (QC) is an essential part of fuel cell technology industrialization, providing means to reduce cost of components, enhancing the reliability of the final product, and offering specification guidance for new entrants in the supply chain. The membrane electrode assembly (MEA), including membrane, catalyst layer (CL), and gas diffusion layer (GDL), as well as bipolar plate (BP), are key components of a proton exchange membrane (PEM) fuel cell, and the attributes of each component strongly correlate with the cell performance and longevity. To ensure the quality of the fuel cell, it is of great importance to characterize the properties with respect to the standardization of component/sub-component specifications. In collaboration with the fuel cell industry, this work aims at establishing compendiums of attributes, or so-called books of attributes, of key fuel cell components for the QC of PEM fuel cells through reviewing, identifying, categorizing, and prioritizing the main attributes/properties that determine their functionalities. The books of attributes for the major PEM fuel cell components include catalyst coated membrane (CCM) as a sub-assembly, GDL, and BP. To address the full spectrum of fuel cell components, gaskets and sub-gaskets are also included.

25 ENERGY STORAGE↗

Applications of Atomic Layer Deposition in the Modification of Carbon Nanotubes

Atomic Layer Deposition (ALD) is a cost-effective nanoadditive-manufacturing technique that allows for conformal coating of substrates with atomic control in a benign temperature and pressure environment. Using paired precursor gases, thin films can be deposited on flat or textured surfaces ranging from glass, polymers, aerogels, and metals. Through atomic layer control, where single layers of atoms are deposited, fabrication of metal transparent films, nano-laminates, and coatings of nano-channels and pores is achievable. Reaction mechanisms in ALD are normally self-limiting, allowing for atomically accurate control of nanometer (nm) thicknesses. Therefore, high uniformity and precise thickness control make ALD an attractive process for the creation of novel nano-scale devices. Decreases in resistivity and density of electrical wire are needed to improve the function of electronics, electric motors and cables. Such improvements may be accomplished by adding ballistically conducting, metallic carbon nanotubes (CNT) to Cu. ALD was used to coat multiple substrates including CNT with Cu in an effort to make CNT-Cu composites which is more conductive and less dense than Cu. In addition, ALD can be used to as a method to deposit the catalyst layer seed layer for CNT growth using Ni. The ALD of copper metallic films can follow multiple reaction pathways depending on the ALD precursors used. For this work the reaction pathway was deposition of copper oxide and then post process annealing in a hydrogen environment. Copper(II) diacetylacetonate (Cu(acac)2) and ozone are used as precursors for copper oxide. As-deposited copper oxide films prepared at 180°C resulted in a growth per cycle of 1.0 A/cycle with low film resistivity.

Dwivedi, Vivek H.↗

Highly Durable Fluorinated High Oxygen Permeability Ionomers for Proton Exchange Membrane Fuel Cells

For proton exchange membrane fuel cells to be cost-competitive in light- and heavy-duty vehicle applications, their Pt content in the catalyst layers needs to be lowered. However, lowering the Pt content results in voltage losses due to high local oxygen transport resistances at the ionomer–Pt interface. It is therefore crucial to use ionomers that have higher oxygen permeability than Nafion. In this paper, novel high oxygen permeability ionomers (HOPIs) are presented, with up to five times higher oxygen permeability than Nafion, synthesized by copolymerization of perfluoro-2,2-dimethyl-1,3-dioxole (PDD) with perfluoro(4-methyl-3,6-dioxaoct-7-ene) sulfonyl fluoride (PFSVE). PDD is the source of higher permeability due to its open ring structure, while PFSVE provides ionic conductivity. Optimization of PDD content and equivalent weight enables increased fuel cell performance, mainly at high current densities, where HOPIs can achieve power densities >1.25 W cm -2 and exceed the 0.8 A cm -2 U.S. Department of Energy durability target by losing only 4.5 mV, which is over six times less than 30 mV. Finally, the interactions between HOPI and SO 3 - groups with a PtCo/C catalyst are also elucidated here at a fundamental level.

25 ENERGY STORAGE↗

X-ray Photoelectron Spectroscopy Analysis of Nafion-Containing Samples: Pitfalls, Protocols, and Perceptions of Physicochemical Properties

X-ray photoelectron spectroscopy (XPS) is one of the most common techniques used to analyze the surface composition of catalysts and support materials used in polymer electrolyte membrane (PEM) fuel cells and electrolyzers, providing important insights for further improvement of their properties. Characterization of catalyst layers (CLs) is more challenging, which can be at least partially attributed to the instability of ionomer materials such as Nafion during measurements. This work explores the stability of Nafion during XPS measurements, illuminating and addressing Nafion degradation concerns. The extent of Nafion damage as a function of XPS instrumentation, measurement conditions, and sample properties was evaluated across multiple instruments. Results revealed that significant Nafion damage to the ion-conducting sulfonic acid species (>50% loss in sulfur signal) may occur in a relatively short time frame (tens of minutes) depending on the exact nature of the sample and XPS instrument. This motivated the development and validation of a multipoint XPS data acquisition protocol that minimizes Nafion damage, resulting in reliable data acquisition by avoiding significant artifacts from Nafion instability. The developed protocol was then used to analyze both thin film ionomer samples and Pt/C-based CLs. Comparison of PEM fuel cell CLs to Nafion thin films revealed several changes in Nafion spectral features attributed to charge transfer due to interaction with conductive catalyst and support species. This study provides a method to reliably characterize ionomer-containing samples, facilitating fundamental studies of the catalyst-ionomer interface and more applied investigations of structure-processing-performance correlations in PEM fuel cell and electrolyzer CLs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗