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At least 55 records · Page 3

Current research in low temperature proton exchange membrane-based electrolysis and a necessary shift in focus

While hydrogen has limited use in energy markets today, significant growth is possible in grid storage and as an energy carrier in other sectors. Along with lower electricity prices, further hydrogen cost reduction can enable electrochemical water splitting, particularly as the use of intermittent, renewable power sources increases and the quantity and duration of storage requirements limit electrical storage options. With the improved viability of large-scale hydrogen production, research in low temperature electrolysis has dramatically increased. The overwhelming majority of research efforts within proton exchange membrane-based systems has focused on catalyst development, although a smaller set have developed transport layers as well. As proton exchange membrane-based electrolysis shifts into higher technology readiness levels, however, there is a growing need for work optimizing materials integration, developing component-specific and device-level accelerated stress tests, and addressing manufacturing considerations. These areas directly impact electrolyzer performance, durability, and cost, and are critical to advancing hydrogen’s value and electrochemical water splitting.

08 HYDROGEN↗

Influence of Supporting Electrolyte on Hydroxide Exchange Membrane Water Electrolysis Performance: Catholyte

Alkaline or hydroxide exchange membrane water electrolysis (HEMWE) is a promising technology for green hydrogen production using platinum group metal-free catalysts and stainless steel, an advantage of alkaline water electrolysis (AWE), and a gas-impermeable membrane, a parallel to proton exchange membrane electrolysis (PEMWE). However, the HEMWE requires supporting electrolytes and there is minimal understanding of their role on the respective reactions. Without SELs, HEMWE performance and durability are worse than PEMWE systems. Herein, consistently feeding potassium hydroxide anolyte, we systematically study the effects of catholyte SELs in HEMWEs including dry vs. wet operation, cation effects, anion effects, and cation/OH ratios on cell potential and stability. We report that (i) hydration of the cathode improves high current density operation by preventing dehydration of the hydroxide exchange membrane (HEM), (ii) there was no correlation between cation type and cell potential, (iii) cell potential and high frequency resistance did not correlate with SEL conductivity, (iv) cathodic carbonate SEL had a significant negative effect on cell performance, (v) increased cation/OH ratio also caused increased cell potentials. Overall, this study concludes that feeding water or potassium hydroxide solution is desirable to improve the AEMWE performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Non-noble metal based electro-catalyst compositions for proton exchange membrane based water electrolysis and methods of making

The invention provides electro-catalyst compositions for an anode electrode of an acid mediated proton exchange membrane-based water electrolysis system. The compositions include a noble metal component selected from the group consisting of iridium oxide, ruthenium oxide, rhenium oxide and mixtures thereof, and a non-noble metal component selected from the group consisting of tantalum oxide, tin oxide, niobium oxide, titanium oxide, tungsten oxide, molybdenum oxide, yttrium oxide, scandium oxide, cooper oxide, zirconium oxide, nickel oxide and mixtures thereof. Further, the non-noble metal component can include a dopant. The dopant can be at least one element selected from Groups III, V, VI and VII of the Periodic Table. The compositions can be prepared using any solution based methods involving a surfactant approach or a sol gel approach. Further, the compositions are prepared using noble metal and non-noble metal precursors. Furthermore, a thin film containing the compositions can be deposited onto a substrate to form the anode electrode.

Kumta, Prashant N.↗

Simulated Start-Stop and the Impact of Catalyst Layer Redox on Degradation and Performance Loss in Low-Temperature Electrolysis

Stress tests are developed that focus on anode catalyst layer degradation in proton exchange membrane electrolysis due to simulated start-stop operation. Ex situ testing indicates that repeated redox cycling accelerates catalyst dissolution, due to near-surface reduction and the higher dissolution kinetics of metals when cycling to high potentials. Similar results occur in situ, where a large decrease in cell kinetics (>70%) is found along with iridium migrating from the anode catalyst layer into the membrane. Additional processes are observed, however, including changes in iridium oxidation, the formation of thinner and denser catalyst layers, and platinum migration from the transport layer. Increased interfacial weakening is also found, adding to both ohmic and kinetic loss by adding contact resistances and isolating portions of the catalyst layer. Repeated shutoffs of the water flow further accelerate performance loss and increase the frequency of tearing and delamination at interfaces and within catalyst layers. These tests were applied to several commercial catalysts, where higher loss rates were observed for catalysts that contained ruthenium or high metal content. These results demonstrate the need to understand how operational stops occur, to identify how loss mechanisms are accelerated, and to develop strategies to limit performance loss.

08 HYDROGEN↗

La–Sr–Co oxide catalysts for oxygen evolution reaction in anion exchange membrane water electrolyzer: The role of electrode fabrication on performance and durability

Anion exchange membrane water electrolysis is an attractive technology for low-cost generation of “green” hydrogen by combining the use of noble metal-free catalysts with pure water feed. By thus addressing main drawbacks of the liquid alkaline electrolysis and proton exchange membrane water electrolysis, anion exchange membrane water electrolysis stands an excellent chance of replacing the two technologies. The development of active and stable platinum group metal (PGM)-free catalysts for oxygen evolution reaction (OER) is crucial for making anion exchange membrane water electrolyzers (AEMWEs) practical. For this work, we synthesized, characterized and tested two La–Sr–Co oxide-based OER catalysts. First, we characterized the catalysts by XRD, SEM, and N 2 physisorption and assessed their OER activity in a three-electrode cell. Next, we focused on electrode fabrication, demonstrating the importance of catalyst-ink application to the porous transport layers (PTLs) and a key role of adding a binder to the catalyst ink to prevent the catalyst detachment from the PTL in pure water. We tested three membrane electrode assemblies prepared using different formulations of the anode catalyst ink. The results show that the optimum ink formulation is essential for the performance on pure-water feed by maximizing OH - conductivity of the catalyst layer and catalyst-membrane interface.

47 OTHER INSTRUMENTATION↗

Anion Exchange Membrane Water Electrolysis Using a Catalyst-Coated Membrane Cathode

A catalyst-coated membrane (CCM) approach to electrode fabrication for high pH water electrolysis offers enhanced interfacial contact between the catalyst layer and the membrane surface in comparison to the catalyst-coated substrate (CCS) electrode configuration. The CCM facilitates enhanced ionic and water transport between the cathode and the anion exchange membrane (AEM). This advantage is particularly significant with AEM water electrolysis (compared to proton exchange membrane water electrolysis) because the cathode typically operates under dry conditions and relies solely on diffusive water transport across the AEM from the liquid-fed anode. This study presents a direct performance comparison between CCS and CCM cathode configurations using identical hydrogen evolution reaction (HER) catalysts and other components. The use of a pseudo-reference electrode integrated into the membrane electrode assembly enabled detailed analysis of the CCM cathode polarization behavior. Surface characterization provided insight into the degradation mechanisms associated with the CCM configuration. Optimization of the cathode ionomer cross-link density improved both the cathode polarization performance and the electrolysis device durability. Further optimization of the HER catalyst loading in the CCM cathode resulted in additional gains in the electrolysis efficiency. Collectively, these findings offer valuable guidance for the design and fabrication of high-performance, durable AEM electrolysis CCMs.

Water electrolysis↗

Proton Exchange Membrane (PEM) Water Electrolysis: Cell-Level Considerations for Gigawatt-Scale Deployment

Hydrogen produced with no greenhouse gas emissions is termed “green hydrogen” and will be essential to reaching decarbonization targets set forth by nearly every country as per the Paris Agreement. Proton exchange membrane water electrolyzers (PEMWEs) are expected to contribute substantially to the green hydrogen market. However, PEMWE market penetration is insignificant, accounting for less than a gigawatt of global capacity. Achieving substantive decarbonization via green hydrogen will require PEMWEs to reach capacities of hundreds of gigawatts by 2030. This paper serves as an overarching roadmap for cell-level improvements necessary for gigawatt-scale PEMWE deployment, with insights from three well-established hydrogen technology companies included. Analyses will be presented for economies of scale, renewable energy prices, government policies, accelerated stress tests, and component-specific improvements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Electro-Sprayed Porous Electrodes on the Performance and Stability of Water Electrolysis

The efficiency of proton exchange membrane water electrolysis (PEMWE) is a critical issue in realizing the production of green hydrogen. Here, the coexistence of three phases in the catalyst layer of PEMWE causes the mass transport limitation at the interfaces between them. In particular, the vigorous production of gaseous hydrogen and oxygen derived from liquid water is generated in the form of bubbles that seriously deactivate the membrane-electrode assembly (MEA). In this study, we investigated the effect of porous structure in the electrode on the efficiency of hydrogen production at high current density, which is highly related to the mass transport limitation. A widely used commercial catalyst (IrO 2 ) were directly coated on the membrane by the electro-spray method. The porous electrodes on the membrane were formed by the charged catalyst particles that repulsed each other due to the electrostatic forces of the particles. Our membrane electrode assembly (MEA) exhibited outstanding electrolysis performances such as 5.3 A cm -2 and 3.2 A cm -2 at 2.0 V and 1.8 V, respectively, which are the highest values compared with the results published in the current studies. In addition to the porosity, it was confirmed that optimum binder contents positively affect the hydrophobicity and contact resistance of MEA. Through a simple porosity-controlled technique, the performance of PEMWE, in which three phases coexist, can be improved by more than 60 %. Accordingly, we expect that our systematic study on the role of porosity in the electrodes opens a new era to efficiently produce green hydrogen.

catalysts↗

Influence of Supporting Electrolyte on Hydroxide Exchange Membrane Water Electrolysis Performance: Anolyte

Hydroxide-exchange-membrane water electrolysis (HEMWE) is an emerging hydrogen-production pathway that combines many advantages of incumbent alkaline water electrolysis (AWE) and proton-exchange-membrane water electrolysis (PEMWE). Advancement in HEMWE has been accelerated with the development of stable and conductive hydroxide exchange membranes (HEMs) and a more comprehensive understanding of alkaline gas-evolving kinetics. However, performance and durability without supporting electrolytes (SELs) remain inferior to PEMWE and AWE and little is known about the role and impact of the SELs. This study investigates the effects of SELs used as anolyte solutions in HEMWEs including cation-type, anion-type, SEL conductivity and pH, presence of carbonates and increased cation/OH- ratios on cell voltage and stability. We report our findings that (i) cell potential and high-frequency resistance did not correlate with anolyte SEL conductivity, (ii) cation-type influences cell voltage at low current densities (<50 mA cm -2 ) as predicted by half-cell measurements, (iii) increased cation/OH- ratio causes increased overpotentials, and (iv) carbonates are exchanged in the HEM but removed via self-purging at high current density. Overall, this study concludes that concentrated KOH is still the best SEL.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

H 2 Production Pathways Cost Analysis (2016 - 2021) (Final Report)

This final report documents cost analysis conducted for the Department of Energy over a five year period (2016 to 2021) pertaining to hydrogen production and delivery system components, focusing on the key remaining challenges of the technology pathways within the Hydrogen Production and Delivery sub-program portfolio. A particular focus was placed on electrolysis for the generation of hydrogen. The effort primarily used the H2A discounted cash flow computational model as a tool to project hydrogen cost ($/kgH 2 ) and determine status improvements resulting from technology advancements. The effort also considered cost as a function of production volume, employed error bars to illustrate uncertainties in the cost estimates, and utilized sensitivity analyses to show the potential for cost reductions. The project examined a range of hydrogen production and delivery related systems. These included WireTough wire-wrapped pressure vessels for hydrogen storage, proton exchange membrane (PEM) electrolysis, solid oxide electrolysis (SOE), anion exchange membrane (AEM) electrolysis, photoelectrochemical (PEC) electrolysis, solar thermochemical hydrogen (STCH) production, the cost of energy transmission, and a study on the necessary price of hydrogen to produce competitively-priced electricity via fuel cell conversion.

08 HYDROGEN↗

High-Throughput Uniformity and Defect Monitoring in Low-Temperature Electrolysis Porous Transport Layers Using X-Ray Radiography

Effective quality control (QC) for manufacturing proton exchange membrane water electrolysis (PEMWE) components is critical to enabling widespread adoption of the technology for hydrogen generation. This study investigates X-ray radiography as a novel, high-throughput, potentially in-line QC technique for detecting defects and assessing material property distributions in titanium-based porous transport layers (PTLs) which constitute a crucial component of low temperature PEMWE stacks. We obtain radiographs of a set of fifteen PTLs and model their absorbance of the broadband radiation as a second-order polynomial to account for the non-monoenergetic radiation source used in this study. The resulting model serves as a basis for predicting the areal density and porosity distributions of the PTLs. We find radiography successful in detecting multiple instances of defects, including holes/depressions, cracks, and excess material on the surface or in the pores of the material, demonstrating its potential as a robust in-line QC tool for PTL manufacturing.

08 HYDROGEN↗

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↗

High-performance multiblock PEMs containing a highly acidic fluorinated-hydrophilic domain for water electrolysis

The present paper describes the design and evaluation of novel hydrophilic–hydrophobic poly(arylene ether sulfone) (PAES) multiblock copolymers for their synergistic effects upon transport properties and their potential use in proton exchange membrane water electrolysis. The multiblock copolymers are prepared via a coupling reaction between (i) a hydrophilic segment consisting of a disulfonated quinone fluorinated biphenyl group that contains fluorine moieties next to the sulfonated groups to increase the acidity, and (ii) hydrophobic segments composed of non-sulfonated biphenyl sulfone to provide dimensional stability. Two different lengths (molecular weights; 5k and 10k, where k represents 10 3 g mol -1 ) of hydrophobic segments are used to investigate the effects of the membrane properties compared with those of Nafion® and PAES random copolymer (i.e., BPSH40). Atomic force microscopy images of the BPSH40 and multiblock membranes are shown to agree closely with a mesoscale simulation, thus confirming the importance of the morphological effect upon the transport properties. Furthermore, the multiblock copolymer with a higher proportion of hydrophilic segments (10 k–5k) was shown to provide enhanced performance (3.41 A cm -2 at 1.9 V) compared to the multiblock copolymer with equal proportions of hydrophilic and hydrophobic segments (10 k–10 k) due to the greater continuity of nano-sized ionic channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanochannel electrodes facilitating interfacial transport for PEM water electrolysis

Proton-exchange membrane water electrolyzers (PEMWEs) are a promising technology for green hydrogen production; however, interfacial transport behaviors are poorly understood, hindering device performance and longevity. Here, we first utilized finite-gap electrolyzer to demonstrate the possibility of proton transfer through water in PEMWEs. The measured high-frequency resistances (HFRs) exhibit a linear trend with increasing gap distance, where extrapolation shows a lower value compared with HFRs in regular zero-gap electrolyzers, indicating that ohmic resistance could be further reduced. We introduce nanochannels to facilitate mass transport, as evidenced by both liquid-fed and vapor-fed electrolysis. Nanochannel electrodes achieve a voltage reduction of 190 mV at 9 A·cm –2 compared with the Ir-PTEs without nanochannels. Furthermore, nanochannel electrodes show negligible degradation through 100,000 accelerated-stress tests and over 2,000 h of operation at 1.8 A·cm –2 with a decay rate of 11.66 μV·h –1 . These results provide new insights into localized transport dynamics for PEMWEs and highlight the significance of interfacial engineering for electrochemical devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Performance and Durability Investigation of Thin, Low Crossover Proton Exchange Membranes for Water Electrolyzers

The goal of this project was to fabricate and study the performance and durability implications of thin, mechanically reinforced membranes containing gas recombination catalysts (GRCs) for advanced proton exchange membrane water electrolysis (PEMWE) systems. The thinner membranes, optimized for a PEMWE environment, dramatically reduced the proton transport resistance across the membrane, improving the overall efficiency of the PEMWE system. At the same time, the GRC technology was deployed to recombine crossover hydrogen from the cathode with oxygen from the anode to form water within the membrane. This reaction mitigated the buildup of hydrogen in the oxygen stream, ensuring safe operation of the PEMWE system. Capabilities to measure the gas crossover in both an ex-situ screening cell and in operando application testing were developed over the course of the project to track membrane progress and quantify deliverables. State of the art roll to roll manufacturing technologies were leveraged to fabricate the membranes on a commercial scale, where the membrane structure was precisely tuned and GRC distributed within the membrane structure.

08 HYDROGEN↗

Dislocation-Activated Low Platinum-Loaded PtCu Nanoparticles Welded onto the Substrate for Practical Acidic Hydrogen Generation

Although transition metal (M) alloying with platinum (Pt) is a promising approach to reduce the Pt dosage required in the hydrogen evolution reaction (HER), the catalytic activity and durability of PtM alloy are often unsatisfactory for acidic HER, especially at high currents, due to a reduced number of highly active sites (Pt) at the atomic level and challenges in stabilizing them to prevent detachment and aggregation. Herein, we report a robust functional structure integrated electrode (D-PtCu/CF) with abundant edge dislocations and very low platinum content (0.1 mg cm -2 ) to achieve high activity and stability in acidic HER within a proton exchange membrane water electrolysis cell (PEMWE). D-PtCu/CF exhibits high Pt mass activity (10.28 A mg Pt -1 ) and excellent operational stability (negligible decay after 200 h). X-ray absorption spectroscopy and in situ electrochemical experiments reveal that the lattice distortion caused by edge dislocations in PtCu mainly affects Pt atoms by compressing strain, reducing their ability to adsorb H. At the same time, Cu atoms are subjected to tensile strain, enhancing the bonding between Cu and H. Therefore, edge dislocations not only improve the intrinsic catalytic activity of Pt atoms but also increase the number of active sites (Cu) available for hydrogen adsorption, which synergistically accelerates the kinetics of the HER reaction. Finally, the PEMWE employing the D-PtCu/CF catalytic electrode can operate stably for 100 h at an industrial-level current density of 500 mA cm -2 with 1.63 V.

30 DIRECT ENERGY CONVERSION↗

Synergistic Co-Ir/Ru Composite Electrocatalysts Impart Efficient and Durable Oxygen Evolution Catalysis in Acid

Exploring highly active and robust catalysts, which have low precious metal content, to boost the kinetically sluggish oxygen evolution reaction (OER) is a key concern for hydrogen production via proton exchange membrane water electrolysis (PEMWE). Here, in this work, rational engineering of the morphology and the local geometric ligand environment of Ir and Ru catalysts are presented by using defect-rich, lanthanum- and lithium-doped Co 3 O 4 nanofiber (LLCF) as substrate that promotes the electrocatalytic OER. Two catalysts, IrCoOx@LLCF and RuCoOx@LLCF, achieve mass activities of 1013.5 A g Ir –1 and 1911.4 A g Ru –1 in 0.1 M HClO 4 at 300 mV overpotential, respectively, which are 26 and 50 times higher than that of commercial IrO 2 and RuO 2 . Operando X-ray absorption spectroscopy unveils the reversible structure of IrCoOx during the OER and the suppression of over-oxidation of Co and Ir, giving rise to high stability. Density functional theory calculations reveal that the local geometric ligand engineering optimizes the binding of oxygenated species to the active sites, resulting in strongly enhanced catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elucidating effects of catalyst loadings and porous transport layer morphologies on operation of proton exchange membrane water electrolyzers

Producing green hydrogen efficiently via proton exchange membrane water electrolysis (PEMWE) is the key for achieving decarbonization targets. Iridium catalyst is expensive, and it is important to minimize its use and to optimize interface between Ir and ionomer or water for higher utilization of catalyst in oxygen evolution reaction. In this work, x-ray computed tomography along with electrochemical and modeling techniques are used to characterize the interface for two different porous transport layers (PTLs) and catalyst layers at various loadings. We show that low porosity sintered PTLs exhibit higher interfacial contact with the catalyst and the membrane that results in improved kinetics. Radiography and modeling results indicate that oxygen taking multiple transport pathways through the PTL results in slug flow through the channels that reduces mass transport overpotential. Based on the results, we suggest design guidelines for high efficiency and durable PEMWE and their components.

08 HYDROGEN↗