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At least 37 records · Page 2

Tantalum oxide stabilized molybdenum-doped ruthenium oxide electrocatalysts for PEM water electrolysis

Proton exchange membrane (PEM) water electrolysis offers key advantages, including high current density, high efficiency, and compact system architecture for hydrogen production. However, its widespread implementation is limited by the scarcity and high cost of Ir-based anodic catalysts. Herein, we report an Ir-free electrocatalyst for the acidic oxygen evolution reaction (OER): tantalum oxide (TaO x )–coated molybdenum-doped RuO 2 (TaO x -MoRuO 2 ). The catalyst exhibits a low overpotential of 180 mV at 10 mA cm -2 and excellent durability, with a degradation rate of 0.034 mV h -1 over a 150-hour test at 50 mA cm -2 —surpassing other Ru-based catalysts evaluated under similar conditions. A PEM electrolyzer employing TaO x -MoRuO 2 as the anode maintained stable operation for 100 hours at 500 mA cm -2 . In conclusion, the TaO x coating layer suppresses Ru and Mo dissolution, thus enhancing their stability likely via interfacial electronic reconfiguration of Ru and Mo mediated by bridging oxygen atoms.

Durability↗

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↗

Impact of Catalyst Ink Dispersing Solvent on PEM Fuel Cell Performance and Durability

The dispersing solvent used for fuel cell catalyst ink preparation plays a vital role in establishing the resulting morphology of the electrode layers, which in turn will impact the performance of proton exchange membrane (PEM) fuel cells. In this study, we report the impact of various ionomer dispersion solvents on PEM fuel cell performance and durability; two aqueous (1-propanol/water and 2-propanol/water) and several non-aqueous dispersing solvents (ethylene glycol and 1,2-butanediol) are compared. The cathode catalyst layer (CCL) fabricated using inks prepared with 1-propanol/water (3:1, w/w) exhibited the best initial performance followed by the CCL prepared using ethylene glycol. The CCLs made from non-aqueous ethylene glycol and 1,2-butanediol exhibited the best durability upon accelerated stress testing. Scanning transmission electron microscopy combined with energy dispersive X-ray spectroscopy indicated that, after the stress test, the distribution of both the Nafion ionomer and Pt nanoparticles within the CCLs prepared with non-aqueous ionomer dispersions underwent less change than those prepared with aqueous dispersions, which is responsible for the improved durability

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Performance Losses and Current-Driven Recovery from Cation Contaminants in PEM Water Electrolysis

Water contaminants are a common cause of failure for polymer electrolyte membrane (PEM) electrolyzers in the field as well as a confounding factor in research on cell performance and durability. In this study, we investigated the performance impacts of feed water containing representative tap water cations at concentrations ranging from 0.5–500 μ M, with conductivities spanning from ASTM Type II to tap-water levels. We present multiple diagnostic signatures to help identify the presence of contaminants in PEM electrolysis cells. Through analysis of polarization curves and impedance spectroscopy to understand the origins of performance losses, we found that a switch from the acidic to alkaline hydrogen evolution mechanism is a key factor in contaminated cell behavior. Finally, we demonstrated that this mechanism switching can be harnessed to remove cation contaminants and recover cell performance without the use of an acid wash. We demonstrated near-complete recovery of cells contaminated with sodium and calcium, and partial recovery of a cell contaminated with iron, which was further investigated by post-mortem microscopy. The improved understanding of contaminant impacts from this work can inform development of strategies to mitigate or recover performance losses as well as improve the consistency and rigor of electrolysis research.

30 DIRECT ENERGY CONVERSION↗

An Acid-Free, Temperature-Based Cation Contamination Removal Strategy for PEM Water Electrolysis

It is widely understood that the durability and reliability of polymer electrolyte membrane (PEM) water electrolyzers are heavily dependent on feedwater purity, with cation contaminants that originate from incomplete water purification and balance of plant materials significantly harming electrolyzer performance. However, contamination remains a challenge and a common cause of failure at the stack level, indicating the need for strategies to recover the performance of contaminated cells. In this study, we investigate the effects of temperature on the uptake, electrochemical impacts, and removal of contaminant calcium and iron cations. Lower operating temperatures increase the sensitivity of the cell performance to contaminant cations, while also decreasing cation uptake and promoting contaminant removal. Computational charge transfer modelling shows that lower temperature increases the concentration of contaminant at the cathode and facilitates their removal from the cell. By testing single cells under scenarios designed to mimic stack temperature dynamics, we investigate low-temperature operation as an approach to stack-relevant contaminant recovery. Together, these results demonstrate that the low-temperature recovery approach is a promising approach for acid-free contamination recovery for PEM water electrolysis to promote stack reliability and durability.

08 HYDROGEN↗

New Approaches to Improved PEM Fuel Cell Catalyst Layers

Polymer-electrolyte membrane (PEM) fuel-cells are one of the most promising energy conversion technologies for renewable clean energy applications. A major challenge preventing the widespread use and commercialization of PEM fuel cells is achieving high performance with low-loadings of platinum group metal (PGM) catalysts. One of the factors driving performance limitations in the cell is the mass transport losses within the cathode catalyst layers (CCL) due to sluggish oxygen-reduction reactions occurring at the platinum-ionomer interface. Any resistance to transport of these ionic and gaseous species within the CCL results in mass-transport limitations and performance losses, especially at high current densities. It is known that mass-transport losses increase with reduced platinum loading, thereby creating a performance-cost tradeoff for fuel cells. A viable solution to reduce the transport resistances in the catalyst layers is to create new ionomers that can provide good ion and oxygen transport needed to accomplish high-performing fuel cell catalysts. Using this approach Tetramer Technologies and LBNL propose improved fuel-cell catalyst ionomers based on Tetramers proprietary polymer chemistry.

30 DIRECT ENERGY CONVERSION↗

Manufacturing Cost Analysis for PEM Electrolyzers and Perspectives for Future Cost Reduction

Electrolyzer capital costs strongly influence the total levelized cost of hydrogen production and have implications for hydrogen deployment. Current electrolyzer costs are high, and large cost reductions may be needed to achieve competitive hydrogen costs and targets. Understanding pathways for cost reduction via R&D and deployment is a critical research area for informed energy planning and enabling hydrogen use. This work presents bottom-up cost estimates of polymer electrolyte membrane (PEM) electrolyzer systems tied to design specifications and discusses perspectives for cost reduction opportunities based on ongoing research. We use a detailed manufacturing and process model for a 1 MW PEM electrolyzer stack and balance of plant (BOP) for rigorous cost estimation. This allows for robust estimates of component and manufacturing costs and examination of key cost contributors. Stack costs are dominated by material costs such as iridium and platinum catalysts, especially at high manufacturing rates; power electronics and hydrogen purification equipment are the largest contributors to BOP cost. At higher manufacturing rates, better equipment utilization could reduce stack costs significantly, and we estimate that experience and bulk purchasing will allow for cost reductions to some BOP components. Still, many well-established BOP technologies and stack material costs are less likely to see significant cost reductions at high manufacturing rates. As such, manufacturing scale is limited in how much it can reduce electrolyzer costs, and additional advances for cost reduction may be needed to achieve cost targets. It will likely take many combined strategies to achieve significant cost reductions for electrolyzers and enable low-cost hydrogen production. We can use our manufacturing cost model to quantify potential cost reductions from the considerations described above and demonstrate pathways to lower cost electrolyzers. This allows for better understanding of cost reduction strategies and enables more informed research, development, and deployment for electrolyzers.

cost↗

Electron and proton conductivity of Fe-N-C cathodes for PEM fuel cells: A model-based electrochemical impedance spectroscopy measurement

Impedance spectra of a PEM fuel cell with three Fe-N-C cathodes have been measured under the H 2 /N 2 testing regime. The spectra have been fitted using a recently developed physics-based impedance model, which takes into account finite proton ($σ_p$) and electron ($σ_e$) conductivity of the oxygen-free cathode catalyst layer. Fitting allowed to extract numerical data for $σ_p$, $σ_e$, the double layer capacitance, and the inductance of cables used for measuring impedance spectra. The values of σp and σe are close to what previously found for standard Pt/C electrodes, which is found for the first time using PGM-free catalysts. The method enables simultaneous measurement of reference proton and electron conductivity of PEMFC cathode.

25 ENERGY STORAGE↗

Advances in benchmarking and round robin testing for PEM water electrolysis: Reference protocol and hardware

While the number of publications in the PEM water electrolysis community increases each year, no common ground concerning reference hardware (test cells and test bench) and testing protocols has been yet established. This would, however, be necessary for the comparability of experimental results. First attempts for such reference hardware and procedures have been made in the framework of the Task 30 Electrolysis within the Technology Collaboration Programme on Advanced Fuel Cells (AFC TCP) of the International Energy Agency (IEA). Since then, improvements of both the test hardware (test cell and components) as well as the measurement protocol were identified, and a revised methodology and key results based on a comprehensive measurement series have been obtained. A detailed protocol for testing commercial reference components with a reference laboratory test cell developed in-house by Fraunhofer ISE is presented. For evaluation of the protocol and the hardware, it was tested at three different institutions at the same time. Impedance spectroscopic and polarization data was acquired and analyzed. The obtained differences in performance were calculated to give the community an expectation window to compare own data to. Finally, the importance of a thorough temperature control and the conditioning phase are demonstrated.

08 HYDROGEN↗

The impacts of membrane pinholes on PEM water electrolysis

Polymer electrolyte membrane (PEM) water electrolysis is a promising technology to efficiently produce green hydrogen. Irregularities in membrane electrode assembly (MEA) component materials caused by manufacturing, processing, handling, or operation can lead to performance loss and failure. One example is the presence of pinholes in the membrane, which can cause increased gas transport (crossover) and lead to electrical shorting. This work investigates the effects of intentionally introduced pinholes with various sizes up to 350μm in diameter. The presence of the pinholes resulted in minimal impacts on the cell voltage (±30 mV at 4Acm -2 ). However, the pinholes significantly increased H 2 crossover, which decreased hydrogen production efficiency and increased the minimum current density for safe operation. The impacts of the pinhole on the H 2 crossover and efficiency are more severe for open pinhole features than tear-like pinhole features. In conclusion, this research demonstrates that even small pinholes cannot be disregarded from a safety, efficiency, and operating strategy perspective.

08 HYDROGEN↗

LTE-P-3 IEC PEM SOP

A procedure for measuring the ion exchange capacity (IEC) of a proton exchange membrane (PEM).

08 HYDROGEN↗

Advanced electrode manufacturing to enable low cost PEM electrolysis

A critical challenge for the implementation of proton exchange membrane (PEM)-based water electrolyzers for the H2@Scale vision is the capital cost, which is largely driven by related factors of overdesign and highly manual legacy manufacturing methods. Typical electrolyzer cells have an order of magnitude higher membrane thickness and catalyst loading vs. fuel cells, in part because the manufacturing methods being used are not capable of producing uniform and reliable electrodes on thin membranes with low loading. Advanced electrode manufacturing is therefore the key enabler to reduce the cost of the electrolyzer stack, particularly roll-to-roll (R2R) manufacturing of catalyst coated layers (CCLs) and catalyst coated membranes (CCMs). The electrolyzer manufacturing process still relies on traditional sheet-to-sheet (S2S) processes, which requires intensive labor to make parts to meet the specification requirements. This project leverages fuel cell expertise (GM) with Proton’s knowledge of electrolyzer components to develop the electrocatalyst ink formulations and coating processes using slot die (ORNL) and gravure (NREL) coatings, with proof of concept at the pilot-scale (Kodak).

08 HYDROGEN↗

Rational Materials and Structure Design for Improving the Performance and Durability of High Temperature Proton Exchange Membranes (HT-PEMs)

Hydrogen energy as the next-generation clean energy carrier has attracted the attention of both academic and industrial fields. A key limit in the current stage is the operation temperature of hydrogen fuel cells, which lies in the slow development of high-temperature and high-efficiency proton exchange membranes. Currently, much research effort has been devoted to this field, and very innovative material systems have been developed. The authors think it is the right time to make a short summary of the high-temperature proton exchange membranes (HT-PEMs), the fundamentals, and developments, which can help the researchers to clearly and efficiently gain the key information. In this paper, the development of key materials and optimization strategies, the degradation mechanism and possible solutions, and the most common morphology characterization techniques as well as correlations between morphology and overall properties have been systematically summarized.

08 HYDROGEN↗

Challenges and strategies for probing the composite interface of PEM electrolyzers and fuel cells using operando AP-XPS

Left: cross-section schematic of a membrane electrode assembly, the working electrode changing state with applied potential. Center: the operando cell design that enables snapshot data acquisition during trajectory movement. Right: resulting spectra. Understanding the surface chemistry of electrocatalyst systems under operando conditions is central to revealing the electrocatalytic cell's working mechanisms. Determination of these catalytic processes on a molecular scale and the involved components is fundamental to streamlining material design for energy conversion and storage applications. X-ray photoelectron spectroscopy (XPS) is an established technique used to study the chemical and electronic states of materials. While the surface sensitivity of XPS is typically high, use of tender X-ray energies and technical advancements have allowed for the direct probing of solid–vapor and solid–liquid interfaces. However, protocols and documentation of experimental considerations for operando XPS probing of working electrolyzers and fuel cells remain scarce. Herein, we report an approach for the study of working polymer electrolyte membrane (PEM) electrolysis cells using ambient pressure X-ray photoelectron spectroscopy (AP-XPS). This approach directly probes the composite electrode surface on the membrane electrode assembly (MEA) in 100% relative humidity to establish a meaningful liquid layer for electrocatalysis. We carry out a systematic investigation from the cell constituent components to a fully assembled working operando electrolytic system and establish a method for AP-XPS study of the complex composite MEA, providing recommendations for data acquisition and component analysis.

Hamlyn, Rebecca↗

The Effect of Proton Conductivity of Fe–N–C–Based Cathode on PEM Fuel cell Performance

A model–based impedance spectroscopy is used to determine proton conductivity, oxygen transport parameter, double layer capacitance and oxygen reduction reaction (ORR) Tafel slope in the Fe–N–C cathode catalyst layer (CCL) of a PEM fuel cell. Experimental spectra of two cells differing by the membrane thickness only are processed using a physics–based model for PEMFC impedance. The spectra have been measured in the range of current densities from 25 to 800 mA cm -2 . The ORR Tafel slope of both the cells shows almost linear growth with the current density. In one of the cells, the CCL proton conductivity σp strongly decays at the current density of 100 mA cm -2 ; this decay is accompanied by the step growth of the double layer capacitance. Other minor variations of proton conductivity and double layer capacitance with the cell current occur also in a counterphase; presumed origin of this effect is discussed. The oxygen diffusion coefficient in the cathode exhibits explosive growth with the cell current. We attribute this effect to formation of temperature and pressure gradients in the CCL due to strongly non–uniform distribution of ORR rate in the electrode.

25 ENERGY STORAGE↗

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)↗