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At least 19 records

Probing Electrode Transformation under Dynamic Operation for Alkaline Water Electrolysis

Alkaline water electrolyzers (AWEs) play a pivotal role in the realm of large-scale hydrogen production. However, AWEs face significant challenges in electrode degradation particularly under dynamic operating conditions, induced by reverse current phenomenon during frequent startup/shutdown. Herein, this study aims to rationalize the degradation mechanisms of AWEs under these conditions. A three-electrode membrane electrode assembly (MEA) setup is first utilized to decouple polarization behaviors of anode and cathode in AWEs. Following a proposed accelerated stress testing protocol, the setup allows for tracking individual electrode performance transformations during frequent reverse current operation. Integrating operando cell studies with in situ and post-mortem characterizations, it is showed that continuous formation of highly active species, nickel (oxy)hydroxides, improves the anode performance for oxygen evolution reaction. On the contrary, irreversible oxidation of nickel to β-nickel hydroxide results in a severe degradation of cathode, leading to material dissolution, poor electrical conductivity and loss of catalytic activity for hydrogen evolution reaction. These results provide insights in nickel-based electrode transformation mechanisms for alkaline water electrolysis and indicate that cathode with higher redox reversibility can potentially improve durability of AWEs under dynamic conditions.

08 HYDROGEN↗

Decoupling electrode kinetics to elucidate reaction mechanisms in alkaline water electrolysis

Alkaline water electrolysis (AWE) presents key advantages, including reduced material costs, enhanced operational stability, and compatibility with non-precious metal catalysts, positioning it as a scalable route for hydrogen production. In this study, we introduce a minimally invasive single-cell configuration incorporating a reference electrode via diaphragm extension to form an internal ion channel. This setup, combined with an interfaced potentiostat and auxiliary electrometer, enables real-time, independent monitoring of anode and cathode behavior, offering high-resolution electrochemical diagnostics. While it is well established that the hydrogen evolution reaction (HER) exhibits sluggish kinetics in alkaline media, our study reveals that this limitation persists even in practical AWE systems where nickel-based substrates are used as electrodes. This observation is supported by both experimental data and voltage breakdown modeling. Arrhenius-type analysis reveals that localized electric fields induced by catalysts shift the reaction kinetics from classical Butler–Volmer behavior toward a Marcus-like regime, where interfacial molecular dynamics and bimolecular charge transfer dominate. We propose a semi-empirical model and a surficial reaction mechanism to describe these dynamics. This work underscores the critical need for cathode innovation and provides a rational framework for designing advanced catalysts and electrode architectures to optimize AWE performance.

08 HYDROGEN↗

Modeling the Effect of Material Properties on Liquid-Alkaline Water Electrolysis

Liquid-alkaline water electrolyzers (LAWEs) use electricity to drive the conversion of water to H 2 and O 2 gas. These devices benefit from the use of low-cost nickel electrodes and metal-oxide separators, but suffer from lower current densities and higher cell voltages than proton-exchange-membrane water electrolyzers. Identifying the inefficiencies that result in this poor performance is key to mitigating losses and optimizing LAWEs. Here, we report an experimentally-validated 1-D continuum model of a LAWE that elucidates the gradients within the cell, simulates H 2 crossover, and projects the energy improvements made possible by modulating the properties of the electrodes and separator. The model captures the Nernstian polarization losses and the distribution of gas- and liquid-phases within the electrodes, enabling quantification of energy losses associated with kinetic, ohmic, and bubble-induced (mass-transport) resistances. Simulations demonstrate that LAWE can achieve energy intensities of 50 kWh kg −1 of H 2 at 1 A cm −2 using improved electrode and separator properties.

08 HYDROGEN↗

Standardization and best practices in single-cell testing for liquid alkaline water electrolysis

The increasing demand for efficient and sustainable hydrogen production has driven significant advancements in water electrolysis technologies. Among these, liquid alkaline water electrolysis (LAWE) stands out for its cost-effectiveness and scalability. This manuscript establishes best practices and standardized testing procedures for single-cell LAWE, focusing on the use of nickel foam as both anode and cathode substrates, while incorporating catalysts such as nickel-iron layered double hydroxide (NiFe-LDH) as the anode material and nickel-molybdenum on carbon (NiMo/C) as the cathode material. By providing detailed guidelines on material preparation, cell assembly, and performance evaluation, this work offers a comprehensive framework to improve reproducibility and ensure consistency. The results demonstrate that applying these best practices minimizes variability across different laboratories and experimental setups, laying the groundwork for more robust comparisons and accelerating progress in LAWE research.

08 HYDROGEN↗

Endurance Test and Evaluation of Alkaline Water Electrolysis Cells

The overall objective of this program is to assess the state of alkaline water electrolysis cell technology and its potential as part of a Regenerative Fuel Cell System (RFCS) of a multikilowatt orbiting powerplant. The program evaluates the endurance capabilities of alkaline electrolyte water electrolysis cells under various operating conditions, including constant condition testing, cyclic testing and high pressure testing. The RFCS demanded the scale-up of existing cell hardware from 0.1 sq ft active electrode area to 1.0 sq ft active electrode area. A single water electrolysis cell and two six-cell modules of 1.0 sq ft active electrode area were designed and fabricated. The two six-cell 1.0 sq ft modules incorporate 1.0 sq ft utilized cores, which allow for minimization of module assembly complexity and increased tolerance to pressure differential. A water electrolysis subsystem was designed and fabricated to allow testing of the six-cell modules. After completing checkout, shakedown, design verification and parametric testing, a module was incorporated into the Regenerative Fuel Cell System Breadboard (RFCSB) for testing at Life Systems, Inc., and at NASA JSC.

Kovach, Andrew J.↗

Endurance test and evaluation of alkaline water electrolysis cells

Utilization in the development of multi-kW low orbit power systems is discussed. The following technological developments of alkaline water electrolysis cells for space power application were demonstrated: (1) four 92.9 cm2 single water electrolysis cells, two using LST's advanced anodes and two using LST's super anodes; (2) four single cell endurance test stands for life testing of alkaline water electrolyte cells; (3) the solid performance of the advanced electrode and 355 K; (4) the breakthrough performance of the super electrode; (5) the four single cells for over 5,000 hours each significant cell deterioration or cell failure. It is concluded that the static feed water electrolysis concept is reliable and due to the inherent simplicity of the passive water feed mechanism coupled with the use of alkaline electrolyte has greater potential for regenerative fuel cell system applications than alternative electrolyzers. A rise in cell voltage occur after 2,000-3,000 hours which was attributed to deflection of the polysulfone end plates due to creepage of the thermoplastic. More end plate support was added, and the performance of the cells was restored to the initial performance level.

Burke, K. A.↗

The dual role of iron in alkaline water electrolysis: A friend or a foe?

Trace iron (Fe) impurities pose a challenge in alkaline water electrolysis (AWE) and can significantly impact long-term performance, yet their comprehensive system-level effects remain poorly understood. Here, we present the mechanistic roles of Fe in AWE, using combined rotation disk electrode studies, zero-gap cell measurements, and durability tests up to 1,000 h. Fundamental electrochemistry shows that Fe deposition proceeds through a solution-mediated pathway, with dendritic growth triggered under specific mass-transport and potential conditions. In single-cell operation, Fe incorporation substantially enhances nickel (Ni)-based anode activity by forming highly active Ni-Fe oxyhydroxides, while cathodic Fe forms either thin films or dendrites, depending on potential, surface morphology, and electrolyte distribution. Although dendrites do not degrade hydrogen evolution performance up to 1,000 h, they reveal partial intrusion into the separator, indicating a potential durability risk. We identify five governing factors controlling Fe dendrite formation and provide design principles for impurity-resilient AWE systems.

Lyu, Xiang [ORNL] (ORCID:0000000208673248)↗

Durable, Ultra-Thin Diaphragms for Liquid Alkaline Water Electrolysis

W. L. Gore & Associates assembled a world class team (De Nora Tech, LLC; New York University; and thyssenkrupp nucera) to develop durable, ultra-low resistance diaphragms that dramatically improve system efficiency, dynamic response, and operational flexibility. To enable the use of ultra-thin diaphragms, an optimized electrode package was chosen as part of an electrode down select study. Ultra-thin diaphragms based on microporous polymer scaffolds imbibed with zirconia nanoparticles were developed and tested. Performance and durability on par with incumbent materials was demonstrated. A transparent electrolyzer to directly observe in-situ diaphragm-bubble interactions was designed and built, and simultaneous optical and electrochemical performance tests were performed. A Pressurized Alkaline Water Electrolysis (PAWE) single cell test station was designed to support advanced R&D in high-pressure electrolysis, particularly for evaluating novel electrode and separator configurations under elevated temperature and pressure operating conditions. Due to early project termination, the original scope could not be fully achieved.

08 HYDROGEN↗

Thin, Highly Selective Polymer Membrane Separators for Advanced Liquid Alkaline Water Electrolysis

Our team will develop novel, dense, polymer electrolyte separators based on polybenzimidazole (PBI) derivatives that will enable tuning of water/KOH uptake in mechanically robust films for advanced liquid alkaline water electrolysis (LAWE). These material advances will enable thinner separators with increased selectivity (hydroxide conductivity/hydrogen permeability), thereby enabling higher operating currents, increased dynamic operating high-temperature stability, and catalyst-coated membranes (zero-gap design advantages) in direct alignment with stated lab call goals.

HYDROGEN↗

Insights into catalyst degradation during alkaline water electrolysis under variable operation

Energy conversion technologies that are key to decarbonization efforts face significant durability challenges due to variable operation. Understanding the impact of variable operation on catalytic stability and identifying the key variables that dictate degradation is crucial for developing robust technologies. Here, we present a comprehensive investigation of the effects of variable operation on liquid alkaline water electrolysis. Our findings reveal that variable operation induces severe degradation of Ni, Fe, and Co catalytic films that is not observed during steady-state operation. By systematically interrogating the electrode discharge during simulated shutdown tests using Raman spectroscopy and mass spectrometry techniques, we uncover significant alterations caused by reverse currents in real time. These include changes in crystal structure, composition, film thickness, electronic conductivity, and dissolution rates. Lab-scale electrolyzer experiments further highlight the impact of variable operation on catalyst materials under relevant conditions. Finally, we provide guidelines for leveraging these insights to advance electrocatalysis research. This work underscores the importance of integrating realistic stressors into stability testing and offers practical guidelines for catalyst design, performance evaluation, and industrial implementation. Collectively, insights from this study will drive the development of more resilient energy conversion technologies.

Marquez, Raul A. [Univ. of Texas, Austin, TX (Unit↗

Alkaline water electrolysis technology for Space Station regenerative fuel cell energy storage

The regenerative fuel cell system (RFCS), designed for application to the Space Station energy storage system, is based on state-of-the-art alkaline electrolyte technology and incorporates a dedicated fuel cell system (FCS) and water electrolysis subsystem (WES). In the present study, emphasis is placed on the WES portion of the RFCS. To ensure RFCS availability for the Space Station, the RFCS Space Station Prototype design was undertaken which included a 46-cell 0.93 cu m static feed water electrolysis module and three integrated mechanical components.

Schubert, F. H.↗

Nanobubble Formation and Coverage during High Current Density Alkaline Water Electrolysis

Gas bubbles are a necessary byproduct of water electrolysis whereby hydrogen and oxygen are produced from water. These attached gases reduce the electrode’s active area, which necessitates a deep understanding of the bubble life cycle starting from nanobubbles. Synchronized with the electrochemistry, the time evolution of the surface nanobubble size and coverage is resolved using grazing incidence small-angle X-ray scattering (GISAXS) and correlated with optical microscopy and theoretical calculations to show that a significant portion of the surface is covered in nanobubbles after larger micron-sized bubbles are observed. Further, these nanobubbles increase in number and decrease in size, toward 2 nm diameter, with the charge passed. The trend in size and number is consistent with an increase in supersaturation, which reduces the nascent bubble size. Altogether, this study suggests a significant portion of the surface contains nanobubbles and that strategies to reduce the dissolved hydrogen would be effective at reducing the nanobubble surface coverage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design considerations for a 10-kW integrated hydrogen-oxygen regenerative fuel cell system

Integration of an alkaline fuel cell subsystem with an alkaline electrolysis subsystem to form a regenerative fuel cell (RFC) system for low earth orbit (LEO) applications characterized by relatively high overall round trip electrical efficiency, long life, and high reliability is possible with present state of the art technology. A hypothetical 10 kW system computer modeled and studied based on data from ongoing contractual efforts in both the alkaline fuel cell and alkaline water electrolysis areas. The alkaline fuel cell technology is under development utilizing advanced cell components and standard Shuttle Orbiter system hardware. The alkaline electrolysis technology uses a static water vapor feed technique and scaled up cell hardware is developed. The computer aided study of the performance, operating, and design parameters of the hypothetical system is addressed.

Hoberecht, M. A.↗

Design considerations for a 10-kW integrated hydrogen-oxygen regenerative fuel cell system

Integration of an alkaline fuel cell subsystem with an alkaline electrolysis subsystem to form a regenerative fuel cell (RFC) system for low earth orbit (LEO) applications characterized by relatively high overall round trip electrical efficiency, long life, and high reliability is possible with present state of the art technology. A hypothetical 10 kW system computer modeled and studied based on data from ongoing contractual efforts in both the alkaline fuel cell and alkaline water electrolysis areas. The alkaline fuel cell technology is under development utilizing advanced cell components and standard Shuttle Orbiter system hardware. The alkaline electrolysis technology uses a static water vapor feed technique and scaled up cell hardware is developed. The computer aided study of the performance, operating, and design parameters of the hypothetical system is addressed.

Hoberecht, M. A.↗

Effect of stoichiometry and hydration level on water domain size and transport in poly(aryl piperidinium) alkaline anion-exchange membranes

Alkaline water electrolysis holds promise in decarbonizing the global economy by enabling renewable hydrogen production with non-precious group metal catalysts. Anion exchange membranes are an important component of alkaline water electrolyzers and would ideally be durable while allowing for high hydroxide conductivity. The poly(aryl piperidinium) (PAP) class of polymers has attracted recent interest due to their good mechanical robustness and high ionic conductivity. Here, in this work, we perform atomistic molecular dynamics (MD) simulations of several PAP polymers at experimentally relevant hydration levels and polymer ion exchange capacities (IECs) to gain nanoscale insight into their properties and to help elucidate the trade-offs that result from tuning the IECs through the polymer stoichiometry. Our MD-predicted macroscopic polymer properties were found to be in good agreement with experimentally available polymer swelling ratios, water-occupied volumes, X-ray scattering, and ionic conductivities. The models show that for hydration levels greater than 8H 2 O per cation a single water cluster will form that percolates through the system. The growth in water cluster size results in large polymer swelling, the creation of larger channels with widths of 7 Å or larger, and nanophase separation between the hydrophilic domains and the polymer with characteristic length scales of approximately 20–30 Å. The experimentally observed lack of a strong X-ray scattering peak at low wavevectors can be explained by a cancellation between the polymer-polymer/water-water and polymer-water correlations and not a loss in nanophase separation. The overlap in coordination environments of the hydroxide oxygen and polymer nitrogen atoms implies that vehicular diffusion between cationic groups could play a role in hydroxide transport. The polymers' hydroxide and water diffusion constants increase by approximately an order of magnitude between hydration levels of 8 and 20H 2 O per cation. However, there are diminishing returns in hydroxide diffusion constant once the IEC exceeds 2.4 meq/g.

08 HYDROGEN↗

Alkaline static feed electrolyzer based oxygen generation system

In preparation for the future deployment of the Space Station, an R and D program was established to demonstrate integrated operation of an alkaline Water Electrolysis System and a fuel cell as an energy storage device. The program's scope was revised when the Space Station Control Board changed the energy storage baseline for the Space Station. The new scope was aimed at the development of an alkaline Static Feed Electrolyzer for use in an Environmental Control/Life Support System as an oxygen generation system. As a result, the program was divided into two phases. The phase 1 effort was directed at the development of the Static Feed Electrolyzer for application in a Regenerative Fuel Cell System. During this phase, the program emphasized incorporation of the Regenerative Fuel Cell System design requirements into the Static Feed Electrolyzer electrochemical module design and the mechanical components design. The mechanical components included a Pressure Control Assembly, a Water Supply Assembly and a Thermal Control Assembly. These designs were completed through manufacturing drawing during Phase 1. The Phase 2 effort was directed at advancing the Alkaline Static Feed Electrolyzer database for an oxygen generation system. This development was aimed at extending the Static Feed Electrolyzer database in areas which may be encountered from initial fabrication through transportation, storage, launch and eventual Space Station startup. During this Phase, the Program emphasized three major areas: materials evaluation, electrochemical module scaling and performance repeatability and Static Feed Electrolyzer operational definition and characterization.

Noble, L. D.↗

Facile synthesis of Co(OH)2 nanoneedle arrays grown on stainless steel for industrial electrochemical oxygen evolution reaction

The electrochemical oxygen evolution reaction (OER) is a critical half-reaction in a variety of energy conversion and storage applications, however, OER suffers from sluggish kinetics due to the four proton-electron transfer processes. To remedy this, interfacial engineering proves an effective strategy to design high active OER catalysts. Herein, we report a facile synthesis of Co(OH)2 nanoneedle (Co-NN) arrays grown on stainless steel (SS) via a one-step hydrothermal reaction, and the resultant impressive OER performance. Particularly, the Co-NN/SS needs 267, 307, and 576 mV overpotentials to reach 10, 100, and 1000 mA cm−2 in 1 M KOH & room temperature, and the overpotentials drop to 199, 257, and 283 mV to achieve the same current densities in 30 wt% KOH & 80 °C. Additionally, an alkaline water electrolysis (AWE) cell coupled with Co-NN/SS anode and PtRu/NiMo cathode only requires 1.65 and 1.73 V iR-free cell voltage to reach 1.0 and 2.0 A cm−2, respectively. The sterling OER performance could be attributed to four possible reasons, the Fe in SS surface tailoring the electronic properties of Co(OH)2, the mixed metal oxides on SS surface accelerating surface reconstruction of Co(OH)2 nanoneedles into CoOOH active species, a Ni-rich surface layer formation cooperatively boosting the OER activity, and a local electric field effect concentrating reactants on the tip surface and accelerating the mass transfer. This work provides a facile approach for synthesizing highly efficient OER catalysts for industrial applications by interfacial engineering.

Lyu, Xiang [ORNL] (ORCID:0000000208673248)↗

Liquid Alkaline Water Electrolyzers: Comparing Performance across Design, Operation, and End-of-Life Scenarios

Liquid alkaline water electrolysis (LAWE) is a demonstrated technology for hydrogen production, yet a comprehensive life cycle assessment (LCA) of their deployment is lacking. Research leading to improvements to the core component, the electrochemical stack, along with auxiliary system materials and dynamic operation of stacks from variable electricity supply offers new data that allows for detailed modeling and evaluation. Here, we present an LCA of two facility designs based on the current state-of-the-art stack and an advanced stack with zero-gap between electrodes, and capture dynamic electricity use from solar, wind, and hybrid sources and stack recycling strategies. We present life cycle impact factors characterizing the production of 1 kg of hydrogen across 12 environmental, human health, and resource impact categories (TRACI and ReCiPe) in the contiguous United States. As expected, the source of electricity will drive impacts (e.g., 83-94% of carbon intensity); however, we find that operating using wind electricity can lower hydrogen leakage and the overall carbon intensity (1.03 kgCO 2 e/kgH 2 ) relative to solar electricity (2.57 kgCO 2 e/kgH 2 ) at matched 1:1 capacity between LAWE and the electricity source. The deployment of the advanced design and stack recycling lowers impacts across all life cycle stages. We highlight opportunities to further reduce potential impacts, including the balance of plant materials and operation cycles associated with the use of variable wind and solar electricity that result in hydrogen leakage.

08 HYDROGEN↗