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At least 109 records · Page 6

Performance-Limiting Factors of Hydrocarbon Ionomeric Binders for Fuel Cells and Electrolyzers

Here, the move toward nonfluorinated hydrocarbon ionomers for fuel cells and electrolyzers is driven by potential restrictions on polyfluoroalkyl substances such as Nafion. This study examines the key limitations of hydrocarbon ionomers through half- and single-cell experiments with model hydrocarbon ionomers. Half-cell tests reveal three major performance barriers: undesirable adsorption, electrochemical oxidation, and low gas permeability. Competitive sulfate adsorption helps counteract ionomer adsorption and oxidation. These findings align with single-cell performance data, which further reveal additional oxygen mass transport limitations likely caused by localized electrode flooding. Together, these findings offer valuable insights to guide the development of high-performance, fluorine-free hydrocarbon ionomers for next-generation fuel cells and electrolyzers.

Choi, Jong-Ho [Los Alamos National Laboratory (LAN↗

Enabling Stable and Salt-Free Formic Acid Production via Reactive Interface Optimization in Forward-Bias Bipolar-Membrane CO2 Electrolyzers

Electrochemical conversion of CO2 to liquid products is limited by parasitic reactions that consume products and destabilize operation. Here, we show that salt-free formic acid synthesis in a forward-bias bipolar-membrane CO2 electrolyzer is governed by a coupled reaction-transport instability driven by parasitic anode formic acid oxidation. Operando mass spectrometry reveals that this process proceeds through CO-mediated poisoning, identifying catalyst tolerance to CO as a key descriptor of anode selectivity. Among the catalysts examined, PtRu/C preferentially promotes hydrogen oxidation over formic acid oxidation. Coupling this catalyst with transport-interface engineering improves product removal, enhances Faradaic and energy efficiency, and enables stable operation at 200 mA/cm2 for 190 h with a voltage decay of 0.64 mV/h. Techno-economic analysis indicates an 18% reduction in minimum selling price and highlights product concentration as the dominant cost lever. These results establish a general framework for suppressing product oxidation in liquid-product electrolyzers.

Hu, Leiming↗

Perovskite Catalysts for Pure-Water-Fed Anion-Exchange-Membrane Electrolyzer Anodes: Co-design of Electrically Conductive Nanoparticle Cores and Active Surfaces

Anion-exchange-membrane water electrolyzers (AEMWEs) are a possible low-capital-expense, efficient, and scalable hydrogen-production technology with inexpensive hardware, earth-abundant catalysts, and pure water. However, pure-water-fed AEMWEs remain at an early stage of development and suffer from inferior performance compared with proton-exchange-membrane water electrolyzers (PEMWEs). One challenge is to develop effective non-platinum-group-metal (non-PGM) anode catalysts and electrodes in pure-water-fed AEMWEs. We show how LaNiO3-based perovskite oxides can be tuned by cosubstitution on both A- and B-sites to simultaneously maintain high metallic electrical conductivity along with a degree of surface reconstruction to expose a stable Co-based active catalyst. The optimized perovskite, Sr0.1La0.9Co0.5Ni0.5O3, yielded pure-water AEMWEs operating at 1.97 V at 2.0 A cm-2 at 70 °C with a pure-water feed, thus illustrating the utility of the catalyst design principles.

Zhai, Tingting↗

Importance of hydrogen oxidation reaction current in quantifying hydrogen crossover in PEM water electrolyzers at high differential pressure

Understanding hydrogen permeation in proton exchange membrane water electrolyzers (PEMWEs) operating at high differential pressures (>25 bar) is critical towards developing effective gas recombination strategies that enable safe operation and high efficiency. Developing this understanding relies on accurate quantification of hydrogen crossover rates in water electrolyzers operating under such conditions. In this work, we show that PEMWEs operating at high differential pressures exhibit noticeable hydrogen oxidation reaction (HOR) currents. As the HOR consumes part of the permeated hydrogen at the anode, neglecting HOR currents leads to severe underestimation of the hydrogen crossover rate. We implemented a new method combining hydrogen oxidation current with online gas chromatography measurements to accurately quantify hydrogen crossover rates as a function of operating current density in PEMWEs operating at high differential pressures (10–30 bar g ).

25 ENERGY STORAGE↗

Highly dense atomic Fe–Ni dual metal sites for efficient CO 2 to CO electrolyzers at industrial current densities

Carbon-supported, atomically dispersed, nitrogen-coordinated metal sites (e.g., Fe and Ni) are arguably the most promising catalysts for the electrochemical reduction of CO 2 to CO due to their unique catalytic properties and the use of earth-abundant elements. However, conventional single metal sites are constrained by their structural simplicity, causing either too weak or too strong absorption/desorption of multiple critical intermediates (e.g., *COOH and *CO). Current catalysts also suffer from ultra-low loadings (<1.0 wt%) of atomic metal active sites in catalysts, leading to inadequate performance for CO 2 -to-CO conversion. Here, we develop dual Ni/Fe metal site catalysts with significantly increased atomically dispersed metal loadings (up to 4.8 wt%). A gas-phase chemical vapor deposition (CVD) approach to introducing single Ni sites was integrated with Fe 2 O 3 /ZIF-8 precursors, followed by an optimal thermal activation. The optimized CVD-Ni/Fe–N–C catalyst exhibited remarkable electrocatalytic performance for the CO 2 reduction to CO in a continuous membrane-electrode-assembly electrolyzer, achieving a maximum CO faradaic efficiency (FE CO ) of 96% at a current density of 700 mA cm −2 in a near-neutral electrolyte. Furthermore, a desirable but challenging acidic flow-cell electrolyzer was designed using this dual metal site catalyst to improve CO 2 utilization, accomplishing a FE CO of up to 95% at a CO partial current density close to 600 mA cm −2 . Density functional theory (DFT) calculations suggest a synergetic effect between Fe–Ni pairs facilitating *COOH intermediate formation and *CO desorption simultaneously during CO 2 to CO conversion. This is key to breaking the linear scaling relationship of conventional single-metal site catalysts during the CO 2 reduction reaction.

36 MATERIALS SCIENCE↗

Cyclic olefin copolymer-based reinforced anion exchange membranes for water electrolyzers

Anion exchange membranes (AEMs) have emerged as a promising technology for water electrolysis in hydrogen production since they offer significant cost reduction in choices of electrocatalysts and bipolar plates. However, AEMs satisfying multiple requirements of high ionic conductivity, good chemical stability, robust mechanical properties, scalable synthesis, and low manufacturing costs are rare. Herein, we introduce quaternary ammonium functionalized cyclic olefin copolymers (COCs) as a new class of chemically stable and low-cost AEM materials. To further enhance the mechanical robustness, we prepared reinforced composite AEMs by impregnating the ionically functionalized COC into a mechanically robust matrix. The resulting reinforced composite membrane exhibits a high hydroxide conductivity of 127 mS cm −1 and excellent mechanical strength. In water electrolyzers, the MEA demonstrated outstanding performance, achieving a current density of 2.24 A cm −2 at 1.8 V, attributable to high conductivity, enhanced mechanical properties, and good alkaline stability of the composite membrane. These results indicate that the COC-based AEMs demonstrate good potential for application in AEM electrolyzers.

08 HYDROGEN↗

Low-frequency electrochemical pulsing to manage flooding and salt precipitation in zero-gap CO 2 -to-ethylene electrolyzers

The electrochemical reduction of carbon dioxide (CO 2 ) to ethylene presents a promising route for utilizing exhaust gases to produce value-added chemicals with broad manufacturing applications. While zero-gap electrolyzer architectures show great potential to enable commercial-scale CO 2 -to-ethylene conversion, their performance is often limited by failure within the first 100 hours. In this work, we demonstrate that a low-frequency electrochemical pulsing protocol effectively mitigates carbonate salt precipitation and flooding by managing water transport to and through the cathode gas diffusion electrode and associated flow fields. Operando neutron imaging further reveals the dynamics of water crossover and flooding, emphasizing the intricate interplay between electrochemical operation and ionic transport. By mitigating short-term flooding and salt precipitation failure modes, this study establishes a foundation for understanding long-term degradation mechanisms and advancing the practical viability of CO 2 electrolyzers for industrial-scale applications.

36 MATERIALS SCIENCE↗

NiFeCo-based catalysts in high current zero-gap anion exchange membrane water electrolyzers

Understanding degradation mechanisms in pure water anion exchange membrane water electrolyzers is essential for developing durable and precious metal-free hydrogen production systems, yet electronic, chemical, and transport-driven pathways often occur simultaneously at the anode. To separate these effects, we establish a morphology invariant Ni/Fe/Co thin film model catalyst platform using physical vapor deposition and systematically compare composition-dependent behavior under both pure water and 0.1 M KOH feeds. Devices were operated under industrially relevant current density conditions, galvanostatically at 1 A cm −2 for 24 hours; metal dissolution, ionomer oxidation, and resistance growth were quantified using inductively coupled plasma mass spectrometry, X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy. Under pure-water operation, Ni-rich films showed voltage increases that correlated with rising total cell resistance (ΔV ≈ 243 mV, ΔR ≈ 0.17 Ω cm 2 ). Co-rich films maintained near constant voltages with minimal resistance change (ΔV < 10 mV, ΔR ≈ 0.03 Ω cm 2 ) but induced pronounced ionomer oxidation observed by XPS. In 0.1 M KOH, ionomer oxidation is suppressed, and impedance growth is minimized (<0.08 Ω cm 2 ) across all compositions, consistent with reduced transport limitations and improved ionic conduction relative to pure-water feeds. These results demonstrate how a controlled thin film model platform can isolate composition electrolyte relationships and provide mechanistic design principles for stable pure water anion exchange membrane electrolyzers.

Milenia Rojas Mendoza, B. [Stanford Univ., CA (Uni↗

Ionomer Optimization for Water Uptake and Swelling in Anion Exchange Membrane Electrolyzer: Oxygen Evolution Electrode

Water electrolysis using an anion conductive, solid polymer electrolyte is an attractive method for point-of-use hydrogen production. Recent advances in catalysts and anion exchange membranes (AEM) have made alkaline devices increasingly competitive with their acidic counterparts. However, less attention has been paid to the anion conductive ionomers (ACI) used in the fabrication of electrodes for AEM electrolyzers. The ACI contributes to ion conduction between the catalyst and bulk electrolyte and serves as a binder for adhering the catalyst to the gas diffusion layer and AEM. Ionic conductivity, water uptake and ionomer swelling are critical properties for electrode performance. High ion exchange capacity (IEC) in the ionomer is desired for reduced electrode resistance, however, it can lead to excess water uptake (WU) and disruptive ACI swelling. In this study, a series of poly(norbornene)-based ionomers were synthesized, characterized and used to fabricate oxygen evolving anodes for low-temperature AEM water electrolysis. The IEC of the ionomers (0 to 4.73 meq g −1 ) was adjusted by controlling the ratio of ion conducting to non-ion conducting norbornene monomers in the ACI tetrablock copolymers. Low conductivity ionomers are shown to yield the best-performing oxygen evolution electrodes, in the absence of ACI polymer cross-linking because they do not experience excessive water swelling. Light cross-linking within the anode ACI was used as a means to independently lower WU of the ionomer without compromising ionic conductivity. This control over water swelling allows higher ionic conductivity within the ACI to be used in water-fed electrolyzer applications. Other methods of water management were compared including the use of hydrophobic additives and adjustment of the ionomer concentration in the electrode. As a result, it was shown that the cell performance greatly benefits from a highly conductive ionomer in the oxygen evolution reaction electrode if the WU is managed.

08 HYDROGEN↗

KOH vs Deionized Water Operation in Anion Exchange Membrane Electrolyzers

Anion exchange membrane water electrolyzers (AEMELs) have recently received significant attention due to their potential advantages over proton exchange membrane electrolyzers (PEMELs). However, some AEMELs feed an aqueous salt solution to the cell where PEMELs typically feed deionized (DI) water. DI water is preferred to keep the system and maintenance costs low. Because of this, many AEMEL researchers report performance both in the salt solution (typically KOH) and DI water. However, the methodology for switching between KOH and DI water is often poorly defined, and it is unclear what impact the residual salt has on cell performance after switching from salt to DI water. Having a fully deionized environment is important because the presence of salts in the water feed increase the effective electrochemical surface area of the catalyst in the three-dimensional electrode and residual salt remaining after switching to DI water feed can have a misleading transient effect on cell performance. This paper focuses on understanding the transition from KOH to DI water testing in AEMELs. It is shown that when switching from salt to DI water feed, a large volume of DI water must be fed over several hours to achieve true DI-water performance. It is also shown that starting AEMELs from the beginning with DI water feed (without any KOH ever being fed to the cell) results in better cell durability. Lastly, a cell is demonstrated having operated exclusively on DI water at 1.0 A cm −2 for 500 h at an operating voltage of ca. 2 V and a low degradation rate.

08 HYDROGEN↗

Electrolyzer Performance Loss from Accelerated Stress Tests and Corresponding Changes to Catalyst Layers and Interfaces

Stress tests are developed for proton exchange membrane electrolyzers that utilize low catalyst loading, elevated potential, and frequent cycling with square- and triangle-waves to accelerate anode catalyst layer degradation during intermittent operation. Kinetics drive performance losses (ohmic/transport secondary) and are accompanied by decreasing exchange current density, decreasing cyclic voltammetric capacitance, and increasing polarization resistance. Decreased kinetics are likely due to a combination of iridium (Ir) migration into electrochemically inaccessible locations in the anode or membrane, Ir particle growth (supported by X-ray scattering), changes in the extent of the Ir oxidation state (supported by X-ray absorption spectroscopy), and anode catalyst layer reordering. Decreasing catalyst/transport layer contact and catalyst/membrane interfacial tearing may add contact resistances and account for increasing ohmic losses. Performance losses for low and moderate catalyst loading, as well as from accelerated and model wind/solar cycling protocols, were likewise dominated by kinetics but vary in severity. Additionally, accelerated cycling (1 cycle per minute) appears to reasonably accelerate relevant loss mechanisms and can be used to project electrolyzer lifetime from anode deterioration. Ongoing accelerated stress test development and studies into performance loss mechanisms will continue to be critical as electrolysis shifts to intermittent power and low-cost applications.

30 DIRECT ENERGY CONVERSION↗

Durability Optimization of CO 2 Electrolyzers for Syngas Evolution

Recently, there has been an increased interest in mitigating anthropogenic CO 2 emissions through the electrochemical conversion of CO 2 into fuels and fuel feedstocks, including hydrogen gas (H 2 ), carbon monoxide (CO), and mixtures of the two to yield syngas. Commercial applications of these systems require high catalytic selectivity for the desired products, while exhibiting operational lifetimes exceeding thousands of hours. Advancements in this field have produced systems that display high selectivity of the desired products at faradaic efficiencies exceeding 95%. Despite the advancements made in CO 2 electrolysis, system durability remains a standing challenge in the field. CO 2 electrolyzer lifetimes are often limited by carbonate fouling, catalyst degradation, detrimental flooding of electrode microporous layers and anion exchange membrane (AEM) failures. In this report, a 5 cm 2 membrane electrode assembly (MEA) device is used to investigate potential failure modes and to optimize AEM CO 2 electrolyzer operation. Key findings of this study include the importance of CO 2 flow rate, use of a thin PiperION PTFE-reinforced membrane, optimizing compression to enhance contact under 40 in-lb compression, and the effect of more compressible, commercial iridium oxide anodes on system durability.

Abouremeleh, Mohammed H. [Lawrence Berkeley Nation↗

Controllers for Distributed Grid Support for Power Systems using Hybrid DER plants with Electrolyzers [SWR-20-06]

This software presents the design and control for a hybrid DER site with integrated dispatchable electrolyzers. It is a comprehensive solution for regulating the dispatch of electrolyzer demand to support the grid using the respective control functions. Multiple control functions (ramp control, frequency support control, dispatch prioritization) are developed to integrate the proposed site for multiple services around load, voltage and frequency control. This allows the site owners to participate in both distribution and bulk system energy markets for grid ancillary services.

Jain, Rishabh↗

Electrolyzer Supply Chain Readiness Level (SCRL)

The U.S. Department of Energy's (DOE's) Office of Manufacturing and Energy Supply Chains (MESC) is revitalizing the U.S. manufacturing base with over $20 billion of direct investment in manufacturing capacity, industrial decarbonization, and workforce development. This work will provide guidance to MESC and other government organizations as to which supply chain components to invest in to reduce material vulnerability for hydrogen electrolyzers as part of the Modeling, Mapping, and Analysis (MMAC) Consortium.

AEC↗

Constructing Highly Porous Low Iridium Anode Catalysts Via Dealloying for Proton Exchange Membrane Water Electrolyzers

Iridium (Ir) is the most active and durable anode catalyst for the oxygen evolution reaction (OER) for proton exchange membrane water electrolyzers (PEMWEs). However, their large-scale applications are hindered by high costs and scarcity of Ir. Lowering Ir loadings below 1.0 mgcm -2 causes significantly reduced PEMWE performance and durability. Therefore, developing efficient low Ir-based catalysts is critical to widely commercializing PEMWEs. Herein, an approach is presented for designing porous Ir metal aerogel (MA) catalysts via chemically dealloying IrCu alloys. In this study, the unique hierarchical pore structures and multiple channels of the Ir MA catalyst significantly increase electrochemical surface area (ECSA) and enhance OER activity compared to conventional Ir black catalysts, providing an effective solution to design low-Ir catalysts with improved Ir utilization and enhanced stability. An optimized membrane electrode assembly (MEA) with an Ir loading of 0.5 mg Ir cm -2 generated 2.0 A cm -2 at 1.79 V, higher than the Ir black at a loading of 2.0 mg Ir cm -2 (1.63 A cm -2 ). The low-Ir MEA demonstrated an acceptable decay rate of ≈40 µV h -1 during durability tests at 0.5 (>1200 h) and 2.0 A cm -2 (400 h), outperforming the commercial Ir-based MEA (175 µV h -1 at 2.0 mg Ir cm -2 ).

36 MATERIALS SCIENCE↗

Regulating the Third Metal to Design and Engineer Multilayered NiFeM (M: Co, Mn, and Cu) Nanofoam Anode Catalysts for Anion-Exchange Membrane Water Electrolyzers

In this study, alkaline anion-exchange membrane water electrolyzers (AEMWEs) for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant platinum group metal (PGM)-free catalysts. Herein, the third metal is incorporated into NiFe-based catalysts to regulate their electronic structures and morphologies, aiming to achieve sufficient oxygen evolution reaction (OER) activity and performance in AEMWEs. The ternary NiFeM (M: Cu, Co, or Mn) catalysts are featured with multiple layered structures and nanofoam network morphologies, consisting of highly OER-active amorphous Ni-rich oxide shells and electrically conductive metallic alloy cores. The physical and electronic perturbations to the NiFe induced by a third element lead to a fine-tuning of the redox ability of the metal sites at the reaction centers, which breaks the scaling relationship between OH* and O* intermediates at the reaction centers. Thus, the unique structural configuration and electronic regulation simultaneously benefit catalytic activity and performance improvements. These NiFeM nanofoam catalysts demonstrated promising anode performance in actual AEMWEs, comparable to the IrO 2 reference, especially at high current densities. Notably, using various electrolytes (e.g., KOH solution or pure water) for AEMWEs exhibited a different performance trend among studied NiFeM catalysts, likely due to dynamic changes of catalysts under various OER environments.

25 ENERGY STORAGE↗

Tuning Catalyst Activation and Utilization Via Controlled Electrode Patterning for Low-Loading and High-Efficiency Water Electrolyzers

An anode electrode concept of thin catalyst-coated liquid/gas diffusion layers (CCLGDLs), by integrating Ir catalysts with Ti thin tunable LGDLs with facile electroplating in proton exchange membrane electrolyzer cells (PEMECs), is proposed. The CCLGDL design with only 0.08 mg Ir cm -2 can achieve comparative cell performances to the conventional commercial electrode design, saving ~97% Ir catalyst and augmenting a catalyst utilization to ~24 times. CCLGDLs with regulated patterns enable insight into how pattern morphology impacts reaction kinetics and catalyst utilization in PEMECs. A specially designed two-sided transparent reaction-visible cell assists the in situ visualization of the PEM/electrode reaction interface for the first time. Oxygen gas is observed accumulating at the reaction interface, limiting the active area and increasing the cell impedances. In this work, it is demonstrated that mass transport in PEMECs can be modified by tuning CCLGDL patterns, thus improving the catalyst activation and utilization. The CCLGDL concept promises a future electrode design strategy with a simplified fabrication process and enhanced catalyst utilization. Furthermore, the CCLGDL concept also shows great potential in being a powerful tool for in situ reaction interface research in PEMECs and other energy conversion devices with solid polymer electrolytes.

08 HYDROGEN↗