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At least 91 records · Page 5

Next-generation anion exchange membrane water electrolyzers operating for commercially relevant lifetimes

Alkaline anion exchange membrane (AEM) water electrolysis has gained increasing attention due to its potential to achieve low-cost, high performance hydrogen production. However, most existing membranes are not durable in industrial settings. In this work, we demonstrate good performance relative to industrial parameters using Sustainion® anion exchange membranes. Long-duration tests showed stable performance of 1 A/cm 2 at 1.85 V with a degradation rate of less than 1 μV/h over 10,000 h. The projected lifetime is thus over 20 years. Daily on/off cycling performance over the course of 30 years was simulated experimentally through accelerated voltage shock tests, resulting in a performance loss of only 0.15 μV/cycle over 11,000 cycles. As shown through impact and crossover testing, an improvement in performance is achieved by the addition of zirconia to the polymer matrix and mechanically reinforcing the membrane.

08 HYDROGEN↗

Co 2 P-Pt Heterostructure Interfaces for Electrocatalytic Hydrogen Evolution

Pt-based electrocatalysts are effective for the hydrogen evolution reaction (HER); however, their limited ability to facilitate water dissociation and suboptimal hydrogen binding energy (H BE ) in alkaline electrolytes result in slow reaction kinetics, which hinders their cost-efficiency and practical applications. This study reports the synthesis of Co 2 P-Pt heterostructure nanorods using a seed-mediated growth method, producing a high density of Co 2 P-Pt interfacial sites. Density functional theory (DFT) calculations indicate that electronic interactions at these interfaces optimize H BE on Pt, while the interfacial sites promote water dissociation. The Co 2 P-Pt nanorods demonstrate an overpotential of 14 mV at 10 mA cm −2 for the HER, highlighting the potential of precisely engineered metal-metal phosphide interfaces for enhancing electrocatalytic efficiency.

36 MATERIALS SCIENCE↗

HydroGEN: Low Temperature Electrolysis

In low temperature electrolysis (LTE), it is imperative to both enhance and explore durability and demonstrate the opportunities for anion exchange membrane-based water electrolysis (AEMWE). The advantage of alkaline-based systems is primarily reduced capital cost: high pH enabling platinum group metal (PGM)-free catalysts and coatings, and the enhanced stability of those components compared to proton exchange membrane (PEM) -based systems. Compared to the water-only fed AEMWE in previous LTE 2.0 work, supporting electrolytes can allow for a significant improvement in performance through higher site-access and stability by reducing utilization and overpotential stresses that lead to catalyst layer delamination.

HYDROGEN↗

Highly sustained electrodes and electrolytes for salty alkaline and neutral water splitting

A corrosion resistant anode is provided for oxygen evolution reaction in water including chloride ions. The anode includes: (1) a substrate; (2) a passivation layer coating the substrate; and (3) an electrocatalyst layer coating the passivation layer. Polyanion adjusted alkaline seawater electrolyte for hydrogen generation by electrolysis is also provided.

Kenney, Michael J.↗

Bipolar membrane polarization behavior with systematically varied interfacial areas in the junction region

The palette of applications for bipolar membranes (BPMs) has expanded recently beyond electrodialysis as they are now being considered for fuel cell and electrolysis applications. Their deployment in emerging electrochemical technologies arises from the need to have a membrane separator that provides disparate pH environments and to prevent species crossover. Most materials research for BPMs has focused on water dissociation catalysts and less emphasis has been given to the design of the polycation–polyanion interface for improving BPM performance. Here, soft lithography fabricated a series of micropatterned BPMs with precise control over the interfacial area in the bipolar junction. Polarization experiments showed that a 2.28× increase in interfacial area led to a 250 mV reduction in the onset potential. Additionally, the same increase in interfacial area yielded marginal improvements in current density due to the junction region being under kinetics-diffusion control. A simple physics model based on the electric field of the junction region rationalized the reduction in the overpotential for water dissociation as a function of interfacial area. Finally, the soft lithography approach was also conducive for fabricating BPMs with different chemistries ranging from perfluorinated polymer backbones to alkaline stable poly(arylene) hydrocarbon polymers. These polymer chemistries are better suited for fuel cell and electrolysis applications. The BPM featuring the alkaline stable poly(terphenyl) anion exchange membrane had an onset potential of 0.84 V, which was near the thermodynamic limit, and was about 150 mV lower than a commercially available variant.

25 ENERGY STORAGE↗

Investigation of oxygen evolution reaction with 316 and 304 stainless-steel mesh electrodes in natural seawater electrolysis

Here, two commercially available stainless steel mesh substrates (316 SS and 304 SS) were evaluated as electrodes for oxygen evolution reaction (OER) in natural seawater electrolysis. The results show the 304 SS is less stable against corrosion under neutral (pH of 8.5) and low alkaline (0.1 M NaOH, pH of 12.8) seawater electrolytes because of the direct metal dissolution and chlorine evolution reaction (CER), and the 316 SS is superior to 304 SS in terms of electrocatalytic activity and resistance to corrosion under the same media. The performance of 304 SS is comparable to 316 SS under the high alkaline (1 M NaOH, pH of 13.7) seawater electrolyte, where the CER and metal dissolution are suppressed by OER. The overpotential for 304 and 316 SS is around 430 mV at 10 mA cm -2 , and the Tafel slopes are below 50 mV dec -1 under the high alkaline (1 M NaOH) seawater electrolyte, showing promising performance. The poor resistance to corrosion of 304 SS is attributed to the low Mo content, and it is supposed that the stability of both 304 and 316 SS can be improved further with the addition of Mo content. This work expands on promising substrates for natural seawater electrolysis, with cost and performance advantages.

Stainless-steel mesh↗

Ether Cleavage Decreases the Ion Exchange Capacity of Anion Exchange Membranes

Anion exchange membranes (AEMs) are integral to fuel cells and water electrolysis systems but suffer from poor durability under alkaline conditions. Ether cleavage is an important failure pathway of poly(arylene ether)-based AEMs that compromises both mechanical stability and ion transport. While this degradation pathway is often studied in terms of polymer fragmentation, the role of newly formed hydrophilic groups has been largely overlooked. Here, we show that polymer scission leads to reduced mechanical rigidity, while the introduction of hydrophilic groups partially mitigates this loss. Under alkaline conditions, phenoxide groups formed during ether cleavage neutralize the polymer cations, leading to a previously unreported loss of ion exchange capacity (IEC). This IEC loss mechanism exacerbates the reduction in ionic conductivity, emphasizing the severity of ether cleavage as a degradation pathway. Recognizing that ether cleavage introduces significant chemical changes beyond polymer fragmentation provides critical insights into its interplay with other degradation mechanisms, such as the direct reduction of cationic sites by E2 and S N 2, and provides molecular-level interpretations for the concurrent effects of polymer scission and increased hydrophilicity on membrane performance.

crystal cleavage↗

Synthetic Calcium Carbonate Production by Carbon Dioxide (CO 2 ) Mineralization of Industrial Waste Brines

The global scale of CO 2 emission has crossed 36 B tons, and the United State represents 14% of the total emissions. In light of the high cost associated with current CO 2 capture processes ($60-to-150 per ton of CO 2 ), carbon capture and utilization (CCU), wherein CO 2 is converted to beneficial products, provides a pragmatic path to overcome the economic barrier for CO 2 emissions control. In particular, CO 2 mineralization offers an attractive route as it produces high-value mineral carbonates that sequester CO 2 in a stable form. For instance, fine precipitated calcium carbonate, a valuable product with unit price in the range of $230-280/t and a global market projected to reach 99 M tons in 2020, can be produced by capturing CO 2 within aqueous Ca 2+ solution. However, two critical challenges need to be overcome—(i) the need for costly processes such as electrolysis or addition of alkali hydroxides to maintain alkalinity during mineralization, and (ii) the geographic availability of Ca-rich solutions (or brines) which often renders efficient integration with power plants impractical. To simultaneously address these challenges, this project developed two novel routes to enable carbonate production based on efficient CO 2 mineralization. In one variation, the project developed a new alkaline carbonation process to capture CO 2 and produce calcite precipitates from coal ashes. Herein, coal ash is carbonated first in a sodium carbonate solution. The carbonation reaction produces sodium hydroxide and raises the solution pH. This high-pH hydroxide solution is then used for CO 2 capture, which converts the sodium hydroxide solution back to sodium carbonate to repeat the carbonation cycle. The carbonated ash residue is refined with a CO 2 pressure swing step to produce high-purity precipitated calcium carbonate. In another variation, Ca-rich produced water brine serves as the Ca-source to mineralize CO 2 . An H + /Na + ion-exchange cycle was designed to provision alkalinity during mineralization and regenerate the ion-exchange reagent in brines with high salinity. Ca-depleted brines can then be treated within a centralized water treatment facility. Both variations beneficially utilize reject streams—such as coal ashes and brines from oil and gas extraction or CO 2 storage operations—that are available at substantial quantities in the vicinity of coal power plants within the U.S. In addition to technology development, this project included techno-economic and life-cycle analysis to identify technically and economically appropriate solutions for power plants in different geographic locations. Taken together, the project provides a unique route to integrate CO 2 emissions control and waste handling/treatment for coal power plants, while producing a high-value product to offset the economic burden associated with waste management. The developed processes utilize post-desulfurization flue gas from coal-fired power plants as is. The CO 2 conversion reactions are performed in alkaline brines at ambient pressure from the flue gas, thereby minimizing the energy burden. By beneficiation of industrial waste streams with low energy input, the processes offers significant technical advantages in energy and CO 2 footprint over the current paradigm of precipitated calcium carbonate production, which involves calcination of limestone at processing temperatures in excess of 800 °C. Overall, this project developed viable CO 2 mineralization processes while strategically maximizing the economic benefit.

01 COAL, LIGNITE, AND PEAT↗

Cutting-edge methods for amplifying the oxygen evolution reaction during seawater electrolysis: a brief synopsis

Electrochemical water splitting has been considered a clean and continual way for hydrogen (H 2 ) production. Direct seawater electrolysis is a potentially attractive technology due to the ample access to seawater and scarce freshwater resources in some regions. However, the presence of impurities (e.g., Cl - , Mg 2+ ) and the resulting corrosion and side reactions, such as the chloride oxidation reaction (ClOR), makes seawater electrocatalysis more challenging than that of fresh or alkaline water due to competition with the oxygen evolution reaction (OER) at the anode. Consequently, much effort has been devoted to developing approaches to enhance OER performance and suppress the ClOR. In this minireview, we summarize three general strategies for enhancing OER activity and selectivity in seawater electrolysis based on three different concepts: (1) the sole development of robust and high-performance OER catalysts in pure seawater electrolytes, (2) the introduction of additives to seawater electrolytes (e.g., alkalis and/or salts without chloride) to enhance the potential equilibrium gap between the ClOR and OER in combination with regular highly active OER catalysts, and (3) a combination of approaches (1) and (2). Finally, the current challenges and potential opportunities for green H 2 production from seawater electrolysis are briefly presented.

08 HYDROGEN↗

Characterizing Sustained Solar-to-Hydrogen Electrocatalysis at Low Cell Potentials Enabled by Crude Glycerol Oxidation

Unassisted solar-driven water electrolysis as a sustainable source for H 2 is limited by the high overpotential necessary to drive the oxygen evolution reaction (OER). Crude glycerol is an extremely alkaline byproduct of biodiesel synthesis that can be valorized or refined to produce more desirable chemicals. Glycerol can also be directly oxidized on an anode, replacing water oxidation, to reduce the applied cell potential requirements of electrolytic H 2 production or CO 2 reduction. An advantage of oxidizing glycerol in its crude form is the opportunity to valorize it without initial refinement. We describe an approach to replace the OER half-reaction with the sacrificial crude glycerol electrooxidation on a layered Au–Pt–Bi electrocatalyst on a Ni substrate. Compared to compositions with fewer components, the AuPtBi–Ni electrocatalyst improved the duration of performance and reduced the overall cell potential for glycerol electrooxidation in the extreme alkaline solutions representative of crude glycerol. These enhancements facilitated extended, unassisted hydrogen evolution from crude glycerol electrolysis, even under the power of a single-junction silicon solar cell at less than 1 sun illumination. We characterized the oxidation products of crude glycerol electrolysis and the subsequent products formed spontaneously in the electrolyte in the highly alkaline solution. This analysis helps to both identify the stoichiometric limits of glycerol oxidation at the low cell potentials of interest here and to understand the chemical control imparted by electrocatalysis on the ultimate compounds formed in the crude solution. Furthermore, the results for the AuPtBi electrocatalyst show that incorporating crude glycerol oxidation into integrated electrochemical systems can simultaneously simplify their design and significantly improve solar-to-hydrogen rates.

08 HYDROGEN↗

Anion exchange membranes: The effect of reinforcement in water and electrolyte

Alkaline anion-conducting polymer-based CO 2 electrolysis and water electrolysis are among two emerging renewable energy conversion technologies. Their system design and integration offer promise of lower capital cost due to utilization of low-cost catalysts, in contrast to platinum group metal catalysts required for cation-conducting polymer-based devices. However, a critical component, the polymer electrolyte membrane, remains an obstacle hampering system performance and durability. In this study, commercially-available Sustainion® membranes with and without PTFE-reinforcement were investigated to understand previously unreported origins of improved device performance when compared to alternative membrane chemistries. We report critical membrane properties, such as morphology, thermal stability, as well as temperature-, hydration-, and counter-ion dependent ion conductivity. Moveover, the changes in uptake and conductivity of membranes in supporting electrolytes of K 2 CO 3 and KOH investigated as a function of their concentration. Presence of reinforcement and supporting electrolyte type alter the membrane's transport functionality, which could help guide device design for improved performance. In conclusion, the obtained results not only show how Sustainion® properties change with operating environment for CO 2 and water electrolysis applications, but also provide understanding for internal and external factors controlling anion-exhcnage membrane functionality in electrochemical devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recovery of Alkaline-Earths into Liquid Bi in Ternary LiCl-KCl-SrCl 2 /BaCl 2 Electrolytes at 500 °C

Electrochemical reduction of Sr 2+ and Ba 2+ into liquid Bi was investigated in dilute concentrations of SrCl 2 /BaCl 2 (0-5 mol%) in LiCl-KCl electrolytes at 500 °C to ascertain the limit of liquid Bi electrodes for alkaline-earth recovery. Analysis of the electrodes after constant current electrolysis to the specific charge of 270 C g -1 showed Sr 2+ ions consuming 29% of charge at 5 mol% before dropping to 8%-10% of the total charge at 0.45-0.72 mol% SrCl 2 . Ba 2+ ions consumed 54% at 5 mol% BaCl 2 before decreasing to 22%-24% at 0.42-0.89 mol% BaCl 2 ; substantial co-deposition of Li was observed in all chemistries, consuming up to 53% of charge. Considering only 1% of the total charge was consumed for depositing Ba 2+ and Sr 2+ ions in ~0.1 mol% SrCl 2 /BaCl 2 electrolyte, the lower recovery limit of Bi for alkaline-earth elements is suggested to be at ~0.4 mol% SrCl 2 /BaCl 2 to achieve appreciable deposition of alkaline-earths (>1.5 mol% Ba/Sr in liquid Bi). The overpotentials of liquid Bi at 5 mol% of SrCl 2 /BaCl 2 were evaluated by electrochemical impedance spectroscopy. The co-deposition of Sr and Li exhibited the largest increase in charge transfer resistances implying sluggish charge transfer kinetics whereas the co-deposition of Ba and Li exhibited a large increase in mass transport resistances due to the slow diffusion of Ba 2+ ions in the electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anion exchange membrane test protocol validation

This study presents the validation of protocols for measuring ion exchange capacity (IEC) and alkaline stability of anion exchange membranes (AEMs) for low-temperature water electrolysis. While protocols are often tested within individual laboratories, their results across multiple laboratories with varying equipment, environmental conditions, and personnel qualification remain unverified. The validation involved Los Alamos National Laboratory (LANL), National Renewable Energy Laboratory (NREL), and University of Oregon (UO) using the same commercially available AEM to assess reproducibility and reliability of the protocols under diverse conditions. For the IEC protocol, results across laboratories were consistent within ±10% of the NMR-determined reference value. The alkaline stability protocol could pose greater challenges due to factors such as variations in sample collection timing, preservation methods, and analytical techniques, but consistent test results for percentage IEC loss were demonstrated across institutions. These results highlight the reliability and applicability of the protocols, emphasizing the importance of validation to ensure consistency in diverse research environments.

08 HYDROGEN↗

Simple processing via thermal treatment and catalyst infiltration to enhance nickel electrode performance for liquid alkaline water electrolyzers

Two simple processes for enhancing liquid alkaline water electrolyzer performance are demonstrated. Both enhance 3D Ni electrodes by introducing a micron-scale rough structure throughout the bulk of the electrode. Oxidation/reduction relies on a simple thermal treatment cycle to create surface roughening through the volumetric expansion during NiO formation and volume contraction during reduction back to Ni metal. Catalyst infiltration introduces a washcoat of additional metal particles throughout the electrode, by flooding the electrode with catalyst precursor and converting it to micron-scale particles via a reducing thermal treatment. Further, the largest improvement in performance (211mV at 1.8Acm -2 ) is observed for infiltrated NiFe-3x catalyst. For Fe-free Ni-only electrodes, oxidation/reduction provides a larger improvement (157 mV at 1.8Acm -2 ) than infiltrated Ni-3X (106mV at 1.8Acm -2 ). For both processes, the observed electrode surface structure and performance is quite sensitive to the thermal treatment temperature.

08 HYDROGEN↗

Oxygen Electrocatalysis on Mixed-Metal Oxides/Oxyhydroxides: From Fundamentals to Membrane Electrolyzer Technology

Catalyzing the oxygen evolution reaction (OER) is important for key energy-storage technologies, particularly water electrolysis and photoelectrolysis for hydrogen fuel production. Under neutral-to-alkaline conditions, first-row transition-metal oxides/(oxy)hydroxides are the fastest-known OER catalysts and have been the subject of intense study for the past decade. Critical to their high performance is the intentional or accidental addition of Fe to Ni/Co oxides that convert to layered (oxy)hydroxide structures during the OER. Unraveling the role that Fe plays in the catalysis and the molecular identity of the true “active site” has proved challenging, however, due to the dynamics of the host structure and absorbed Fe sites as well as the diversity of local structures in these disordered active phases. In this Account, we highlight our work to understand the role of Fe in Ni/Co (oxy)hydroxide OER catalysts. We first discuss how we characterize the intrinsic activity of the first-row transition-metal (oxy)hydroxide catalysts as thin films by accounting for the contributions of the catalyst-layer thickness (mass loading) and electrical conductivity as well as the underlying substrate’s chemical interactions with the catalyst and the presence of Fe species in the electrolyte. We show how Fe-doped Ni/Co (oxy)hydroxides restructure during catalysis, absorb/desorb Fe, and in some cases degrade or regenerate their activity during electrochemical testing. We highlight the relevant techniques and procedures that allowed us to better understand the role of Fe in activating other first-row transition metals for OER. We find several modes of Fe incorporation in Ni/Co (oxy)hydroxides and show how those modes correlate with activity and durability. We also discuss how this understanding informs the incorporation of earth-abundant transition-metal OER catalysts in anion-exchange-membrane water electrolyzers (AEMWE) that provide a locally basic anode environment but run on pure water and have advantages over the more-developed proton-exchange-membrane water electrolyzers (PEMWE) that use platinum-group-metal (PGM) catalysts. We outline the key issues of introducing Fe-doped Ni/Co (oxy)hydroxide catalysts at the anode of the AEMWE, such as the oxidative processes triggered by Fe species traveling through the polymer membrane, pH-gradient effects on the catalyst stability, and possibly limited catalyst utilization in the compressed stack configuration. We also suggest possible mitigation strategies for these issues. Lastly, we summarize remaining challenges including the long-term stability of Fe-doped Ni/Co (oxy)hydroxides under OER conditions and the lack of accurate models of the dynamic active surface that hinder our understanding of, and thus ability to design, these catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Separation of Alkaline-Earth Elements from Molten Salts Using Liquid Metal Electrodes

Closing the nuclear fuel cycle requires recycling used nuclear fuel. Additional waste is generated during recycling due to fission products accumulating in processing salts (LiCl-KCl). Reducing waste generated during recycling entails recovering alkaline-earth fission products (Ba 2+ /Sr 2+ ) from molten chlorides with a minimal loss of bulk electrolyte constituents (Li + /K + ). Electrochemical co-deposition of Ba 2+ /Li + and Sr 2+ /Li + into liquid metal (Bi, Sb, Sn, Pb) and alloy (Bi-Sb) electrodes was investigated in LiCl-KCl-(BaCl 2 , SrCl 2 ) electrolytes at 500 °C and 650 °C. For the pure Bi (500 °C) and Sb (650 °C) electrodes, the greatest percentage of charge was used to deposit Ba and Sr. Effective recovery of Ba/Sr by liquid Bi and Sb electrodes is supported via experimentally determined activity values of Ba/Sr in Bi and Sb. Alloying Sb with Bi increased Ba recovery but decreased Sr recovery, as compared to recovery using the liquid Bi electrode. Here, the results suggest that alkaline-earth fission products can be recovered from molten chlorides by liquid metal electrodes via electrochemical separation, thereby providing a methodology to reduce the generation of nuclear waste from nuclear fuel recycling.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Tuning Alkaline Anion Exchange Membranes through Crosslinking: A Review of Synthetic Strategies and Property Relationships

Alkaline anion exchange membranes (AAEMs) are an enabling component for next-generation electrochemical devices, including alkaline fuel cells, water and CO2 electrolyzers, and flow batteries. While commercial systems, notably fuel cells, have traditionally relied on proton-exchange membranes, hydroxide-ion conducting AAEMs hold promise as a method to reduce cost-per-device by enabling the use of non-platinum group electrodes and cell components. AAEMs have undergone significant material development over the past two decades; however, challenges remain in the areas of durability, water management, high temperature performance, and selectivity. In this review, we survey crosslinking as a tool capable of tuning AAEM properties. While crosslinking implementations vary, they generally result in reduced water uptake and increased transport selectivity and alkaline stability. We survey synthetic methodologies for incorporating crosslinks during AAEM fabrication and highlight necessary precautions for each approach.

08 HYDROGEN↗

Optimizing Direct Air Capture Solvents to Minimize Energy Consumption of CO 2 Release in a Carbonate Electrolyzer

Addressing climate change by carbon management is critical to achieving the goal of net zero carbon emissions by 2050. In this work, we examined the electrochemically-driven recovery of CO 2 during alkaline solvent regeneration for solvent-based direct air capture. A mathematical model was developed by incorporating carbonate chemistry with water electrolysis to predict the energy consumption per unit of CO 2 released. The predicted results were consistent with the experimental data, in which the experimental work was achieved by characterizing alkalinity and carbon loading values of solvent collected from a flow carbonate electrolyzer. Through this study, we learned that minimizing the energy expended on CO 2 release can be achieved by using an anolyte with a lower alkalinity, increasing the electric charge input to the electrolyzer, and reducing the ohmic resistance of the electrolyzer. Furthermore, using a supporting electrolyte, e.g., Na 2 SO 4 in the present work, effectively compensates for the higher ohmic resistance from using an anolyte with a lower alkalinity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗