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At least 73 records · Page 4

Assessing the Long-Term Stability of Anion Exchange Membranes for Electrochemical CO 2 Reduction

Materials and cell components used in CO 2 electrolysis have largely been adapted from technologies initially developed for water electrolysis and fuel cells. However, electrochemical CO 2 reduction introduces distinct material challenges due to the unique chemical environment in this process. Here, in this study, we conducted ex-situ 1000 h stability tests on commonly used anion exchange membranes, exposing them exclusively to electrolytes and organic molecules used or produced during CO 2 electrolysis, at concentrations relevant to and compatible with postseparation processes. Notably, 15% w/w n-propanol and 5 M acetic acid caused complete dissolution or partial disintegration of the membranes unless cross-linking was present and remained stable throughout the test. When the membranes stayed physically intact, most of them exhibited excellent chemical stability in alkaline medium containing alcohols or formic acid, which was confirmed by vibrational spectroscopy and ion exchange capacity measurements. However, exposure to alcohol-and acid-containing solutions led to a substantial increase in swelling and water uptake, with potential implications for mechanical stability, ion/product crossover, and compression management of adjacent components. The potential effects of CO 2 electroreduction products on membrane stability, their subsequent impact on electrolyzer performance, and mitigation strategies are discussed.

CO2RR↗

Computer-aided design of stability enhanced nicotinamide cofactor biomimetics for cell-free biocatalysis

Cell-free biocatalysis (CFB) is an efficient and environmentally friendly method to synthesize molecules such as pharmaceuticals, biochemicals, and biofuels through the in vitro use of enzyme cascades. These enzymes often require redox cofactors to drive chemical reactions. Natural redox cofactors (NAD(P)H) are expensive to isolate, motivating synthetic nicotinamide cofactor biomimetics (NCBs) as a cost-effective solution. A select handful of NCBs have been identified as potential NAD(P)H alternatives with comparable or improved redox capabilities, however, they display a tendency to degrade in common buffers. In this study, a library of 132 NCB candidates is systematically generated, over 85% of which have not been characterized in the literature, to expand the diversity of currently explored NCBs. The decomposition mechanism of NCBs in phosphate is evaluated using density functional theory (DFT), revealing protonation at the nicotinamide C5 position as a reporter of cofactor stability. Based on this result, we trained a linear regression model on DFT calculated descriptors to predict NCB stability in phosphate buffer, achieving mean absolute error (MAE) and root mean squared error (RMSE) values within computational accuracy. Analysis of key atomic descriptors and qualitative trends in our dataset informed the design of novel NCB candidates we propose with optimized stability. This work enables researchers to predict the relative stability of NCBs before synthesis, thereby streamlining the process to make CFB more affordable and viable at industry scales.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure, electrical characteristics, and high-temperature stability of aerosol jet printed silver nanoparticle films

Printed electronics has emerged as a versatile eco-friendly fabrication technique to create sintered nanoparticle (NP) films on arbitrary surfaces with an excellent control over the film microstructure. While applicability of such films for high-temperature applications is not explored previously, herein we report the high-temperature electrical stability of silver (Ag) metal NP films fabricated using an Aerosol Jet based printing technique and demonstrate that this behavior is dictated by changes in the film microstructure. In-situ high temperature (24–500 °C) impedance spectroscopy measurements show that the real part of the impedance increases with increasing temperature up to 150 °C, at which point a decreasing trend prevails until 300 °C, followed again by an increase in impedance. The electrical behavior is correlated with the in-situ grain growth of the Ag NP films, as observed afterwards by scanning electron microscopy and X-ray diffraction (XRD), and could be tailored by controlling the initial microstructure through sintering conditions. Using combined diffraction and spectroscopic analytical methods, it is demonstrated the Aerosol Jet printed Ag NP films exhibit enhanced thermal stability and oxidation resistance. In addition to establishing the conditions for stability of Ag NP films, the results provide a fundamental understanding of the effect of grain growth and reduction in grain boundary area on the electrical stability of sintered NP films.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Investigation of tearing mode stability near ideal stability boundaries via asymptotic matching techniques

A number of improvements to the TJ toroidal tearing mode code [Fitzpatrick, Phys. Plasmas 31, 102507 (2024)] are documented. The TJ code is also successfully benchmarked against the STRIDE toroidal tearing mode code [Glasser and Koleman, Phys. Plasmas 25, 082502 (2018)]. Finally, the new capabilities of the TJ code are used to investigate the stability of tearing modes in tokamak plasmas as an ideal stability boundary, associated with either an external-kink or an internal-kink mode, is approached. All elements of the tearing stability matrix are found to tend to infinity as an ideal stability boundary is approached. Furthermore, as the stability boundary is approached, the eigenfunctions of the various tearing modes in the plasma, which are decoupled by sheared plasma rotation, are all found to morph into that of the marginally stable ideal mode. However, the growth-rates and real frequencies of the various “ideal-tearing-modes” are different from one another. Moreover, the growth-rate of the ideal-tearing-mode that reconnects magnetic flux at the rational surface that lies closest to the edge of the plasma is the one that tends to a very large value as the stability boundary is approached. A relatively simple test for ideal stability that is capable of detecting stability boundaries for external-kink and internal-kink modes, even in the presence of a very close-fitting ideal wall, is described and verified.

FOS: Physical sciences↗

Turbulent transport stabilization by ICRH minority fast ions in low rotating JET ILW L-mode plasmas

The first experimental demonstration that fast ion induced stabilization of thermal turbulent transport takes place also at low values of plasma toroidal rotation has been obtained in JET ILW (ITER-like wall) L-mode plasmas with high ( 3 He)-D ICRH (ion cyclotron resonance heating) power. A reduction of the gyro-Bohm normalized ion heat flux and higher values of the normalized ion temperature gradient have been observed at high ICRH power and low NBI (neutral beam injection) power and plasma rotation. Gyrokinetic simulations indicate that ITG (ion temperature gradient) turbulence stabilization induced by the presence of high-energetic 3 He ions is the key mechanism in order to explain the experimental observations. Two main mechanisms have been identified to be responsible for the turbulence stabilization: a linear electrostatic wave-fast particle resonance mechanism and a nonlinear electromagnetic mechanism. The dependence of the stabilization on the 3 He distribution function has also been studied.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Stability enhancement module for grid-following converters: Hardware implementation and validation

Low-frequency oscillations limit power delivery of voltage-source converter interfaced resources, for example, wind and solar, operating in grid-following control mode. Our prior research identified the instability mechanism as the coupling between real power and voltage at point of common coupling. In turn, a stability enhancement control was proposed to weaken the coupling by introducing a simple voltage-based feedback loop. The stability enhancement control has been validated via electromagnetic transient simulation testbeds. The objectives of this paper are (a) to provide a more insightful explanation of the enhancement module by examining the impedance of the grid-following converter and (b) to verify the performance of the stability module using a hardware testbed. The theoretic examination demonstrates that stability enhancement module effectively reduces the negative resistance effect of $Z_{qq}$ and thus boosts stability. The experimental research leads to a hardware testbed of a grid-following converter with the ability of demonstrating low-frequency oscillations. Finally, the experimental results demonstrate the efficacy of the proposed stability enhancement control and the readiness of commercial realization of the stability enhancement unit.

42 ENGINEERING↗

Thermal stability and phase transformation in fully indium oxide (InO{sub 1.5}) stabilized zirconia

Indium oxide (InO{sub 1.5}) stabilized zirconia (InSZ) is an attractive material as electrolyte, or electrode, in solid oxide fuel cells (SOFCs), and as corrosion resistant top coat in thermal barrier coatings. However, little is known about the phase stability of cubic InSZ at temperatures that simulate the conditions in an operating SOFC or turbine. This article provides an investigation of the phase stability and phase transformations in cubic InSZ after heat treatments at 800, 1000, and 1200 °C for periods up to 2000 h. The results revealed that cubic InSZ is not stable during annealing at 1000 and 1200 °C, owing to a fast destabilization of the initial cubic phase to tetragonal, and eventually to monoclinic (c → t → m). The c → t → m transition in InSZ is intimately associated with the indium volatilization. On the other hand, cubic InSZ remained stable for 2000 h at 800 °C, although the partial formation of the tetragonal phase was observed along with a 0.25% contraction in the unit cell volume of the cubic phase, caused by short-range ordering. These results demonstrate that technological applications of cubic InSZ are restricted to temperatures at which the volatilization of the InO{sub 1.5} stabilizer does not occur. - Highlights: •Phase stability of fully InO{sub 1.5} stabilized zirconia (cubic InSZ) was evaluated. •Cubic InSZ is instable at temperatures ≥ 1000 °C, owing to the cubic-to-tetragonal-to-monoclinic destabilization. •Cubic InSZ undergoes the cubic-to-tetragonal transformation at ~ 800 °C. •Owing to the low phase stability, applications of cubic InSZ in TBCs or SOFCs are restricted.

36 MATERIALS SCIENCE↗

Phase stabilities at a glance: Stability diagrams of nickel dipnictides

In the course of the recent advances in chemical structure prediction, a straightforward type of diagram to evaluate phase stabilities is presented based on an expedient example. Crystal structures and energetic stabilities of dipnictides NiPn{sub 2} (Pn = N, P, As, Sb, Bi) are systematically investigated by first principles calculations within the framework of density functional theory using the generalized gradient approximation to treat exchange and correlation. These dipnictides show remarkable polymorphism that is not yet understood systematically and offers room for the discovery of new phases. Relationships between the concerned structures including the marcasite, the pyrite, the arsenopyrite/CoSb{sub 2}, and the NiAs{sub 2} types are highlighted by means of common structural fragments. Electronic stabilities of experimentally known and related AB{sub 2} structure types are presented graphically in so-called stability diagrams. Additionally, competing binary phases are taken into consideration in the diagrams to evaluate the stabilities of the title compounds with respect to decomposition. The main purpose of the stability diagrams is the introduction of an image that enables the estimation of phase stabilities at a single glance. Beyond that, some of the energetically favored structure types can be identified as potential new phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced Stability of Lithium Metal Anode by using a 3D Porous Nickel Substrate

Lithium (Li) metal is considered the “holy grail” anode for high energy density batteries, but its applications in rechargeable Li metal batteries are still hindered by the formation of Li dendrites and low Coulombic efficiency for Li plating/stripping. An effective strategy to stabilize Li metal is by embedding Li metal anode in a three-dimensional (3D) current collector. Here, a highly porous 3D Ni substrate is reported to effectively stabilize Li metal anode. Using galvanostatic intermittent titration technique combined with scanning electron microscopy, the underlying mechanism on the improved stability of Li metal anode is revealed. It is clearly demonstrated that the use of porous 3D Ni substrate can effectively suppress the formation of “dead” Li and forms a dense surface layer, whereas a porous “dead” Li layer is accumulated on the 2D Li metal which eventually leads to mass transport limitations. X-ray photoelectron spectroscopy results further revealed the compositional differences in the solid-electrolyte interphase layer formed on the Li metal embedded in porous 3D Ni substrate and the 2D copper substrate.

Yu, Lu↗

Stability Considerations Using a Microscopic Stability Model Applied to a 2G Thin Film Coated Superconductor

A numerical, finite element simulation of local temperature fields, critical current and transport current distributions is applied to a 2G thin film coated high-temperature superconductor. The focus is on simulation of quenches originating from transport current locally exceeding critical current density. As in previous reports, a statistical treatment of superconductor parameters (critical temperature, current and magnetic field) is applied for this analysis; it shall take into account uncertainties possibly arising from shortcomings in conductor manufacture or during measurements of their properties. The results of the calculations are used as quasi-boundary (driving) conditions for a subsequent transient microscopic numerical stability analysis. Traditionally, stability analysis usually applies analytic stability functions that incorporate conventional, phonon-related timescales, t and disturbances. The question is whether decay of electron pairs and subsequent relaxation of the excited state to a new dynamic equilibrium carrier concentration, the “electron aspect” of the stability problem, under the same disturbances, proceeds on another timescale, t{sup ′}. Is this timescale identical to the traditional (phonon) timescale, t? If not, how large are the differences? The recently reported microscopic stability model, now applied to a thin film conductor, is consulted to find an answer to these questions. A time limit, t{sub Quench}, can be extracted from the simulations, as the time of immediate onset of a quench. This is a new approach in stability considerations since, conventionally, a temperature limit, T < T{sub Crit}, is set as stability criterion. If electrical operation or cooling conditions cannot immediately respond to this challenge, the thin film superconductor, if this time limit is exceeded, will hardly be able to return to zero loss current transport.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Assessment of the Effectiveness of Three Aftermarket Gasoline Fuel Stabilizers in Preventing Gum Formation and Loss of Oxidation Stability

We note that fuel stabilizers have long been marketed to consumers to prevent oxidation and gum formation. In the past, gasoline storage for long periods of time was commonly limited to off-road equipment that was used infrequently. Cars and trucks that were driven regularly consumed the fuel in their tanks rapidly enough to avoid excessive fuel aging. However, plug-in hybrid electric vehicles (PHEVs) may be operated frequently without engine operation, raising the possibility that fuel may be stored in the tank for longer periods of time. Studies of the oxidation of gasoline have provided scientific understanding of the process, but there is little if any scientifically backed information aimed at aiding consumers in assessing the need to use an aftermarket fuel stabilizer if they anticipate lengthy periods of fuel storage in their fuel tank. This study was conceived to address this information gap by evaluating three aftermarket stabilizer products alongside baseline gasoline using sealed samples over a period of 12 months of aging. The aging was carried out under ambient temperature conditions with an additional series of samples kept in refrigerated storage. Analyses of vapor pressure, copper strip corrosion, oxidation stability, existent gums, and potential gums were carried out using standard ASTM tests to evaluate the samples as aging progressed. The results show that baseline gasoline remained compliant with relevant specifications to at least 12 months of aging without the use of aftermarket stabilizer additives. Use of two of the aftermarket additives increased the oxidation stability of the baseline gasoline, but this added stability was not necessary to comply with gasoline specifications.

42 ENGINEERING↗

Unveiling the Stabilities of Nickel–Based Layered Oxide Cathodes at an Identical Degree of Delithiation in Lithium–Based Batteries

Bulk, surface, and interfacial instabilities that impact the cycle and thermal performances are the major challenges with high-energy-density LiNi 1–x–y Mn x Co y O 2 (NMC) cathodes with high nickel contents. It is generally believed that the instabilities and performance losses become exponentially aggravated as the nickel content increases. Disparate from this prevailing belief, it is herein demonstrated that NMC cathodes with higher Ni contents may imply better overall stability than “lower-Ni” cathodes under an identical degree of delithiation (charging) conditions. With two representative cathodes, LiNi 0.8 Mn 0.1 Co 0.1 O 2 and LiNiO 2 , a systematic investigation into their stabilities with control of the degree of delithiation is presented. Electrochemical tests indicate that LiNiO 2 displays better cyclability than LiNi 0.8 Mn 0.1 Co 0.1 O 2 at the same delithiation state. Comprehensive structural and interphase investigations unveil that the inferior cyclability of LiNi 0.8 Mn 0.1 Co 0.1 O 2 predominantly results from aggravated parasitic reactions, and the interphase stability may be more critical than lattice stability in dictating cyclability. Also, LiNiO 2 delivers similar or better thermal behavior than LiNi 0.8 Mn 0.1 Co 0.1 O 2 . Finally, the findings demonstrate a strong correlation of the stability of NMC cathodes to the degree of delithiation state rather than the Ni content itself, highlighting the importance of reassessing the true implications of Ni content and structural and interphasial tuning on the stabilities of NMC cathodes.

25 ENERGY STORAGE↗

Improve First-Cycle Efficiency and Rate Performance of Layered-Layered Li 1.2 Mn 0.6 Ni 0.2 O 2 Using Oxygen Stabilizing Dopant

The poor first-cycle Coulombic efficiency and rate performance of the Li-rich layered-layered oxides are associated with oxygen gas generation in the first activation charging and sluggish charge transportation along the layers. In this work, we report that barium doping improves the first-cycle efficiency of Li-rich layered-layered Li1.2Mn0.6Ni0.2O2 via suppression of the oxidation of O2– ions in the first charging. This effect can be attributed to the stabilizing effect of the barium cations on the oxygen radical intermediates generated during the oxidation of O2–. Meanwhile, because the stabilized oxygen radicals likely facilitate the charge transportation in the layered-layered structure, the barium-doped Li1.2Mn0.6Ni0.2O2 exhibits significant improvement in rate performance. Stabilizing the oxygen radicals could be a promising strategy to improve the electrochemical performance of Li-rich layered-layered oxides.

36 MATERIALS SCIENCE↗

Stabilization of Pt monolayer catalysts under harsh conditions of fuel cells

We employed density functional theory to explore the stability of core (M = Cu, Ru, Rh, Pd, Ag, Os, Ir, Au)-shell (Pt) catalysts under harsh conditions, including solutions and reaction intermediates involved in the oxygen reduction reaction (ORR) in fuel cells. A pseudomorphic surface alloy (PSA) with a Pt monolayer (Pt{sub 1ML}) supported on an M surface, Pt{sub 1ML}/M(111) or (001), was considered as a model system. Different sets of candidate M cores were identified to achieve a stable Pt{sub 1ML} shell depending on the conditions. In vacuum conditions, the Pt{sub 1ML} shell can be stabilized on the most of M cores except Cu, Ag, and Au. The situation varies under various electrochemical conditions. Depending on the solutions and the operating reaction pathways of the ORR, different M should be considered. Pd and Ir are the only core metals studied, being able to keep the Pt{sub ML} shell intact in perchloric acid, sulfuric acid, phosphoric acid, and alkaline solutions as well as under the ORR conditions via different pathways. Ru and Os cores should also be paid attention, which only fall during the ORR via the *OOH intermediate. Rh core works well as long as the ORR does not undergo the pathway via *O intermediate. Our results show that PSAs can behave differently from the near surface alloy, Pt{sub 1ML}/M{sub 1ML}/Pt(111), highlighting the importance of considering both chemical environments and the atomic structures in rational design of highly stable core-shell nanocatalysts. Finally, the roles that d-band center of a core M played in determining the stability of supported Pt{sub 1ML} shell were also discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermodynamic stabilization of nanocrystalline aluminum

Nanocrystalline metals are generally unstable due to a large volume fraction of high-energy grain boundaries associated with a small grain size. Preferential dopant segregation to the high-energy grain boundaries is observed to enhance the stability of the material’s microstructure by minimizing its energy. Nanocrystalline aluminum-dopant systems were evaluated for thermodynamic stability against grain growth and phase precipitation via the mechanism of grain boundary segregation according to a modified regular nanocrystalline solution model. Fifty-one potential dopant elements have been evaluated for their efficacy in stabilizing nanostructures with three potential candidates, magnesium, lanthanum, and silicon, identified possessing the characteristics to promote grain boundary segregation and a state of thermodynamic stability in aluminum’s nanocrystalline regime. Here, the minimum dopant content required to achieve nanocrystalline microstructure stability is identified for each of the three candidate elements. Beyond this minimum content, further addition of the dopant elements decreased the final microstructure’s stability with no effects on the existence of a stable nanocrystalline state.

36 MATERIALS SCIENCE↗

Photocatalytic Facet Selectivity in BiVO 4 Nanoparticles: Polaron Electronic Structure and Thermodynamic Stability Considerations for Photocatalysis

Selective charge separation among different crystal facets of a semiconductor is an intriguing phenomenon for which there is no firm and full theoretical foundation currently. In this work, we report on a density functional theory + U characterization of band alignment and electron and hole polaron stabilities among the (010), (110), and (011) facets of bismuth vanadate BiVO 4 (BVO). Computation-derived band alignment indicates that the conduction band minima are at nearly the same level among the three facets but that the valence band maxima exhibit a shift. We also modeled electron and hole polarons as localized electrons and holes on vanadium and oxygen, respectively, and determined their relative stabilities from a “bulk” region to a surface region. Calculated stabilities reveal similar stability profiles across the various facets, with electron polarons most stable when localized on subsurface V atoms and hole polarons most stable on surface O atoms. Calculations indicate a small stability preference for electron polarons toward the (011) facet and for hole polarons toward the (110) facet, whereas, experimentally, interfacial reduction is observed to take place selectively on the (010) facet and oxidation on the (110) and (011) facets. Facet selectivity could be occurring on the basis of thermodynamics (electron or holes showing a stronger affinity for some facets over others) or kinetics (electron or hole transport and/or redox processes being more efficient toward/on some facets over others) or a combination of both. This work establishes that thermodynamic stability alone is not responsible for the observed facet selectivity in BVO. Furthermore, we surmise that polaron transport kinetics and interfacial redox kinetics are likely to have a role in facet selectivity in BVO. These issues will be the subject of future publications.

14 SOLAR ENERGY↗