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At least 343 records · Page 19

Multi-Species Test of Ion Cyclotron Resonance Heating at High Altitudes

Observations of ion distributions and plasma waves obtained by the Dynamics Explorer 1 satellite in the high-altitude, nightside auroral zone are used to study ion energization for three ion species. A number of theoretical models have been proposed to account for the transverse heating of these ion populations. One of these, the ion cyclotron resonance heating (ICRH) mechanism, explains ion conic formation through ion cyclotron resonance with broadband electromagnetic wave turbulence in the vicinity of the characteristic ion cyclotron frequency. The cyclotron resonant heating of the ions by low-frequency electromagnetic waves is an important energy source for the transport of ions from the ionosphere to the magnetosphere. In this paper we test the applicability of the ICRH mechanism to three simultaneously heated and accelerated ion species by modelling the ion conic formation in terms of a resonant wave-particle interaction in which the ions extract energy from the portion of the broadband electromagnetic wave spectrum which includes the ion cyclotron frequency. Using a Monte Carlo technique we evaluate the ion heating produced by the electromagnetic turbulence at low frequencies and find that the wave amplitudes near the ion cyclotron frequencies are sufficient to explain the observed ion energies.

Persoon, A. M.↗

Neutral gas analysis for JET DT operation

Neutral gas analysis, the measurement and evaluation of total and partial pressures, is a key technique to study the impact of neutral gas dynamics on retention, recycling and release processes of fuel or impurity species in fusion devices. At JET, the experiment closest to ITER in terms of operating parameters and size, various detectors and techniques for partial pressure and total pressure measurements are deployed together to characterise neutral gas dynamics during and after plasma operation on various toroidal and poloidal locations. An extensive modification of JET's sub-divertor neutral gas diagnostic system aims at retaining and extending established measurement capabilities in the forthcoming Deuterium-Tritium (DT) experiments (DTE2). To achieve DT compatibility, a separation of radiation-sensitive electronics from the sensor and adequate radiation shielding is required, as well as utilisation of a DT compatible differential pumping system with adjustable throughput to account for the strong pressure variation in the sub-divertor region. Finally, the sub-divertor neutral gas diagnostic will be equipped with multiple Residual Gas Analysers (RGAs), utilising quadrupole mass spectrometry and electrostatic ion-trap-principles, all operating with remote electronics located behind the biological radiation shield. These RGAs will record data in a fast selected discrete mass mode during plasma pulses (cycle ~2 s) and will automatically switch back to continuous data recording (cycle ~100 s) afterwards. They will be complemented by a newly improved Penning gauge spectroscopy configuration in particular supporting the He and D 2 separation relevant for DT operation. The distance between these devices and their associated control unit is typically 15m . A newly developed RGA with a cable length of 80 m, compatible with the ITER environment, will also be employed for the first time. Finally, this set-up and its operation in DTE2 will provide vital input to the development of the ITER divertor RGA in the most relevant environment currently available.

47 OTHER INSTRUMENTATION↗

Langevin and Fokker-Planck analyses for diffusion-mediated passing of circular and discorectangular species in two-dimensional channels

The propensity for pairs of diffusing species to pass each other within narrow channels or pores is of basic interest as a first-passage-type problem. It is also of relevance for solution-phase transport in nanoporous materials, and in particular for catalytic conversion reactions where high yield requires that product species can efficiently pass reactant species to exit the pores. Here, we analyze a two-dimensional model with nonoverlapping circular and discorectangular species confined to a rectangular channel, and where passing is mediated by Brownian dynamics in an implicit solvent. For narrower channels where passing is still possible, the discorectangle must align with the channel to pass the circular species. Behavior of the passing propensity, 𝑃, can be assessed by strongly damped Langevin simulations, or within an equivalent Fokker-Planck equation (FPE) formalism. The latter corresponds to a diffusion problem in a “higher-dimensional channel” with a constriction. We assess the variation of the passing propensity, 𝑃, for a broad range of channel width including its scaling just above the threshold where passing is sterically blocked. Analysis of 𝑃 versus the rotational diffusion coefficient 𝐷 𝑟 of the discorectangle reveals a significant decrease in 𝑃 for lower 𝐷 𝑟 for moderate channel width. This prompts a direct analysis of the regime where 𝐷 𝑟 → 0 , for which the FPE can be reduced to a three-dimensional diffusion problem, precise analysis of which is facilitated by adaptive-mesh finite element methods. The dependence of 𝑃 on the aspect ratio of the discorectangle is also assessed.

Rahman, Md Khaledur [Ames Laboratory (AMES), Ames,↗

High-Current Light-Ion Cyclotron for Applications in Nuclear Security and Radioisotope Production

In this article, we propose the conceptual design, with supporting beam dynamics results, of a normal conducting, separated-sector cyclotron with a strong-focusing field gradient designed to accelerate light ions with a charge-to-mass ratio of 1/2 up to 15–20 MeV/u. The design can support a host of applications for therapy, radiobiology, material science, and instrumentation development. The light-ion species, which can include a mixed ion beam, can be dynamically chosen to provide a range of characteristic signals appropriate for specific material identification such as special nuclear materials. A conservative baseline concept is presented which has been optimized for radioisotope production of alpha emitters and theranostic radiopharmaceuticals. The modular design is also demonstrated to be scalable in gross physical parameters by a factor of 2–3, thereby reducing the size, weight, and power requirements (SWaP) and enabling near-term security applications.

07 ISOTOPE AND RADIATION SOURCES↗

A two-dimensional model study of the QBO signal in SAGE II NO2 and O3

Calculations of the quasi biennial oscillation (QBO) signal in Stratospheric Aerosol and Gas Experiment (SAGE) II O3 and NO2 data between 1984 and 1991 are presented and have been investigated by using a two-dimensional model. The isentropic 2D model is a fully interactive radiative-dynamical-chemical model in which the eddy fluxes of chemical species are calculated in a consistent manner. The QBO in the model has been forced by relaxing the equatorial zonal wind toward the observations at Singapore allowing the comparison of the model with observations from specific years. The model reproduces the observed vertical structure of the equatorial ozone anomaly with the well-known transition from dynamical to photochemical control at around 28km. The model also reproduces the observed vertical structure of the SAGE II observed NO2 anomaly. The model studies have shown that it is the QBO modulation of NO2 which the main cause of QBO signal in O3 above 30 km. The model also reproduces the observed latitudinal structure of the QBO signals in O3 and NO2. Due to the differing horizontal distribution of O3 and NO(y) the ozone signal shows a distinct phase change in the subtropics whereas the NO2 anomaly gives a broader signal.

Chipperfield, M. P.↗

Mapping Chaparral in the Santa Monica Mountains Using Multiple Spectral Mixture Models

California chaparral is one of the most important natural vegetation communities in Southern California, representing a significant source of species diversity and, through a high susceptibility to fire, playing a major role in ecosystem dynamics. Due to steep topographic gradients, harsh edaphic conditions and variable fire histories, chaparral typically forms a complex mosaic of different species dominants and age classes, each with unique successional responses to fire and canopy characteristics (e.g. moisture content, biomass, fuel load) that modify fire susceptibility. The high human cost of fire and intimate mixing along the urban interface combine to modify the natural fire regime as well as provide additional impetus for a better understanding of how to predict fire and its management. Management problems have been further magnified by nearly seventy years of fire suppression and drought related die-back over the last few years resulting in a large accumulation of highly combustible fuels. Chaparral communities in the Santa Monica Mountains exemplify many of the management challenges associated with fire and biodiversity. A study was initiated in the Santa Monica Mountains to investigate the use of the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) for providing improved maps of chaparral coupled with direct estimates of canopy attributes (e.g. biomass, leaf area, fuel load). The Santa Monica Mountains are an east-west trending range located approximately 75 kilometers north of Los Angeles extending westward into Ventura County. Within the Santa Monica Mountains a diverse number of ecosystems are located, including four distinct types of chaparral, wetlands, riparian habitats, woodlands, and coastal sage scrub. In this study we focus on mapping three types of chaparral, oak woodlands and grasslands. Chaparral mapped included coastal sage scrub, chamise chaparral and mixed chaparral that consisted predominantly of two species of Ceanothus.

Green Robert O.↗

Ca-dimers, solvent layering, and dominant electrochemically active species in Ca(BH4)2 in THF

Abstract Divalent ions (Mg, Ca, and Zn) are being considered as competitive, safe, and earth-abundant alternatives to Li-ion electrochemistry, but present challenges for stable cycling due to undesirable interfacial phenomena. We explore the formation of electroactive species in the electrolyte Ca(BH 4 ) 2 ∣THF using molecular dynamics coupled with a continuum model of bulk and interfacial speciation. Free-energy analysis and unsupervised learning indicate a majority population of neutral Ca dimers and monomers with diverse molecular conformations and an order of magnitude lower concentration of the primary electroactive charged species – the monocation, $${\rm{CaBH}}_{4}^{+}$$ CaBH 4 + – produced via disproportionation of neutral complexes. Dense layering of THF molecules within ~1 nm of the electrode surface strongly modulates local electrolyte species populations. A dramatic increase in monocation population in this interfacial zone is induced at negative bias. We see no evidence for electrochemical activity of fully-solvated Ca 2+ . The consequences for performance are discussed in light of this molecular-scale insight.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The neutral mass spectrometer on Dynamics Explorer B

A neutral gas mass spectrometer has been developed to satisfy the measurement requirements of the Dynamics Explorer mission. The mass spectrometer, a quadrupole, will measure the abundances of neutral species in the region 300-500 km in the earth's atmosphere. These measurements will be used in concert with other simultaneous observations on Dynamics Explorer to study the physical processes involved in the interactions of the magnetosphere-ionosphere-atmosphere system. The instrument, which is similar to that flown on Atmosphere Explorer, employs an electron beam ion source operating in the closed mode and a discrete dynode multiplier as a detector. The mass range is 22 to 50 amu. The abundances of atomic oxygen, molecular nitrogen, helium, argon, and possibly atomic nitrogen will be measured to an accuracy of about + or - 15% over the specified altitude range, with a temporal resolution of one second.

Carignan, G. R.↗

Control of core–shell nanoparticles properties through plasma synthesis: a computational study

The improved properties of core–shell nanoparticles (CSNPs) over homogeneous nanoparticles (NPs) have expanded and diversified the applications of these nanomaterials. However, controlling the properties of CSNPs can be a challenging task. Low temperature plasmas have proven to be an effective method of producing NPs with uniform size and morphology, and high yield. That said, NP transport and growth dynamics are sensitive to LTP properties. We report on a computational investigation of the evolution of Ge–Si CSNP properties as a function of operating conditions through the modeling of a flowing, two-zone inductively coupled plasma (ICP) reactor. Ar/GeH 4 and Ar/SiH 4 gas mixtures were supplied to separate plasma zones at a pressure of 1 Torr to promote growth of Ge cores and Si shells. The negatively charged CSNPs are trapped electrostatically in the vicinity of the antennas where the plasma is generated and where the majority of particle growth occurs. Particles that grow to a critical size are then de-trapped by fluid drag due to neutral gas flow. A two-dimensional hybrid plasma model coupled with a three-dimensional kinetic NP transport model were utilized to resolve plasma chemistry and NP growth processes that take place on distinct timescales. The trends in CSNP properties and trapping mechanisms associated with flow rate, applied ICP power and inlet precursor fraction are discussed. While the spatial distribution of plasma produced radical species can have significant impact on the NP growth process, the NP transport dynamics are what ultimately dictates the growth environment that is unique to each particle and so determines their final dimension and composition. The key to optimizing reactor conditions involves controlling the spatial density of growth species and plasma profile as a means to tailor particle trapping dynamics suitable to produce CSNPs for a specific application.

36 MATERIALS SCIENCE↗

Theoretical Perspective on Operando Spectroscopy of Fluxional Nanocatalysts

Improvements in operando spectroscopy have enabled the catalysis community to investigate the dynamic nature of catalysts under operating conditions with increasing detail. Still, the highly dynamic nature of some catalysts, such as fluxional supported subnano clusters, presents a formidable challenge even for the most state-of-the-art techniques. Here, the reason is that such fluxional catalytic interfaces contain a variety of thermally accessible states. Operando spectroscopies used in catalysis generally fall into two categories: ensemble-based techniques, which provide spectra containing the signals of the entire ensemble of states of the catalyst and are not necessarily dominated by the most active species, and localized techniques, which provide atomistic-level information about the dynamics of active sites in a very small area, which might not include the most active species. Combining many different kinds of techniques can provide detailed insight; however, we propose that effective utilization of specific computational techniques and approaches within the fluxionality paradigm can fill the gap and enable atomistic characterization of the most relevant catalytic sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Activation of Single-Atom Catalysts by Reaction Intermediates: Conversion of Formic Acid on Rh/Fe 3 O 4 (001)

The stability and activity of supported single-atom catalysts (SACs) represent critical yet opposing factors limiting our ability to explore and exploit their unique properties. Here, this study demonstrates the operation of a switchable catalyst that is activated in the presence of surface intermediates and reverts back to a stable but inactive form when the reaction is completed. We employ atomically defined Rh-Fe 3 O 4 (001) catalysts to demonstrate how structurally stable Rh, bound in surface octahedral Fe sites, gets destabilized to form highly active Rh adatoms and small clusters. Conversion of formic acid, leading initially to surface formate and hydroxyl species, is employed as a model reaction to probe the dynamics of such processes. We find that surface hydroxyl recombination to water through the Mars van Krevelen mechanism reduces Rh coordination, triggering its conversion to active Rh adatoms. Since such lattice oxygen exchange is observed in many acid-base and redox chemistries, the process can be broadly applicable to controlling the activation of the range of SACs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An experimental and kinetic modeling study of the pyrolysis of isoprene, a significant biogenic hydrocarbon in naturally occurring vegetation fires

Isoprene dominates the carbon flux emitted by vegetation and constitutes 40% of non-methane biogenic emissions worldwide. Despite pyrolysis experiments at temperatures above 1000 K showing a link between isoprene combustion and aromatic species formation, comprehensive mechanistic research on isoprene is scarce in the literature. Here, in this work, we carry out an experimental and theoretical study to build, for the first time, a chemical kinetic model describing isoprene pyrolysis. The formation of polycyclic aromatic hydrocarbon (PAH) precursor species, often observed in vegetation fire plumes, is partially explained by isoprene pyrolysis experiments and theoretical modeling. Molecular dynamics (MD) simulations unveil reaction pathways from allylic isoprenyl radicals to allene and cyclopentadiene (CPD) intermediates, two relevant species detected in the experiments. Rate constants for these identified pathways are calculated using variational transition state theory to update the kinetic model, which is validated against single-pulse shock tube (SPST), and jet-stirred reactor (JSR) experimental data in the temperature range of 850–1690 K. The kinetic model presents satisfactory agreement with the SPST experimental data, and a reaction pathway analysis shows that association of propargyl radicals results in benzene formation. The JSR pathway analysis also identifies the prominent reactions for CPD, benzene, styrene, and toluene formation. Our model does not reproduce the CPD experimental profiles, indicating that additional studies are necessary. Overall, our findings advance the understanding of isoprene pyrolysis and its related atmospheric pollutants in naturally occurring vegetation fires where smoldering and oxygen-deficient combustion processes are present.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Brown watersnakes (Nerodia taxispilota) as bioindicators of mercury contamination in a riverine system

Herein, mercury (Hg) is a contaminant that enters the environment through natural or anthropogenic means. Ecological risk assessments have examined Hg bioaccumulation and effects in many taxa, but little is known about Hg dynamics in reptiles, or their potential use as bioindicator species for monitoring Hg in aquatic systems. Numerous snake species, like North American watersnakes (Nerodia spp.), are piscivorous and are exposed to Hg through their diet. The purpose of this study was to identify factors associated with Hg accumulation in a common watersnake species and compare Hg concentrations of the snakes to those in fish occupying the same habitats. To this end, we sampled brown watersnakes (Nerodia taxispilota) from the Savannah River, a major river system in the southeastern U.S., and compared N. taxispilota Hg accumulation trends to those of bass (Micropterus salmoides), catfish (Ictalurus and Ameiurus spp.), and panfish (Lepomis and Pomoxis spp.) collected from the same reach. Total Hg (THg) in N. taxispilota tail tips ranged from 0.020 to 0.431 mg/kg (wet weight; mean: 0.104 ± 0.008). Snake tail THg was significantly correlated with blood THg, which ranged from 0.003 to 1.140 mg/kg (0.154 ± 0.019). Snake size and site of capture were significantly associated with tail THg. Snake tail THg increased at sites along and downstream of the area of historic Hg pollution, consistent with fish THg. Snake muscle THg was predicted based on tail THg and ranged from 0.095 to 1.160 (0.352 ± 0.022). To gauge Hg biomagnification in N. taxispilota, we compared predicted snake muscle THg concentrations to THg in fish of consumable size. Average biomagnification factors for THg in N. taxispilota were 3.1 (panfish) and 5.4 (catfish), demonstrating N. taxispilota likely biomagnify Hg through their diet. These results reveal N. taxispilota to be an effective bioindicator species for monitoring Hg in aquatic environments.

54 ENVIRONMENTAL SCIENCES↗

Mechanistic Insights on Permeation of Water over Iron Cations in Nanoporous Silicon Oxide Films for Selective H 2 and O 2 Evolution

Electrocatalysts encapsulated by an ultrathin and semipermeable oxide layer offer a promising avenue for efficient, selective, and cost-effective production of hydrogen through photoelectrochemical water splitting. This architecture is especially attractive for Z-scheme water splitting, for which a nanoporous oxide film can be leveraged to mitigate undesired, yet kinetically facile, reactions involving redox shuttles, such as aqueous iron cations, by limiting transport of these species to catalytically active sites. In this work, molecular dynamics simulations were combined with electrochemical measurements to provide a mechanistic understanding of permeation of water and Fe(III)/Fe(II) redox shuttles through nanoporous SiO 2 films. It is shown that even for SiO 2 pores with a width as small as 0.8 nm, water does not experience any energy barrier for permeating into the pores due to a favorable interaction with hydrophilic silanol groups on the oxide surface. In contrast, permeation of Fe(III) and Fe(II) into microporous SiO 2 pores is limited due to high energy barriers, which stem from a combination of distortion and dehydration of the second and third ion solvation shells. Furthermore, our simulations and experimental results show that SiO 2 coatings can effectively mitigate undesired Fe(III)/Fe(II) redox reactions at underlying electrodes by attenuating permeation of iron cations, while allowing water to permeate and thus participate in water splitting reactions. In a broader context, our study demonstrates that selectivity of solvated cations can be manipulated by controlling the pore size and surface chemistry of oxide films.

14 SOLAR ENERGY↗

Linking Pressure to Electrochemical Evolution in Solid-State Conversion Cathode Composites

Conversion-type cathodes, such as sulfur, FeS 2 , and FeF 3 , offer high theoretical capacities in solid-state lithium batteries but are hindered by substantial volume changes during cycling, leading to interfacial contact loss, crack formation, and microstructural degradation. Here, we investigate the relationships between electrochemical, mechanical, and structural evolution in solid-state electrode composites with these three active materials. Using real-time stack-pressure monitoring, synchrotron X-ray absorption spectroscopy, and electrokinetic modeling, we elucidate how stress evolution is linked to reversible and irreversible redox reactions. Nonlinear stack pressure evolution in cells with sulfur, FeS 2 , and FeF 3 electrode composites is found to arise from material-specific volume changes, the balance of volume change between the working and counter electrode, and the formation of distinct reaction intermediates. The three materials exhibit distinct stack pressure evolution, which is closely related to the different reaction processes in the materials, as demonstrated with X-ray absorption spectroscopy measurements. Through mesoscale modeling, we relate the experimental measurements to species evolution at the particle scale and track the dynamic coexistence of intermediate phases. Our findings highlight the importance of designing for volume changes of a given active material in solid-state battery systems.

batteries↗

Probing Heterogeneous Charge Distributions at the α-Al 2 O 3 (0001)/H 2 O Interface

Unlike metal or semiconductor electrodes, the surface charge resulting from the protonation or deprotonation of insulating mineral oxides is highly localized and heterogeneous in nature. In this work the Stark active C≡N stretch of potassium thiocyanate is used as a molecular probe of the heterogeneity of the interfacial electrostatic potential at the α-Al 2 O 3 (0001)/H 2 O interface. Vibrational sum frequency generation (vSFG) measurements performed in the OH stretching region suggest that thiocyanate species organize interfacial water similarly to halide ions. Changes in the electrostatic potential are then tracked via Stark shifts of the vibrational frequency of the thiocyanate stretch. Our vSFG measurements show that we can simultaneously measure the vSFG response of SCN – ions experiencing charged and neutral surface sites. We assign local potentials of +308 and -154 mV to positively and negatively charged aluminol groups that are present at pH = 4 and pH = 10, respectively. Thiocyanate anions at positively charged surface sites and negatively charged surface sites and those participating in contact ion pairing adopt similar orientations and are oppositely oriented relative to thiocyanate ions near neutral surface sites. All four species followed Langmuir adsorption isotherms. Density functional theory–molecular dynamics (DFT-MD) simulations of SCN – near the neutral α-Al 2 O 3 (0001)/H 2 O interface show that the vSFG response in the C≡N stretch region originates from a SCN–H–O–Al complex, suggesting the surface site specificity of these experiments. To our knowledge this is the first spectroscopic measurement of local potentials associated with a heterogeneously charged surface. The ability to probe the evolution of local charges in situ could provide vital insight into many industrial, electrochemical, and geochemically relevant interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interactions of Oxide Surfaces with Water Revealed with Solid-State NMR Spectroscopy

Hydrous materials are ubiquitous in the natural environment and efforts have previously been made to investigate the structures and dynamics of hydrated surfaces for their key roles in various chemical and physical applications, with the help of theoretical modeling and microscopy techniques. However, an overall atomic-scale understanding of the water–solid interface, including the effect of water on surface ions, is still lacking. Herein, we employ ceria nanorods with different amounts of water as an example and demonstrate a new approach to explore the water–surface interactions by using solid-state NMR in combination with density functional theory. NMR shifts and relaxation time analysis provide detailed information on the local structure of oxygen ions and the nature of water motion on the surface: the amount of molecularly adsorbed water decreases rapidly with increasing temperature (from room temperature to 150 °C), whereas hydroxyl groups are stable up to 150 °C, and dynamic water molecules are found to instantaneously coordinate to the surface oxygen ions. Additionally, the applicability of dynamic nuclear polarization for selective detection of surface oxygen species is also compared to conventional NMR with surface selective isotopic-labeling: the optimal method depends on the feasibility of enrichment and the concentration of protons in the sample. These results provide new insight into the interfacial structure of hydrated oxide nanostructures, which is important to improve performance for various applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Locally Confined Polysulfide-Reactive Electrolytes for Shuttle-Free Sodium–Sulfur Batteries

Sodium-sulfur batteries promise high-energy-density and sustainable electrochemical energy storage but suffer from uncontrolled polysulfides dissolution and high sodium reactivity. These challenges fundamentally originate from poor electrolyte-electrode compatibility. Current electrolyte research inadequately addresses the trade-off between minimal polysulfides solvation and stabilizing sodium interfaces. Here, we present a locally-confined polysulfide-reactive electrolyte strategy that mediates the polysulfide dissolution dynamics and sodium stability by leveraging an electrophilic solvating species with a localized high-concentration electrolyte. This design enables shuttle-free cell operation by synergistically restricting the global solvating power of the electrolyte through intermolecular interactions and locally scavenging sparingly dissolved polysulfides via electrolyte electrophilicity. The precisely confined surface reaction facilitates a protective cathode-electrolyte interface, realizing a quasi-solid-state sulfur conversion in our liquid ether-based electrolyte, which crucially avoids crossover-induced catastrophic sodium-metal degradation. The proposed electrolyte demonstrates long-term cycling of high-mass-loading sulfur cathodes (> 3 mg S cm −2 with commercial carbon host and 70 wt% sulfur content), which afford 710 mA h g −1 over 400 cycles in coin cells and steady pouch cell operation over 180 cycles. Furthermore, this work establishes a scalable electrolyte design protocol that regulates the reaction chemistry of highly reactive electrodes, offering a pathway toward sustainable renewable energy storage.

25 ENERGY STORAGE↗