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At least 649 records · Page 36

Lattice-Oxygen-Driven Selective Oxidation Strategy for Stable Argyrodite Solid-State Lithium Metal Batteries

All-solid-state lithium metal batteries (ASSLMBs) with Li6PS5Cl argyrodite electrolytes and high-voltage LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes offer high energy density but suffer from rapid capacity fading due to the layered-to-rock-salt transition of NMC811 and structural degradation of Li6PS5Cl from parasitic interfacial reactions. Here, we demonstrate a catholyte engineering strategy using a Li2S scavenging additive to suppress interfacial reactivity and preserve the structural and electrochemical stability of both NMC811 and Li6PS5Cl. Incorporating 0.10 wt.% Li2S enables exceptional cycling stability, achieving 76% capacity retention after 550 cycles at C/10 and 88% retention after 800 cycles at C/3 at 60 degrees C, compared with rapid failure in pristine cells. Spectroscopic, electrochemical, and morphological analyses confirm that Li2S maintains electrode integrity by sustaining particle contact and suppressing phase decomposition. This work elucidates interfacial degradation pathways in NMC811/argyrodite systems and introduces a low-cost, scalable strategy to stabilize nickel-rich oxide cathodes in ASSLMBs, advancing their practical viability.

25 ENERGY STORAGE↗

Synthesis of Cu-Fe{sub 3}O{sub 4}@graphene composite: A magnetically separable and efficient catalyst for the reduction of 4-nitrophenol

Highlights: • The Cu-Fe{sub 3}O{sub 4}@GE composite was prepared by one-step solvent–thermal method. • The Cu-Fe{sub 3}O{sub 4}@GE composite exhibited the highest catalytic activity with excellent stability. • The Cu-Fe{sub 3}O{sub 4}@GE composite was magnetically separable. - Abstract: In this work, the Cu-Fe{sub 3}O{sub 4}@GE composite was prepared easily by a one-step solvent–thermal method, which achieved the formation of Cu nanoparticles (Cu NPs), Fe{sub 3}O{sub 4} nanoparticles (Fe{sub 3}O{sub 4} NPs) and reduction of GO simultaneously. The morphology and structure of the composite was fully characterized by means of X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy, transmission electron microscopy (TEM). The time-dependent adsorption spectra of the reaction mixture was measured by UV–vis absorption spectroscopy. The results demonstrated that the Cu NPs and Fe{sub 3}O{sub 4} NPs were densely and evenly deposited on the graphene (GE) sheets. It was found that the Cu-Fe{sub 3}O{sub 4}@GE composite exhibited high catalytic activities on the reduction of p-nitrophenol to p-aminophenol. Furthermore, the composite catalyst can be easily recovered due to its magnetic separability and high stability.

36 MATERIALS SCIENCE↗

Structural and Magnetic Properties of Thermal- and Deformation-Induced Martensite in an Fe-27%Ni-4%Mn-1%Zn Alloy

Deformation- and thermal-induced martensite properties were examined according to existing martensite morphology and magnetic properties for same prior austenite homogenization conditions in Fe-27%Ni-4%Mn-1%Zn alloy. Scanning electron microscope (SEM) and vibrating sample magnetometer (VSM) characterization techniques were employed for the investigation. Scanning electron microscope observations showed that while martensite formation in the austenite phase of alloy exhibited a lath morphology by thermal effect, elongated deformation-induced martensite morphology exists after deformation. The Curie temperatures were detected at about 201 K for thermal-induced martensite and at about 226 K for deformation-induced martensite from VSM measurements. The magnetic saturation values were determined as about 21 emu g{sup −1} for thermal-induced martensite and 23 emu g{sup −1} for deformation-induced martensite. We found that magnetic saturation increased with deformation effect. On the other hand, VSM offered the soft ferromagnetic characteristic with coersive values of 36 Oe for thermal-induced martensite and the soft ferromagnetic characteristic with 47 Oe for deformation-induced martensite. The changes in the magnetic properties resulting from the thermal and deformation affect were clearly determined. Deformation caused magnetic stabilization in Fe-27%Ni-4%Mn-1%Zn alloy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Stability domain of alumina thermally grown on Fe–Cr–Al-based model alloys and modified surface layers exposed to oxygen-containing molten Pb

The paper gives experimental results concerning the morphology, composition, structure and thickness of the oxide scales grown on Fe–Cr–Al-based bulk alloys during exposure to oxygen-containing molten lead. The results are discussed and compared with former results obtained on Al-containing surface layers, modified by melting with intense pulsed electron beam and exposed to similar conditions. Here, the present and previous results provide the alumina stability domain and also the criterion of the Al/Cr ratio for the formation of a highly protective alumina layer on the surface of Fe–Cr–Al-based alloys and on modified surface layers exposed to molten lead with 10 –6 wt.% oxygen at 400–600 °C. The protective oxide scales, grown on alumina-forming Fe–Cr–Al alloys under the given experimental conditions, were transient aluminas, namely, kappa-Al 2 O 3 and theta-Al 2 O 3 .

14 SOLAR ENERGY↗

The effects of microstructural stability on the compressive response of two cast aluminum alloys up to 300 °C

Here in this study, the high temperature compressive response of cast aluminum alloys 319 and RR350 is compared in light of their microstructures. The 319 alloy is widely used in thermally critical automotive applications and provides a baseline for comparison with the RR350 alloy, whose microstructural stability at high homologous temperatures was recently reported. Cylindrical compression samples from each alloy were tested at four temperatures up to 300 °C at a constant true strain rate that was varied over four orders of magnitude. Although both alloys are strengthened by metastable precipitates (nominally Al 2 Cu) in the as-aged condition, their mechanical response diverges at temperatures greater than 250 °C as the strengthening precipitates evolve in the 319 alloy and retain their as-aged morphology in the RR350 alloy. Deformation mechanisms of each alloy are examined using microstructural analysis and empirical activation energy calculations. The stability of the θ' phase in the RR350 alloy leads to effective precipitation hardening at homologous temperatures up to 0.6 and an extensive regime of grain boundary controlled deformation.

36 MATERIALS SCIENCE↗

Synthesis of ZnO/Ag/graphene composite and its enhanced photocatalytic efficiency

Highlights: ► ZnO/Ag/graphene composite was synthesized via a facile aqueous reaction. ► ZnO/Ag composite nanoparticles are anchored on a two-dimensional graphene sheet. ► Enhanced photocatalytic efficiency was obtained compared to ZnO/Ag composite. ► The composite shows excellent stability after four photodegradation cycling runs. - Abstract: ZnO/Ag/graphene composite was synthesized via a facile low-temperature aqueous solution reaction. The morphology and crystal phase of the obtained samples were well characterized by SEM, TEM, and XRD. The results indicated that ZnO/Ag nanoparticles (NPs) are anchored on the two-dimensional graphene sheet. The photocatalytic trials confirmed that the ZnO/Ag/graphene composite exhibited improved photocatalytic efficiency compared with the ZnO/Ag NPs and pristine ZnO NPs. The increased photocatalytic activity of ZnO/Ag/graphene was attributed to the effective charge separation and the suppressed recombination of photogenerated electron–hole pairs. Moreover, the ZnO/Ag/graphene sample showed excellent stability after four photodegradation cycling runs.

36 MATERIALS SCIENCE↗

Experimental Studies of the Interaction Between a Parallel Shear Flow and a Directionally-Solidifying Front

It has long been recognized that flow in the melt can have a profound influence on the dynamics of a solidifying interface and hence the quality of the solid material. In particular, flow affects the heat and mass transfer, and causes spatial and temporal variations in the flow and melt composition. This results in a crystal with nonuniform physical properties. Flow can be generated by buoyancy, expansion or contraction upon phase change, and thermo-soluto capillary effects. In general, these flows can not be avoided and can have an adverse effect on the stability of the crystal structures. This motivates crystal growth experiments in a microgravity environment, where buoyancy-driven convection is significantly suppressed. However, transient accelerations (g-jitter) caused by the acceleration of the spacecraft can affect the melt, while convection generated from the effects other than buoyancy remain important. Rather than bemoan the presence of convection as a source of interfacial instability, Hurle in the 1960s suggested that flow in the melt, either forced or natural convection, might be used to stabilize the interface. Delves considered the imposition of both a parabolic velocity profile and a Blasius boundary layer flow over the interface. He concluded that fast stirring could stabilize the interface to perturbations whose wave vector is in the direction of the fluid velocity. Forth and Wheeler considered the effect of the asymptotic suction boundary layer profile. They showed that the effect of the shear flow was to generate travelling waves parallel to the flow with a speed proportional to the Reynolds number. There have been few quantitative, experimental works reporting on the coupling effect of fluid flow and morphological instabilities. Huang studied plane Couette flow over cells and dendrites. It was found that this flow could greatly enhance the planar stability and even induce the cell-planar transition. A rotating impeller was buried inside the sample cell, driven by an outside rotating magnet, in order to generate the flow. However, it appears that this was not a well-controlled flow and may also have been unsteady. In the present experimental study, we want to study how a forced parallel shear flow in a Hele-Shaw cell interacts with the directionally solidifying crystal interface. The comparison of experimental data show that the parallel shear flow in a Hele-Shaw cell has a strong stabilizing effect on the planar interface by damping the existing initial perturbations. The flow also shows a stabilizing effect on the cellular interface by slightly reducing the exponential growth rate of cells. The left-right symmetry of cells is broken by the flow with cells tilting toward the incoming flow direction. The tilting angle increases with the velocity ratio. The experimental results are explained through the parallel flow effect on lateral solute transport. The phenomenon of cells tilting against the flow is consistent with the numerical result of Dantzig and Chao.

Zhang, Meng↗

Exploration of the Effect of Chitosan and Crosslinking Agent Concentration on the Properties of Dual Responsive Chitosan-g-Poly (N-Isopropylacrylamide) Co-polymeric Particles

The objective of the present study was to synthesize and evaluate the effect of change in concentration of chitosan (CS) and N,N-methylenebisacrylamide (MBA)- a cross linking agent, on various properties such as lower critical solution temperature (LCST), zeta potential, particle size and poly dispersity index (PDI) of the synthesized co-polymer. Nine different formulations of chitosan-g-poly (N-isopropylacrylamide) (CS-g-PNIPAAm) co-polymer with varying CS and MBA concentrations were synthesized by a surfactant free dispersion copolymerization method. The synthesized co-polymer was further characterized and confirmed for its structure, morphology, particle size, zeta-potential, thermo and pH responsive properties, in-vitro cyto-compatability and stability studies using various analytical tools. The data confirms the successful synthesis of co-polymer. The increase in the concentrations of CS and MBA during the polymerization of co-polymer, resulted in proportional increase of LCST and zeta potential with decrease in particle size of co-polymeric nanoparticles. pH responsive studies showed that as the pH of the medium increases particle size and zeta potential decreases with increase in LCST of co-polymeric nanoparticles. From the results, it can be inferred that the synthesized co-polymeric nanoparticles exerted thermo and pH responsive properties with biocompatibility. By varying the CS and MBA concentrations in the co-polymer, desired LCST, particle size and zeta potential for co-polymeric nanoparticles can be obtained and thus the synthesized co-polymer may have great potential to be used as a drug carrier (nanoform) with both thermo and pH responsiveness.

36 MATERIALS SCIENCE↗

Highly permeable polyethersulfone substrates with bicontinuous structure for composite membranes in CO 2 /N 2 separation

Substrate morphology has a significant effect on the CO 2 transport performance of a thin-film composite (TFC) membrane. In this study, a new mixed solvent comprising 2-pyrrolidone (2-PD) and 2-methoxyethanol (2-ME) was used to prepare polyethersulfone (PES) substrates with bicontinuous structure by water vapor-induced phase separation, followed by immersion in water as nonsolvent. Here, compared with the commonly used solvent, N-methyl-2-pyrrolidone (NMP), the 2-PD/2-ME mixed solvent is more hydrophilic and can decrease the thermodynamic stability of the casting solution significantly. As a result, the phase separation was induced via the spinodal decomposition mechanism. The open morphology bestowed the optimized substrate with a very high CO 2 permeance of 133,226 ± 3,870 GPU (1 GPU = 10 –6 cm 3 (STP) s –1 cm –2 cmHg –1 = 3.3464 × 10 -9 kg-mol s –1 m –2 Pa –1 ), which was 5 times more permeable than the baseline substrate synthesized with NMP. By using this new substrate, the prepared TFC membrane containing amines showed an increased CO 2 permeance of 908 ± 8 GPU at 57°C, which was 48 GPU higher than that with the baseline substrate. Meanwhile, the CO 2 /N 2 selectivity was retained at 162 ± 4 at 57°C. In addition, the good scalability of the new PES substrate was demonstrated by roll-to-roll fabrication of a 50' long scale-up PES substrate with a width of 21".

2-Pyrrolidone↗

Acid Etching‐Driven Self‐Assembly of Mn‐Shell Inducing Rock‐Salt Phase for Enhanced Single‐Crystal Ni‐Rich Cathodes

With the wide adoption of Li‐ion batteries, Ni‐rich cathode is considered as one of the most promising candidates of cathodes due to its high energy density and low cost. However, stability decreased with increasing Ni content in the Ni‐rich cathode. To solve this bottleneck, many strategies, such as coating, doping, surface modification, and special morphologies, have been developed. Herein, we introduce a groundbreaking approach for enhancing Ni‐rich cathode through an innovative acid etching process that promotes Mn shell self‐assembly, inducing a rock‐salt phase on the surface. This method not only simplifies the Ni‐rich cathode modification process, but also significantly improves the structural stability and electrochemical performance of Ni‐rich cathode. Our findings demonstrate that developed single‐crystal Ni‐rich cathode shows 3–34 % better stability compared to both commercial modified Ni‐rich cathode and unmodified counterparts. The unique Mn shell effectively mitigates reversible phase shifts during cycling, contributing to a remarkable enhancement in cycling stability. Additionally, this novel fabrication technique paves the way for cost‐effective production of high‐performance cathode materials, offering substantial benefits for lithium‐ion battery technology. And this study proves the potential of this method in advancing the design and development of durable, high‐capacity cathode materials for next‐generation batteries.

Ni-rich cathode↗

Synthesis of titania wrapped cadmium sulfide nanorods for photocatalytic hydrogen generation

Highlights: • TiO{sub 2}@CdS nanorods with core/shell morphology prepared by simple hydrothermal method. • TiO{sub 2} shell thickness optimized for enhanced photocatalytic activity. • Initial concentration of sacrificial agent and solution pH were optimized for H{sub 2} generation. • Optimized photocatalyst C{sub 3}T{sub 3} displayed stable and continuous H{sub 2} evolution for 20 h. • Optimised catalyst showed 12-folds efficient H{sub 2} production under UV–vis vs visible light. - Abstract: Herein we report a simplified synthetic approach for a semiconductor photocatalyst (CdS) wrapped with a nanoscale thin-layer of semiconducting material (TiO{sub 2}) to overcome the instability issues, besides the improved catalytic efficiency. Images of HR-TEM and elemental mapping evidenced the presence of CdS that covered by ultra thin-layer of TiO{sub 2} as shell. The UV–vis diffuse reflectance spectra showed red-shift in absorption edge in visible region. The photocatalytic water splitting towards hydrogen production using Na{sub 2}S/Na{sub 2}SO{sub 4} as sacrificial agent was evaluated under UV–vis and visible light irradiation. The essential variables such as thickness of TiO{sub 2} shell, amount of sacrificial agent and solution pH were fine tuned to achieve hydrogen generation of 5791 mL h{sup −1} g{sup −1} of catalyst. The higher efficiency is ascribed to core/shell morphology of CdS/TiO{sub 2} system that channelled the excitons to the surface for the red-ox reactions rather than recombination. The catalytic stability result ascertained that the photo-corrosion is greatly suppressed.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Syntheses of Colloidal F:In 2 O 3 Cubes: Fluorine-Induced Faceting and Infrared Plasmonic Response

Cube-shaped nanocrystals (NCs) of conventional metals like gold and silver generally exhibit localized surface plasmon resonance (LSPR) in the visible region with spectral modes determined by their faceted shapes. Yet, faceted NCs exhibiting LSPR response in the infrared (IR) region are relatively rare. Here, we describe the colloidal synthesis of nanoscale fluorine-doped indium oxide (F:In 2 O 3 ) cubes with LSPR response in the IR region, wherein fluorine was discovered to both direct the cubic morphology and act as an aliovalent dopant. Single-crystalline 160 nm F:In 2 O 3 cubes terminated by (100) facets and concave cubes were synthesized using a colloidal heat-up method. The presence of fluorine was found to impart higher stabilization to the (100) facets through density functional theory calculations that evaluated the energetics of F-substitution at surface oxygen sites. These calculations suggest that the cubic morphology results from surface binding of F atoms. In addition, fluorine acts as an anionic aliovalent dopant in the cubic bixbyite lattice of In 2 O 3 , introducing a high concentration of free electrons leading to LSPR. We confirmed the presence of lattice fluorine dopants in these cubes using solid-state 19 F and 115 In nuclear magnetic resonance spectroscopy. The cubes exhibit narrow, shape-dependent multimodal LSPR extinction peaks due to corner- and edge-centered modes. The spatial origin of these different contributions to the spectral response is directly visualized by electron energy loss spectroscopy in a scanning transmission electron microscope.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mining experimental magnetized liner inertial fusion data: Trends in stagnation morphology

In magnetized liner inertial fusion (MagLIF), a cylindrical liner filled with fusion fuel is imploded with the goal of producing a one-dimensional plasma column at thermonuclear conditions. However, structures attributed to three-dimensional effects are observed in self-emission x-ray images. Despite this, the impact of many experimental inputs on the column morphology has not been characterized. We demonstrate the use of a linear regression analysis to explore correlations between morphology and a wide variety of experimental inputs across 57 MagLIF experiments. Results indicate the possibility of several unexplored effects. For example, we demonstrate that increasing the initial magnetic field correlates with improved stability. Although intuitively expected, this has never been quantitatively assessed in integrated MagLIF experiments. We also demonstrate that azimuthal drive asymmetries resulting from the geometry of the “current return can” appear to measurably impact the morphology. In conjunction with several counterintuitive null results, we expect the observed correlations will encourage further experimental, theoretical, and simulation-based studies. Finally, we note that the method used in this work is general and may be applied to explore not only correlations between input conditions and morphology but also with other experimentally measured quantities.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Crystal Orientation-Dependent Reactivity of Oxide Surfaces in Contact with Lithium Metal

Understanding ionic transport across interfaces between dissimilar materials and the intrinsic chemical stability of such interfaces is a fundamental challenge spanning many disciplines and is of particular importance for designing conductive and stable solid electrolytes for solid-state Li-ion batteries. In this work, we establish a surface science-based approach for assessing the intrinsic stability of oxide materials in contact with Li metal. Through a combination of experimental and computational insights, using Nb-doped SrTiO3 (Nb/STO) single crystals as a model system, we were able to understand the impact of crystallographic orientation and surface morphology on the extent of the chemical reactions that take place between surface Nb, Ti, and Sr upon reaction with Li. By expanding our approach to investigate the intrinsic stability of the technologically relevant, polycrystalline Nb-doped lithium lanthanum zirconium oxide (Li6.5La3Zr1.5Nb0.5O12) system, we found that this material reacts with Li metal through the reduction of Nb, similar to that observed for Nb/STO. These results clearly demonstrate the feasibility of our approach to assess the intrinsic (in)stability of oxide materials for solid-state batteries and point to new strategies for understanding the performance of such systems.

36 MATERIALS SCIENCE↗

Programmable Site‐Specific Functionalization of DNA Origami with Polynucleotide Brushes

Abstract Combining surface‐initiated, TdT (terminal deoxynucleotidyl transferase) catalyzed enzymatic polymerization (SI‐TcEP) with precisely engineered DNA origami nanostructures (DONs) presents an innovative pathway for the generation of stable, polynucleotide brush‐functionalized DNA nanostructures. We demonstrate that SI‐TcEP can site‐specifically pattern DONs with brushes containing both natural and non‐natural nucleotides. The brush functionalization can be precisely controlled in terms of the location of initiation sites on the origami core and the brush height and composition. Coarse‐grained simulations predict the conformation of the brush‐functionalized DONs that agree well with the experimentally observed morphologies. We find that polynucleotide brush‐functionalization increases the nuclease resistance of DONs significantly, and that this stability can be spatially programmed through the site‐specific growth of polynucleotide brushes. The ability to site‐specifically decorate DONs with brushes of natural and non‐natural nucleotides provides access to a large range of functionalized DON architectures that would allow for further supramolecular assembly, and for potential applications in smart nanoscale delivery systems.

Yang, Yunqi↗

Binary Atomically Dispersed Metal-Site Catalysts with Core–Shell Nanostructures for O 2 and CO 2 Reduction Reactions

Engineering atomically dispersed metal site catalysts with controlled local coordination environments and 3D nanostructures effectively improves the catalytic performance for the oxygen reduction reaction (ORR) and the carbon dioxide reduction reaction (CO 2 RR), which are critical for clean energy conversion and chemical production. Herein, an innovative approach for preparing core-shell nanostructured catalysts with different single-metal sites in the core and the shell, respectively, is developed. In particular, as the shell precursors, covalent organic polymers with a thin layered structure that is polymerized in situ and coated on a metal-doped ZIF-derived carbon core are used, followed by a controlled thermal activation. The selective combination and construction of different metal sites increase active site density in the surface layers, promote structural robustness, facilitate mass/charge transfer, and yield a possible synergy of active sites in the core and the shell. The p-FeNC(shell)@CoNC(core), consisting of a polymerized FeTPPCl-derived carbon layer (p-FeNC) on a Co-doped ZIF-derived carbon (CoNC), exhibits remarkable ORR activity and stability in acidic media along with encouraging durability in H 2 –air fuel cells. Likewise, a p-FeNC(shell)@NiNC(core) catalyst demonstrates outstanding CO 2 RR activity and stability. Hence, integrating two appropriate single-metal sites in core and shell precursors, respectively, can modulate morphological and catalytic properties for a possible synergy toward different electrocatalysis processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Annatto-colored Poly(3-hydroxybutyrate): A Comprehensive Study on Photodegradation

Annatto natural colorant was extracted from annatto seeds (Bixa Orellana L.) by using ultrasound. Structural characterization of the extract was done by FTIR. The aim of the present work was the developement and characterization of biodegradable colored films based on poly(3-hydroxybutyrate) by using annatto colorant. The annatto content in the films was varied from 0.2 to 3.0% (w/w). The lightfastness of colored films when exposed to UVA radiation was controlled by using RGB color system. In color image processing, a pixel is often defined by three values corresponding to the tristimuli R (Red), G (Green) and B (Blue). With the addition of the annatto colorant, photodegradation of films under UVA exposure seemed to be improved. The good thermal stability of the colored film with 3.0% (w/w) of annatto colorant was confirmed by thermogravimetric analysis. Surface morphology of the colored film with 3.0% (w/w) of annatto colorant was examined by SEM prior and after 240 h of UVA exposure. The SEM micrographs suggested that annatto colorant has acted as hiding agent, reducing the photodegradation processes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Multiscale Electrochemomechanics Interaction and Degradation Analytics of Sn Electrodes for Sodium-Ion Batteries

Sodium-ion batteries have emerged as a strong contender among the beyond lithium-ion chemistries due to elemental abundance and the low cost of sodium. Tin (Sn) is a promising alloying electrode with high capacity, redox reversibility, and earth abundance. Tin electrodes, however, undergo a series of intermediate reactions exhibiting multiple voltage plateaus upon sodiation/desodiation. Phase transformations related to incomplete sodiation in tin during cycling, in the presence of a frail solid electrolyte interphase layer, can quickly weaken the structural stability. The structural dynamics and reactivity of the electrode/electrolyte interface, being further dependent on the size and morphology of the active material particle in the presence of different electrolytes, dictate the electrode degradation and survivability during cycling. Here, we paint a comprehensive picture of the underpinnings of the electrochemical and mechanics coupling and electrode/electrolyte interfacial interactions in alloying Sn electrodes. We elicit the fundamental role of electrode/electrolyte complexations in the Sn electrode structure-property-performance relationship based on multimodal analytics, including electrochemical, microscopy, and tomography analyses.

25 ENERGY STORAGE↗