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At least 667 records · Page 37

Observation and Analysis of In Situ Carbonaceous Matter in Naklha

The search for indigenous carbon components on Mars has been a challenge. The first attempt was the Viking GC-MS in situ experiment which gave inconclusive results at two sites on Mars [1]. After the discovery that the SNC meteorites were from Mars [2], [3-5] reported C isotopic compositional information which suggested a reduced C component present in the martian meteorites. [6 & 7] reported the presence of reduced C components (i.e., polycyclic aromatic hydrocarbons) associated with the carbonate globules in ALH84001. Jull et al. [8] noted in Nakhla there was an acid insoluble C component present with more than 75% of its C lacking any C-14, which is modern-day carbon. This C fraction was believed to be either indigenous martian or ancient meteoritic carbon. Fisk et al. [9, 10] have shown textural evidence along with C-enriched areas within fractures in Nakhla and ALH84001. To further understand the nature of possible indigenous reduced C components, we have carried out a variety of measurements on martian meteorites. For this presentation we will discuss only the Nakhla results. Interior samples from the Nakhla SNC meteorite, recently made available by the British Museum of Natural History, were analyzed. Petrographic examination [11, McKay et al., this volume] of Nakhla showed evidence of fractures (approx.0.5 micron wide) filled with dark brown to black dendritic material [Fig. 1] with characteristics similar to those observed by [10]. Iddingsite is also present along fractures in olivine. Fracture filling and dendritic material was examined by SEM-EDX, TEM-EDX, Focused Electron Beam microscopy, Laser Raman Spectroscopy, Nano-SIMS Ion Micro-probe, and Stepped-Combustion Static Mass Spectrometry.

Gibson, E. K., Jr.↗

Dynamic Mechanical Properties and Fracture Surface Morphologies of Core-Shell Rubber (CSR) Toughened Epoxy at Liquid Nitrogen (Ln2) Temperatures

The dynamic mechanical properties and fracture surface morphologies were evaluated for a commercial epoxy resin toughened with two types of core-shell rubber (CSR) toughening agents (Kane Ace(Registered TradeMark) MX130 and MX960). The impact resistance (R) was evaluated by the resulting breaking energy measured in Charpy impact tests conducted on an instrumented drop tower. The resulting fracture surface morphologies were examined using Scanning Electron Microscopy (SEM). Fractographic observations of the CSR toughened epoxy tested at ambient temperature, showed a fracture as characterized by slender dendrite textures with large voids. The increasing number of dendrites and decreasing size of scale-like texture with more CSR particles corresponded with increased R. As the temperature decreased to Liquid Nitrogen (LN 2), the fracture surfaces showed a fracture characterized by a rough, torn texture containing many river markings and deep furrows.

Wang, J.↗

Organic Carbon Exists in Mars Meteorites: Where is it on the Martian Surface?

The search for organic carbon on Mars has been a major challenge. The first attempt was the Viking GC-MS in situ experiment which gave inconclusive results at two sites oil. After the discovery that the SNC meteorites were from Mars, reported C isotopic compositional information which suggested a reduced C component present in the Martian meteorites reported the presence of reduced C components (i.e., polycyclic aromatic hydrocarbons) associated with the carbonate globules in ALH84001. Jull et al. noted in Nakhla there was acid insoluble C component present with more than 75% of its C lacking any C-14, which is modern-day terrestrial carbon. This C fraction was believed to be either indigenous martian or ancient meteoritic carbon. Fisk et al. have shown textural evidence along with C-enriched areas within fractures in Nakhla and ALH84001. Westall et al. have shown the presence of a large irregular fragment of organic material completely embedded within a chip of ALH84001. Interior samples from the Naklnla SNC made available by the British Museum of Natural History, were analyzed. Petrographic examination of Nakhla showed evidence of fractures (approx.0.5 microns wide) filled with dark brown to black dendritic material with characteristics similar to those observed by. Iddingsite is also present along fractures in olivine. Fracture filling and dendritic material was examined by SEM-EDX, TEM-EDX, Focused Electron Beam microscopy, Laser Raman Spectroscopy, Nano-SIMS Ion Micro-probe, and Stepped-Combustion Static Mass Spectrometry. Observations from the first three techniques are discussed.

McKay, D. S.↗

Evaluation of Model Microphysics Within Precipitation Bands of Extratropical Cyclones

Recent studies evaluating the bulk microphysical schemes (BMPs) within cloud resolving models (CRMs) have indicated large uncertainties and errors in the amount and size distributions of snow and cloud ice aloft. The snow prediction is sensitive to the snow densities, habits, and degree of riming within the BMPs. Improving these BMPs is a crucial step toward improving both weather forecasting and climate predictions. Several microphysical schemes in the Weather Research and Forecasting (WRF) model down to 1.33‐km grid spacing are evaluated using aircraft, radar, and ground in situ data from the Global Precipitation Mission Coldseason Precipitation Experiment (GCPEx) experiment, as well as a few years (15 winter storms) of surface measurements of riming, crystal habit, snow density, and radar measurements at Stony Brook, NY (SBNY on north shore of Long Island) during the 2009-2012 winter seasons. Surface microphysical measurements at SBNY were taken every 15 to 30 minutes using a stereo microscope and camera, and snow depth and snow density were also recorded. During these storms, a vertically-pointing Ku-band radar was used to observe the vertical evolution of reflectivity and Doppler vertical velocities. A Particle Size and Velocity (PARSIVEL) disdrometer was also used to measure the surface size distribution and fall speeds of snow at SBNY. For the 15 cases at SBNY, the WSM6, Morrison (MORR), Thompson (THOM2), and Stony Brook (SBU-YLIN) BMPs were validated. A non-spherical snow assumption (THOM2 and SBU-YLIN) simulated a more realistic distribution of reflectivity than spherical snow assumptions in the WSM6 and MORR schemes. The MORR, WSM6, and SBU-YLIN schemes are comparable to the observed velocity distribution in light and moderate riming periods. The THOM2 is ~0.25 meters per second too slow with its velocity distribution in these periods. In heavier riming, the vertical Doppler velocities in the WSM6, THOM2, and MORR schemes were ~0.25 meters per second too slow, while the SBU-YLIN was 0.25 to 0.5 meters per second too fast. Overall, the BMPs simulate a size distribution close to the observed for D < 4 mm in the dendritic, plates, and mixed habit periods. The model BMPs underestimate the size distribution when large aggregates were observed. For D > 6 mm in the dendrites, side planes, and mixed habit periods, the BMPs are likely not simulating enough aggregation to create a larger size distribution, although the MORR (double moment) scheme seemed to perform best. These SBNY results will be compared with some results from GCPEx for a warm frontal snow band observed at 18 February 2012.

Colle, Brian A.↗

Evaluation of Model Microphysics within Precipitation Bands of Extratropical Cyclones

Recent studies evaluating the bulk microphysical schemes (BMPs) within cloud resolving models (CRMs) have indicated large uncertainties and errors in the amount and size distributions of snow and cloud ice aloft. The snow prediction is sensitive to the snow densities, habits, and degree of riming within the BMPs. Improving these BMPs is a crucial step toward improving both weather forecasting and climate predictions. Several microphysical schemes in the Weather Research and Forecasting (WRF) model down to 1.33‐km grid spacing are evaluated using aircraft, radar, and ground in situ data from the Global Precipitation Mission Coldseason Precipitation Experiment (GCPEx) experiment, as well as a few years (15 winter storms) of surface measurements of riming, crystal habit, snow density, and radar measurements at Stony Brook, NY (SBNY on north shore of Long Island) during the 2009-2012 winter seasons. Surface microphysical measurements at SBNY were taken every 15 to 30 minutes using a stereo microscope and camera, and snow depth and snow density were also recorded. During these storms, a vertically-pointing Ku-band radar was used to observe the vertical evolution of reflectivity and Doppler vertical velocities. A Particle Size and Velocity (PARSIVEL) disdrometer was also used to measure the surface size distribution and fall speeds of snow at SBNY. For the 15 cases at SBNY, the WSM6, Morrison (MORR), Thompson (THOM2), and Stony Brook (SBU-YLIN) BMPs were validated. A non-spherical snow assumption (THOM2 and SBU-YLIN) simulated a more realistic distribution of reflectivity than spherical snow assumptions in the WSM6 and MORR schemes. The MORR, WSM6, and SBU-YLIN schemes are comparable to the observed velocity distribution in light and moderate riming periods. The THOM2 is approx 0.25 m/s too slow with its velocity distribution in these periods. In heavier riming, the vertical Doppler velocities in the WSM6, THOM2, and MORR schemes were approx 0.25 m/s too slow, while the SBU-YLIN was 0.25 to 0.5 m/s too fast. Overall, the BMPs simulate a size distribution close to the observed for D < 4 mm in the dendritic, plates, and mixed habit periods. The model BMPs underestimate the size distribution when large aggregates were observed. For D > 6 mm in the dendrites, side planes, and mixed habit periods, the BMPs are likely not simulating enough aggregation to create a larger size distribution, although the MORR (double moment) scheme seemed to perform best. These SBNY results will be compared with some results from GCPEx for a warm frontal snow band observed at 18 February 2012.

Colle, Brian A.↗

A New Type of Foreign Clast in A Polymict Ureilite: A CAI or AL-Rich Chondrule

Introduction: Polymict ureilites are breccias interpreted to represent regolith formed on a ureilitic asteroid [1-3]. They consist of approximately 90-95% clasts of various ureilite types (olivine-pyroxene rocks with Fo 75-95), a few % indigenous feldspathic clasts, and a few % foreign clasts [4-20]. The foreign clasts are diverse, including fragments of H, L, LL and R chondrites, angrites, other achondrites, and dark clasts similar to CC [6,7,9-19]. We report a new type of foreign clast in polymict ureilite DaG 999. Methods: Clast 8 in Dar al Gani (DaG) 999/1 (Museum fur Naturkunde) was discovered during a survey of feldspathic clasts in polymict ureilites [19,20]. It was studied by BEI, EMPA, and X-ray mapping on the JEOL 8530F electron microprobe at ARES, JSC. Petrography and Mineral Compositions: Clast 8 is sub-rounded to irregular in shape, approximately 85 micrometers in diameter, and consists of approximately 68% pyroxene and 32% mesostasis (by area). Part of the pyroxene (top half of clast in Fig. 1a and 2) shows a coarse dendritic morphology; the rest appears massive. Mesostasis may be glassy and contains fine needles/grains of pyroxene. The pyroxene has very high CaO (23.5 wt.%) and Al2O3 (19.7 wt.%), with the formula: (Ca(0.91)Mg(0.63)Fe(0.01)Al(sup VI) (0.38)Cr(0.01)Ti(0.05)1.99 Si2O6. The bulk mesostasis also has very high Al2O3 (approximately 26 wt.%). A bulk composition for the clast was obtained by combining modal abundances with phase compositions (Table 1, Fig. 3). Discussion: The pyroxene in clast 8 has a Ca-Al-(Ti)- rich (fassaitic) composition that is clearly distinct from compositions of pyroxenes in main group ureilites [22] or indigenous feldspathic clasts in polymict ureilites [4-8]. It also has significantly higher Al than fassaite in angrites (up to approximately 12 wt.% [23]), which occur as xenoliths in polymict ureilites. Ca-Al-Ti rich pyroxenes are most commonly found in CAIs, Al-rich chondrules and other types of refractory inclusions in chondrites [21,24-31]. However, the clast 8 pyroxene matches only the most Al-Ca-rich of these, e.g., pyroxenes in type B CAIs in CV3 chondrites [25,30,31], a pyroxene-hibonite spherule and a pyroxene-anorthitespinel fragment from unique CC Acfer 094 [29], and one Al-rich chondrule from Chainpur (LL3.4) [21]. The mineralogy of clast 8 is not consistent with the mineral assemblages of any of these objects (since it lacks hibonite, spinel and/or anorthite), which suggests that it is unrepresentatively sectioned or is a fragment of a more mineralogically diverse object. Its bulk composition (Table 1; Fig. 3) is similar to bulk compositions of some Al-rich chondrules, as well as those of Type C CAIs (which plot in the sp+An+L field in Fig. 3), although it is enriched in silica relative to type C CAIs [e.g., 31]. This suggests a more likely affinity to Al-rich chondrules, although most Al-rich chondrules have less Al-Ca-rich pyroxene [21,26,27]. These bulk compositional comparisons may not be definitive, however, if the clast is unrepresentatively sampled. One of eleven Al-rich chondrules from UOCs described by [21] has textural and compositional characteristics that make it a possible progenitor type for clast 8. This chondrule (Chainpur 1251-14-2) is anorthiteporphyritic, with an interstitial dendritic intergrowth of pyroxene (similar in composition to that in clast 8) and plagioclase [21]. Clast 8 is conceivably a fragment from the interstitial area of such an object. The occurrence of glassy mesostasis (in clast 8) rather than plagioclase may not be a significant difference; it could result from a difference only in cooling rate. Al-rich chondrules with glassy mesostasis are rare, and known occurrences are Ca-poor [26], unlike clast 8. Polymict ureilites are known to contain xenoliths of various chondrites (including OC, R and CC) as well as individual ferromagnesian and silica-pyroxene chondrules probably derived from OC or RC [6,9,15,16,18]. This is the first report of an individual chondritic refractory inclusion as a xenolith in a polymict ureilite. An RC-like sample from anomalous polymict ureilite Almahata Sitta contains CAIs, but they are spinel-rich and not similar to clast 8 [13,14]. Further studies of this clast (which, unfortunately, may not be possible), or the discovery of additional (more representative?) materials of this type would be needed to determine the exact nature of this xenolith and the type of chondrite from which it is derived.

Goodrich, C. A.↗

Solidification and Morphological Evolution of Al-Si Eutectics in Convector-Diffusive Conditions

The Al-Si material system is an important and has been studied for over half century with a focus on industrial applications in high strength and high conductivity alloys. A great deal of researches have been focused on controlling the morphology and hence performance through the addition of small impurities and by processing conditions. Most of the structure-property correlations are based on the post solidified micromorphology and growth conditions. This material system is unique and has been explored for heat spreader, controlling coefficient of expansion by adjusting composition of silicon and in designing composites. The Al-Si system is very interesting system for understanding the dendritic (Al-rich side) eutectic transition. Recently this system has been of great interest because of its applications in designing heat spreader, low temperature flux to grow SiC large substrates and in controlling the coefficient of expansion of Al-based alloys. We have performed extensive experiments to understand eutectic transition and to understand the morphological evolution in presence of impurities. We will discuss the results of dendritic transition into faceted long grains in convector-diffusive conditions. In this presentation we will present morphological transition in presence of carbon impurity and development of novel morphology.

Singh, N. B.↗

Development of Large Bandgap Materials Using Reactive Growth in Al-SI Eutectic for Optical and RF Applications

Carbon was utilized as reactive element to modify the microstructure using forced mixing during crystallization of the Al-Si alloy by rotation and stirring. We nucleated the material on SiC substrates while the Al-Si melt was rotated with a speed of 30rpm in a graphite crucible. Several experiments were performed and parameters such as time of mixing, soaking temperature, rotation rate of the substrate and rate of cooling during the solidification was changed. We observed dendrite and cell morphologies during the solidification of rotating melt. The microstructure was characterized by optical microscopy and SEM-EDX and compositional spectroscopy. The effect of carbon impurities was studied on the solidifying microstructure. When we used the longer soak time of the melt in presence of carbon impurities we observed the destruction of dendritic morphology and the formation of cellular and colony structures. Similar approach has been used for Ga2O3, a novel large bandgap material also.

Singh, N. B.↗

Three-dimensional in Situ Observations of Polycrystalline Microstructure Evolution During Directional Solidification of Transparent Alloys Aboard the ISS and Quantitative Comparison with Numerical Modeling

Cellular/dendritic microstructures formed during solidification have a crucial influence on the mechanical properties of a wide range of structural alloys. By minimizing the amount of gravity-induced convection in the liquid, directional solidification experiments using transparent organic alloys conducted in the DECLIC-DSI onboard the International Space Station have provided unique 3D in situ observations of the spatiotemporal evolution of the solid-liquid interface during the formation of cellular and dendritic microstructures under purely diffusive growth conditions in polycrystalline samples containing several grains with a small misorientation with respect to the temperature gradient. Those observations have made it possible to perform benchmark quantitative comparisons with the predictions of state-of-the-art phase-field simulations of microstructure formation in 3D on experimentally relevant length and time scales. This talk will report quantitative comparisons between microgravity experiments and phase-field simulations in succinonitrile-camphor alloys of two different compositions that shed new light on the role of subgrain boundaries in the spatiotemporal evolution of the primary cellular spacing and the selection of dendritic array structures.

Kaihua Ji↗

Preparation of Thick NI/AL Reactive Multilayer Films and Prospective Use for Self-Powered Brazing of TI-6AL-4V

In this study we demonstrate a new method for depositing thick reactive multilayer films (RMFs) (thickness > 14 µm) by using Ti interlayer integration and substrate preheating during fabrication. These two adjustments are designed to alleviate internal planar stresses that cause delamination between deposited layers and peeling off the substrate. Decreasing the distance between Ti interlayers helps to eliminate delamination between deposited layers. Through high speed camera measurements, the reaction propagation speed of an RMF sample with preheating is 42% slower than the same RMF that was not preheated, indicating a slower heat release rate. The preliminary experiments on brazing Ti-6Al-4V coated with BAlSi-4 brazing material revealed dendritic structure branching out from the RMF surface into the brazing material. The dendrite structures most likely form because of rapid melting and solidification of the brazing material. However, this rapid melting and solidification cycle does not appear to occur uniformly across the BAlSi-4RMF interface which is linked to its low bonding strength. When the Ti-6Al-4V substrate is heated to 150 °C prior to ignition, the strength increases to 0.47 MPa when the total RMF thickness is 84 µm and 15 MPa of pressure is applied.

Cheng, Jinquan↗

Three-Dimensional In Situ Observations of Polycrystalline Microstructure Evolution During Directional Solidification of Transparent Alloys Aboard the ISS and Quantitative Comparison with Numerical Modeling

Cellular/dendritic microstructures formed during solidification have a crucial influence on the mechanical properties of a wide range of structural alloys. By minimizing the amount of gravity-induced convection in the liquid, directional solidification experiments using transparent organic alloys conducted in the DECLIC-DSI onboard the International Space Station have provided unique 3D in situ observations of the spatiotemporal evolution of the solid-liquid interface during the formation of cellular and dendritic microstructures under purely diffusive growth conditions. Those observations have made it possible to perform benchmark quantitative comparisons with the predictions of state-of-the-art phase-field simulations of microstructure formation in 3D on experimentally relevant length and time scales. This talk will report quantitative comparisons between microgravity experiments and phase-field simulations in succinonitrile-camphor alloys of two different compositions, which shed new light on the selection of dendritic array structures, and on roles of macroscopic curvatures and subgrain boundaries between grains with a small misorientation with respect to the temperature gradient in the spatiotemporal evolution of the primary cellular spacing.

Kaihua Ji↗

Finite Element Simulation of the Direct Energy Deposition using Comsol Multiphysics

Direct Energy Deposition (DED) is an emerging technology extensively employed in metal Additive Manufacturing (AM). Despite its widespread industrial application, mathematical modeling in this domain remains challenging. This complexity arises from the intricate nature of the modeling approach and the nonlinear behavior of material parameters across a broad temperature range. Consequently, experimentalists often resort to a trial-and-error method to achieve structures with desired properties. However, this approach can be time-consuming and may not always yield parts with the requisite characteristics, highlighting the necessity for mathematical modeling to enhance manufacturing success. This study focuses on thin-walled manufacturing with a single bead thickness, adjusting laser parameters to produce such structures. The laser cladding speed, typical for DED manufacturing, is considered to be on the order of centimeters per second. The various wall thicknesses and heights are explored to discern the general characteristics of walls manufactured via this DED approach. Our modeling approach diverges from the conventional DED modeling based on activation-deactivation of predefined mesh domains, commonly implemented in many finite element codes. Instead, a method is proposed that effectively models layer cladding and melt pool dynamics, enabling predictions of the microstructure in the resulting structures. The formation mechanisms of cellular, dendritic columnar, and stray (equiaxed) grains, which arise from the interplay between nucleation and growth from the surface is analyzed. The study also examines the feasibility of microstructure formation to demonstrate the various thermal characteristics inherent in wall manufacturing. Our results illustrate how different process parameters influence the temperature gradient and cooling rate of the molten pool, subsequently affecting the primary dendrite arm spacing (PDAS). This modeling technique allows for the investigation of diverse thermal conditions, facilitating the prediction of microstructure and residual stresses in the manufactured parts.

modeling↗

The Effect of Artificial SEIs on Lithium Metal Anode Morphology and Conductivity

Lithium metal has often been termed the “holy grail” of battery technology, due to its high capacity (2,061 mAh/cm3) and low electrochemical potential (-3.04 V vs. SHE). However, lithium’s beneficially low potential also causes it to be highly reactive in the presence of organic solvents, making it difficult to harness the high energy capabilities for rechargeable batteries. Common failure of lithium metal batteries occurs by rapid dendrite growth leading to a hazardous short-circuit. Various methods have been brought forth to better understand the fundamental mechanisms of lithium metal batteries, as well as modifications made to better stabilize lithium metal. A common route of modification is done through interface engineering, with attempts to artificially provide a stable, homogeneous solid-electrolyte interface (SEI). The stability of the SEI has direct effects on the heterogeneity of the electrode surface, which initiates a waterfall effect of for progressive reactions such as dendrite growth, dead lithium accumulation, and electrolyte consumption. This work aims to produce a mixed LiI-LiF artificial SEI to improve ionic conductivity while retaining a high elastic modulus.

25 ENERGY STORAGE↗

Effects of Size on Characteristics of Electroslag Remelted (ESR) HAYNES®282® alloy ingots

The effects of varying ingot diameters on the characteristics of round ESR ingots of 282 alloy are evaluated through a combined experimental and modeling study. Ingots of four different diameters --100 mm, 150 mm, 200 mm and 500 mm, were sectioned and analyzed using metallography to assess spatial variations in dendritic structure (primary / secondary dendrite arm spacings – PDAS/SDAS) across these ingots. Melt parameters of the processes were input into the simulation code, MeltFlow-ESR™ to theoretically predict PDAS/SDAS in the ingots. The values for PDAS/SDAS predicted by the simulations are compared with those measured by experiments and quantitative differences in these values are discussed in the context of the capability and limitations of the model and measurement methods. Both the predicted and measured values show that the PDAS/SDAS values increase with increasing ingot size. In addition, the relation with other ingot characteristics, such as local solidification time as well as the likelihood for freckle formation are discussed. The implication of these results for down-stream ingot processing and for ingot soundness are discussed.

Krishnamurthy, Ramanathan↗

A Self-Healing, Flowable, Yet Solid Electrolyte Suppresses Li-Metal Morphological Instabilities

In this article, lithium metal (Li 0 ) solid-state batteries encounter implementation challenges due to dendrite formation, side reactions, and movement of the electrode–electrolyte interface in cycling. Notably, voids and cracks formed during battery fabrication/operation are hot spots for failure. Here, a self-healing, flowable yet solid electrolyte composed of mobile ceramic crystals embedded in a reconfigurable polymer network is reported. This electrolyte can auto-repair voids and cracks through a two-step self-healing process that occurs at a fast rate of 5.6 µm h -1 . A dynamical phase diagram is generated, showing the material can switch between liquid and solid forms in response to external strain rates. The flowability of the electrolyte allows it to accommodate the electrode volume change during Li 0 stripping. Simultaneously, the electrolyte maintains a solid form with high tensile strength (0.28 MPa), facilitating the regulation of mossy Li 0 deposition. The chemistries and kinetics are studied by operando synchrotron X-ray and in situ transmission electron microscopy (TEM). Solid-state NMR reveals a dual-phase ion conduction pathway and rapid Li + diffusion through the stable polymer-ceramic interphase. This designed electrolyte exhibits extended cycling life in Li 0 –Li 0 cells, reaching 12 000 h at 0.2 mA cm -2 and 5000 h at 0.5 mA cm -2 . Furthermore, owing to its high critical current density of 9 mA cm -2 , the Li 0 –LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) full cell demonstrates stable cycling at 5 mA cm -2 for 1100 cycles, retaining 88% of its capacity, even under near-zero stack pressure conditions.

25 ENERGY STORAGE↗

Achieving Electrode Smoothing by Controlling the Nucleation Phase of Metal Deposition Through Polymer‐Substrate Binding

Polymer additives [like polyethylene oxide (PEO)] are widely used for smooth electrode deposition in aqueous zinc and many other battery systems. However, the precise mechanism by which they regulate morphology and suppress dendrite formation remains unclear. In this study, the knowledge gap is addressed by using in situ electrochemical atomic force microscopy to directly observe the interfacial evolution during Zn electrodeposition and polymer adsorption on Cu substrates in the presence of varying concentrations of ZnSO 4 and PEO. Contrary to previous literature assumptions, which emphasize the binding to the growing Zn crystal surfaces or Zn 2+ ions, the results demonstrate that PEO smooths Zn films by promoting nucleation of (002)-oriented Zn platelets through interactions with the Cu substrate. Density functional theory simulations support this finding by showing that PEO adsorption on Cu modifies the interfacial energy of Zn/Cu/electrolyte interfaces, favoring the stabilization of Zn (002) on the Cu substrate, as well as confines Zn electrodeposition to a narrow near-surface region. In conclusion, these findings elucidate a novel design principle for electrode smoothing, emphasizing the importance of substrate selection paired with polymer additives that exhibit an attractive interaction with the substrate but minimal interaction with growing crystals, offering a mechanistic perspective for improved battery performance.

Electrodeposition↗

Intermetallics Based on Sodium Chalcogenides Promote Stable Electrodeposition–Electrodissolution of Sodium Metal Anodes

Sodiophilic micro-composite films of sodium-chalcogenide intermetallics (Na 2 Te and Na 2 S) and Cu particles are fabricated onto commercial copper foam current collectors (Na 2 Te@CF and Na 2 S@CF). For the first time a controllable capacity thermal infusion process is demonstrated. Enhanced wetting by the metal electrodeposition leads to state-of-the-art electrochemical performance. For example, Na 2 Te@CF-based half-cells demonstrate stable cycling at 6 mA cm -2 and 6 mAh cm -2 , corresponding to 54 µm of Na electrodeposited/electrodissolved by geometric area. Sodium metal batteries with Na 3 V 2 (PO 4 ) 3 cathodes are stable at 30C (7 mA cm -2 ) and for 10 000 cycles at 5C and 10C. Cross-sectional cryogenic focused ion beam (cryo-FIB) microscopy details deposited and remnant dissolved microstructures. Sodium metal electrodeposition onto Na 2 Te@CF is dense, smooth, and free of dendrites or pores. On unmodified copper foam, sodium grows in a filament-like manner, not requiring cycling to achieve this geometry. Substrate–metal interaction critically affects the metal–electrolyte interface, namely the thickness and morphology of the solid electrolyte interphase. Density functional theory and mesoscale simulations provide insight into support-adatom energetics, nucleation response, and early-stage morphological evolution. On Na 2 Te sodium atomic dispersion is thermodynamically more stable than isolated clusters, leading to conformal adatom coverage of the surface.

36 MATERIALS SCIENCE↗

Interface Design for High‐Performance All‐Solid‐State Lithium Batteries

All‐solid‐state batteries suffer from high interface resistance and lithium dendrite growth leading to low Li plating/stripping Coulombic efficiency (CE) of <90% and low critical current density at high capacity. Here, in this work, both challenges are simultaneously addressed and the Li plating/stripping CE is significantly increased to 99.6% at 0.2 mA cm −2 /0.2 mAh cm −2 , and critical current density (CCD) of > 3.0 mA cm −2 /3.0 mAh cm −2 by inserting a mixed ionic‐electronic conductive (MIEC) and lithiophobic LiF‐C‐Li 3 N‐Bi nanocomposite interlayer between Li 6 PS 5 Cl electrolyte and Li anode. The highly lithiophobic LiF‐C‐Li 3 N‐Bi interlayer with high ionic conductivity (10 −5 S cm −1 ) and low electronic conductivity (3.4×10 −7 S cm −1 ) enables Li to plate on the current collector (CC) surface rather than on Li 6 PS 5 Cl surface avoiding Li 6 PS 5 Cl electrolyte reduction. During initial Li plating on CC, Li penetrates into porous LiF‐C‐Li 3 N‐Bi interlayer and lithiates Bi nanoparticles into Li 3 Bi. The lithiophilic Li 3 Bi and Li 3 N nanoparticles in LiF‐C‐Li 3 N‐Li 3 Bi sub‐interlayer will move to CC along with plated Li, forming LiF‐C/Li 3 N‐Li 3 Bi lithiophobic/lithiophilic sublayer during the following Li stripping. This interlayer enables Co 0.1 Fe 0.9 S 2 /Li 6 PS 5 Cl/Li cell with an areal capacity of 1.4 mAh cm −2 to achieve a cycle life of >850 cycles at 150 mA g −1 . The lithiophobic/lithiophilic interlayer enables solid‐state metal batteries to simultaneously achieve high energy and long cycle life.

25 ENERGY STORAGE↗