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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 487 records · Page 27

Wet chemical synthesis and properties of argyrodite sulfide solid electrolytes for solid state lithium batteries

The commercialization of the lithium-ion battery (LIB) in 1991 was responsible for the explosion in portable electronic technologies that has been seen over the past 30 years. With the advent of electric vehicles and other high-powered technologies, there is tremendous demand for LIBs with higher energy density and high safety. To achieve this, new electrode materials must be explored. The obvious choice of anode material would be pure metal lithium, which has a theoretical specific capacity of 3860 mAh g-1 . Unfortunately, metal lithium anodes have not been widely commercialized due to their tendency to react violently with the flammable liquid electrolytes used in today’s batteries. Battery safety can best be achieved by adopting solid electrolytes in place of liquid electrolytes. Solid electrolytes are nonvolatile and nonflammable, safely allowing for the combination of high-capacity cathode materials with a Li metal anode. Argyrodite sulfide solid electrolytes such as halogen-doped Li6PS5X (X = Cl, Br, I) are noted for their high ionic conductivity. But before sulfides can be commercially adopted, they possess several disadvantages which must be addressed, including time- and energy-consuming synthesis processes, poor electrochemical stability, and intrinsically poor air stability. This dissertation seeks to address each of these challenges through materials design an synthesis strategies. In this work, we pioneer a solvent-based approach for the synthesis of argyrodite solid electrolytes Li7PS6 and Li6PS5Xinstead of a stringent solid-state synthesis. Nontoxic ethanol is employed as the solvent, enabling a rapid synthetic approach to produce argyrodite solid electrolytes with high phase purity and compositional flexibility. Compared with Li7PS6, halogen doping (i.e. X = F, Cl, Br, I) not only increases the ionic conductivity, but also enhances the electrochemical stability at the interface towards Li metal. Specifically, F-doped argyrodites produce a robust SEI layer containing LiF, contributing to enhanced interfacial stability. Finally, to address the air instability challenge, argyrodite-incorporated composite solid electrolytes (CSEs) are designed and prepared to produce stable and flexible membranes that are demonstrated in solid-state Li metal batteries. These advances push argyrodite sulfide solid electrolyte research further and pave the way for the proliferation of next generation lithium metal batteries.

25 ENERGY STORAGE↗

Leveraging Military Veteran Talent Through SkillBridge Training: Recommendations for the Solar Industry

Solar Energy International (SEI), in partnership with IREC, has published a white paper, Leveraging Military Veteran Talent Through SkillBridge Training: Recommendations for the Solar Industry. This resource presents SkillBridge as a key strategy for solar employers to attract, develop, and retain qualified veteran talent, and provides model training frameworks aligned with four key occupations, including solar installation, operations and maintenance, technical sales, and solar design.

Howes, Megan↗

Advanced battery modeling for interfacial phenomena and optimal charging

Lithium ion batteries are one of the most promising energy storage systems for portable devices, transportation, and renewable grids. To meet the increasing requirements of these applications, higher energy density and areal capacity, long cycle life, fast charging rate and enhanced safety for lithium ion battery (LIBs) are urgently needed. To solve these challenges, the relevant physics at different length scale need to be understood. However, experimental study is time consuming and limited in small scale’s study. Modeling techniques provide us powerful tools to get a deep understanding of the relevant physics and find optimal solutions. This work focuses on studying the mechanism in advanced battery engineering techniques and developing a new charging algorithm by model-based optimization. The research topics are divided into six topics and each topic is reported as a form of journal publication. Paper Ⅰ provides a new aspect of how ALD coating improves the lithium ion diffusion at electrode particles. Paper Ⅱ explains the mechanisms by which 3D electrodes enhance battery performance and reveals guidelines for optimized 3D electrode designs by a 3D electrochemical-mechanical battery model. Paper Ⅲ investigates the electrolyte concentration impact on SEI layer growth and Li plating, especially under high charge rates. Paper Ⅳ proposes an optimized charging protocol for fast charging for reducing the charging time with minimal degradation. Paper Ⅴ reports a comprehensive degradation model for degradation estimation and life predication of energy storage system (ESS). Paper Ⅵ is a study of temperature-dependent state of charge (SOC) estimation for battery pack.

25 ENERGY STORAGE↗

Surface heterogeneity propagation and homogenization for pouch cell-scale Li metal anodes

Li metal anode is a promising candidate for next-generation energy storage systems and is widely explored in Li-ion and solid-state batteries. Despite its potential, Li metal anodes face instabilities during long-term cycling, especially when paired with NMC or sulfur-based cathodes, where Li is cycled at high capacities of 6-8 mAh/cm2, equivalent to a thickness of 30-40 µm. During such extensive utilization, degradation mechanisms such as excessive solid electrolyte interphase (SEI), dendrites, and dead Li emerge, and ultimately lead to sudden failure and reduced cycle life. The origin of the degradation mechanisms stem from surface heterogeneities introduced during Li foil manufacturing and storage [1, 2]. As cycling progresses, the local heterogeneities propagate, resulting in uneven Li utilization and degradation-prone regions across the electrode [3], which consequently induce performance variations at the cell level. This heterogeneity propagation is particularly pronounced in large-format pouch cells in practical applications, where the surface effects are magnified. Without a clear understanding of the multi-scale heterogeneities and the development of surface homogenization methods, the performance consistency will be compromised, hindering the commercialization of Li metal batteries. In this presentation, we investigate the evolution of surface heterogeneity propagation on commercially available Li foils. We discover that inhomogeneous Li utilization appears as early as the first half-cycle of formation, manifesting as localized clusters and pits. In pouch cell configurations, these features exhibit areal density variations across the electrode on a scale of millimeters. To improve Li utilization homogeneity, a scalable mechanical brushing method is introduced to remove the chemically heterogeneous surface passivation layer. Furtherore, the influence of utilization homogeneity on cell-to-cell consistency is evaluated using 32 Li-NMC811 pouch cells divided into as-received and brushed Li groups. On the brushed Li, clusters and pits are no longer observable, and the cells exhibit significantly improved consistency in discharge capacity trajectories and cycle lifetime. Overall, this study highlights the role of Li surface utilization homogeneity on long-term cycling performance. Our research provides a pathway for improving large-area electrode uniformity and establishing evaluation methods for cell-to-cell consistency, both are key steps toward the commercialization of Li metal batteries and beyond. [1] Otto, Svenja-K., et al. "In-depth characterization of lithium-metal surfaces with XPS and ToF-SIMS: toward better understanding of the passivation layer." Chemistry of Materials 33.3 (2021): 859-867. [2] Hatzell, Kelsey, et al. "Aligning lithium metal battery research and development across academia and industry." Joule (2024). [3] Kim, Sangwook, et al. "Calendar life of lithium metal batteries: Accelerated aging and failure analysis." Energy Storage Materials 65 (2024): 103147.

25 - ENERGY STORAGE↗

Enhanced CO 2 Methanation Activity of Sm 0.25 Ce 0.75 O 2-δ –Ni by Modulating the Chelating Agents-to-Metal Cation Ratio and Tuning Metal–Support Interactions

Highly active and selective CO 2 methanation catalysts are critical to CO 2 upgrading, synthetic natural gas production, and CO 2 emission reduction. Wet impregnation is widely used to synthesize oxide-supported metallic nanoparticles as the catalyst for CO 2 methanation. However, as the reagents cannot be homogeneously mixed at an atomic level, it is challenging to modulate the microstructure, crystal structure, chemical composition, and electronic structure of catalysts via wet impregnation. In this work, a scalable and straightforward catalyst fabrication approach has been designed and validated to produce Sm 0.25 Ce 0.75 O 2-δ -supported Ni (SDC–Ni) as the CO 2 methanation catalyst. By varying the chelating agents-to-total metal cations ratio (C/I ratio) during the catalyst synthesis, we can readily and simultaneously modulate the microstructure, metallic surface area, crystal structure, chemical composition, and electronic structure of SDC–Ni, consequently fine-tuning the oxide–support interactions and CO 2 methanation activity. The optimal C/I ratio (0.1) leads to an SDC–Ni catalyst that facilitates C–O bond cleavage and significantly improves CO 2 conversion at 250 °C. A CO 2 -to-CH 4 yield of >73% has been achieved at 250 °C. Furthermore, a stable operation of >1500 hours has been demonstrated, and no degradation is observed. Extensive characterizations were performed to fundamentally understand how to tune and enhance CO 2 methanation activity of SDC–Ni by modulating the C/I ratio. The correlation of physical, chemical, and catalytic properties of SDC–Ni with the C/I ratio is established and thoroughly elaborated in this work. This study could be applied to tune the oxide–support interactions of various catalysts for enhancing the catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Autonomously Responsive Membranes for Chemical Warfare Protection

Stimuli-responsive materials offer new opportunities to resolve long-standing material challenges and are rapidly gaining pivotal roles in diverse applications. For example, smart protective garments that rapidly transport water vapor and autonomously block chemical threats are expected to enable an effective new paradigm of adaptive personal protection. However, the incorporation of these seemingly incompatible properties into a single responsive system remains elusive. Herein, a bistable membrane that can rapidly, selectively, and reversibly transition from a highly breathable state in a safe environment to a chemically protective state when exposed to organophosphate threats such as sarin is demonstrated. Dynamic response to chemical stimuli is achieved through the physical collapse of an ultrathin copolymer layer on the membrane surface, which efficiently gates transport through membrane pores composed of single-walled carbon nanotubes (SWNTs). The adoption of nanometer-wide SWNTs for ultrafast moisture conduction enables a simultaneous boost in size-sieving selectivity and water-vapor permeability by decreasing nanotube diameter, thereby overcoming the breathability/protection trade-off that limits conventional membrane materials. Adaptive multifunctional membranes based on this platform greatly extend the active use of a protective garment and present exciting opportunities in many other areas including separation processes, sensing, and smart delivery.

36 MATERIALS SCIENCE↗

High-Performance Hemofiltration via Molecular Sieving and Ultra-Low Friction in Carbon Nanotube Capillary Membranes

Conventional dialyzer membranes typically comprise of unevenly distributed polydisperse, tortuous, rough pores, embedded in relatively thick ≈20–50 µm polymer layers wherein separation occurs via size exclusion as well as differences in diffusivity of the permeating species. However, transport in such polymeric pores is increasingly hindered as the molecule size approaches the pore dimension, resulting in significant retention of undesirable middle molecules (≥15–60 kDa) and uremic toxins. Enhanced removal of middle molecules is usually accompanied by high albumin loss (≈66 kDa) causing hypoalbuminemia. Here, the scalable bottom-up fabrication of wafer-scale carbon nanotube (CNT) membranes with highly aligned, low-friction, straight-channels/capillaries and narrow pore-diameter distributions (≈0.5–4.5 nm) is demonstrated, to overcome persistent challenges in hemofiltration/hemodialysis. Using fluorescein isothiocyanate (FITC)-Ficoll 70 and albumin in phosphate buffered saline (PBS) as well as in bovine blood plasma, it is shown that CNT membranes can allow for significantly higher hydraulic permeability (more than an order of magnitude when normalized to pore area) than commercial high-flux hemofiltration/hemodialysis membranes (HF 400), as well as greatly enhance removal of middle molecules while maintaining comparable albumin retention. These findings are rationalized via an N-pore transport model that highlights the critical role of molecular flexing and deformation during size-selective transport within nanoscale confinements of the CNTs. In conclusion, the unique transport characteristics of CNTs coupled with size-exclusion and wafer-scale fabrication offer transformative advances for hemofiltration, and the obtained insight into molecular transport can aid advancements in several other bio-systems/applications beyond hemofiltration/hemodialysis.

36 MATERIALS SCIENCE↗

Dendrite–Free Potassium Metal Anodes in a Carbonate Electrolyte

Potassium (K) metal anodes suffer from a challenging problem of dendrite growth. In this study, it is demonstrated that a tailored current collector will stabilize the metal plating–stripping behavior even with a conventional KPF 6 –carbonate electrolyte. A 3D copper current collector is functionalized with partially reduced graphene oxide to create a potassiophilic surface, the electrode being denoted as rGO@3D–Cu. Potassiophilic versus potassiophobic experiments demonstrate that molten K fully wets rGO@3D–Cu after 6 s, but does not wet unfunctionalized 3D–Cu. Electrochemically, a unique synergy is achieved that is driven by interfacial tension and geometry: the adherent rGO underlayer promotes 2D layer–by–layer (Frank–van der Merwe) metal film growth at early stages of plating, while the tortuous 3D–Cu electrode reduces the current density and geometrically frustrates dendrites. The rGO@3D–Cu symmetric cells and half–cells achieve state–of–the–art plating and stripping performance. Here, the symmetric rGO@3D–Cu cells exhibit stable cycling at 0.1–2 mA cm –2 , while baseline Cu prematurely fails when the current reaches 0.5 mA cm –2 . The half–cells cells of rGO@3D–Cu (no K reservoir) are stable at 0.5 mA cm –2 for 10 000 min (100 cycles), and at 1 mA cm –2 for 5000 min. The baseline 3D–Cu, planar rGO@Cu, and planar Cu foil fails after 5110, 3012, and 1410 min, respectively.

25 ENERGY STORAGE↗

Enhanced Electrolyte Transport and Kinetics Mitigate Graphite Exfoliation and Li Plating in Fast–Charging Li–Ion Batteries

Despite significant progress in energy retention, lithium-ion batteries (LIBs) face untenable reductions in cycle life under extreme fast-charging (XFC) conditions, which primarily originate from a variety of kinetic limitations between the graphite anode and the electrolyte. Through quantitative Li + loss accounting and comprehensive materials analyses, it is directly observed that the operation of LIB pouch cells at 4 C||C/3 (charging||discharging) results in Li plating, disadvantageous solid-electrolyte-interphase formation, and solvent co-intercalation leading to interstitial decomposition within graphite layers. It is found that these failure modes originate from the insufficient properties of conventional electrolytes, where employing a designed ester-based electrolyte improved the capacity retention of these cells from 55.9% to 88.2% after 500 cycles when operated at the aforementioned conditions. These metrics are the result of effective mitigation of the aforementioned failure modes due to superior Li + transport and desolvation characteristics demonstrated through both experimental and computational characterization. Finally, this work reveals the vital nature of electrolyte design to XFC performance.

25 ENERGY STORAGE↗

Enhancement of Magneto‐Mechanical Actuation of Micropillar Arrays by Anisotropic Stress Distribution

Abstract Magnetically active shape‐reconfigurable microarrays undergo programmed actuation according to the arrangement of magnetic dipoles within the structures, achieving complex twisting and bending deformations. Cylindrical micropillars have been widely used to date, whose circular cross‐sections lead to identical actuation regardless of the actuating direction. In this study, micropillars with triangular or rectangular cross‐sections are designed and fabricated to introduce preferential actuation directions and explore the limits of their actuation. Using such structures, controlled liquid wetting is demonstrated on micropillar surfaces. Liquid droplets pinned on magnetic micropillar arrays undergo directional spreading when the pillars are actuated as depinning of the droplets is enabled only in certain directions. The enhanced deformation due to direction dependent magneto‐mechanical actuation suggests that micropillar arrays can be fundamentally tailored to possess application specific responses and opens up opportunities to exploit more complex designs such as micropillars with polygonal cross sections. Such tunable wetting of liquids on microarray surfaces has potential to improve printing technologies via contactless reconfiguration of stamp geometry by magnetic field manipulation.

Park, Jeong Eun↗

High-yield growth kinetics and spatial mapping of single-walled carbon nanotube forests at wafer scale

Emerging commercial applications of vertically aligned, single-walled carbon nanotube (SWCNT) “forests” require synthesis that minimizes nanotube diameter while maximizing number density across substrate areas exceeding centimeter scale. To address this need, we synthesized SWCNT forests on full silicon wafers with notable reproducibility and uniformity, and co-optimized growth for small diameters and high densities across large areas to access new territory in this 3D parameter space. We mapped the spatial uniformity of key structural features using Raman microscopy, synchrotron X-ray scattering, and Rutherford backscattering spectrometry. Low C 2 H 2 flux over sub-nm Fe/Mo catalysts produced small-diameter SWCNTs (2.1 nm) at high number densities (2.26 × 10 12 cm -2 ) on wafers up to 6 in. Although removing Mo resulted in larger SWCNT diameters and lower densities (<0.7 × 10 12 cm -2 ), mass conversion rates from C 2 H 2 to SWCNT product were high and remarkably invariant for catalyst compositions and densities (i.e., 47.7% or 1.30 × 10 6 % g-catalyst -1 on 4-in. wafers). These carbon conversion efficiencies far exceed typical benchtop reactors and are on par with the best reported literature values. Our detailed elucidation of correlations among structural characteristics within this resource-efficient process is expected to guide future scale-up efforts of SWCNT forest growth beyond wafer scale.

36 MATERIALS SCIENCE↗

Synthesis of wafer-scale SWCNT forests with remarkably invariant structural properties in a bulk-diffusion-controlled kinetic regime

Robust synthesis of vertically aligned carbon nanotubes (VACNT) at large scale is required to accelerate deployment of numerous cutting-edge devices to emerging commercial applications. To address this need, this work demonstrates that the structural characteristics of single-walled CNTs (SWCNTs) produced in a growth regime dominated by bulk diffusion of the gaseous carbon precursor are remarkably invariant over a broad range of process conditions (precursor concentration increased up to 30-fold, catalyst substrate area from 1 cm 2 to 180 cm 2 , growth pressure from 20 to 790 mbar, and gas flowrates up to 8-fold). A simple growth kinetics model is derived that accounts for both reactant bulk diffusion and competing byproduct formation in the presence of excess hydrogen, which quantitatively reproduces the experimental data in the entire isothermal parameter space. The model enables critical predictions for process scale-up optimization including a potential 6-fold increase in CNT production rate, a ~90% carbon conversion efficiency in select conditions, and elimination of reaction rate decay observed at high pressures by using a hydrogen-free growth environment. This model-guided opportunity to substantially improve synthesis throughput and efficiency, in conjunction with the remarkably invariant CNT properties, is appealing for reliable VACNT device fabrication at both small and industrial scales.

36 MATERIALS SCIENCE↗

Growth of carbon nanotube forests on flexible metal substrates: Advances, challenges, and applications

Owing to their remarkable properties and ordered architecture, vertically aligned CNT forests (VACNT) hold promises for countless applications ranging from energy storage to multifunctional fiber production. Over the last three decades, studies of carbon nanotube (CNT) growth have provided invaluable insight into the CNT nucleation and growth mechanism and enabled critical advancements in nanotechnology. Nevertheless, the ability to fully harness the exceptional VACNT properties in commercial devices is bottlenecked by compatibility of current CNT synthesis processes with large-scale manufacturing. Metal foil substrates present an economic alternative to traditional insulating substrates, like silicon or quartz, and are compatible with both roll-to-roll and automated, large-scale, batch processes. Compared to CNT growth on Si substrates, metal foils present additional challenges, such as increased roughness and reactivity at high temperatures. Nonetheless, many successful VACNT growths on conducting metal foils have been reported, which demonstrate the feasibility of metal substrate use for large-volume production of high-quality CNTs. Here, in this review, we discuss advancements in the field of VACNT growth on metal foil and specifically examine different choices for metal substrates, barrier and catalyst layers, deposition and growth methods, resulting CNT characteristics, and highlight a number of applications that benefit from CNT growth on metal substrates and transition to large-scale manufacturing.

36 MATERIALS SCIENCE↗