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At least 19 records

Novel One-Step Production of Carbon-Coated Sn Nanoparticles for High-Capacity Anodes in Lithium-Ion Batteries

Lithium-ion batteries offer the highest energy density of any currently available portable energy storage technology. By using different anode materials, these batteries could have an even greater energy density. One material, tin, has a theoretical lithium capacity (994 mAh/g) over three-times higher than commercial carbon anode materials. Unfortunately, to achieve this high capacity, bulk tin undergoes a large volume expansion, and the material pulverizes during cycling, giving a rapid capacity fade. To mitigate this issue, tin must be scaled down to the nano-level to take advantage of unique micromechanics at the nanoscale. Synthesis techniques for Sn nanoparticle anodes are costly and overly complicated for commercial production. A novel one-step process for producing carbon-coated Sn nanoparticles via spark plasma erosion (SPE) shows great promise as a simple, inexpensive production method. The SPE method, characterization of the resulting particles, and their high-capacity reversible electrochemical performance as anodes are described. With only a 10% addition of these novel SPE carbon-coated Sn particles, one anode composition demonstrated a reversible capacity of ~460 mAh/g, achieving the theoretical capacity of that particular electrode formulation. These SPE carbon-coated Sn nanoparticles are drop-in ready for present commercial lithium-ion anode processing and would provide a ~10% increase in the total capacity of current commercial lithium-ion cells.

25 ENERGY STORAGE↗

Carbon and carbon-coated electrodes for multistage depressed collectors for electron-beam devices - A technology review

Various aspects of carbon and carbon-coated multistaged depressed collector (MDC) electrode technology are reviewed. The physical properties of untreated graphite electrodes, ion-textured graphite electrodes, and textured, carbon-coated copper electrodes, and surface treatment procedures for these electrodes are described. The secondary electron emissions of the three electrode types are analyzed. MDC fabrication methods are discussed. The performances of MDCs fabricated with untreated graphite electrodes, ion-textured graphite electrodes, and textured, carbon-coated copper electrodes are evaluated. MDC and TWT efficiency levels for tubes fabricated with the three materials are measured.

Curren, Arthur N.↗

One-Step Spark Plasma Erosion Processing of Carbon-Coated Sn-Si Nanoparticles for Lithium-Ion Battery Anodes

High density portable energy storage is desirable owing to the energy requirements of portable electronics and electric vehicles. The Li-ion battery’s high energy density could be even further improved through the utilization of alternative materials (instead of carbon) for the anode, such as Sn or Si. Nonetheless, the large volume expansion upon lithiation, up to ~300% for Li 22 Si 5 , causes pulverization and rapid capacity degradation during cycling. Sn also forms a Li 22 Sn 5 compound with the equivalent stoichiometric Li capacity but with enhanced ductility. Nano-sized Si and Sn have demonstrated distinctive nanoscale properties, facilitating the retention of higher capacities, particularly when coated with carbon, which improves mechanical stability. To date, the methods of synthesizing coated Si, Sn, or Si-Sn alloyed nanoparticles are complicated, costly, and not readily scalable to meet the demands of cost-effective manufacturing. Spark plasma erosion in a hydrocarbon dielectric has been explored as a one-step process to produce Sn-Si alloy nanoparticles coated with a thin carbon film, offering a scalable and cost-effective processing route. The resulting Sn-Si particles exhibited a bi-modal size distribution at ~5 nm and ~500 nm and were carbon-coated, as intended, from the hydrocarbon dielectric breakdown. The spark-eroded nanoparticles were thoroughly characterized using TEM/EDS, XPS, AES, SSNMR, and TGA, and their improved electrochemical performance was assessed through half-cell experiments.

25 ENERGY STORAGE↗

Learning heterogeneous reaction kinetics from X-ray videos pixel by pixel

Reaction rates at spatially heterogeneous, unstable interfaces are notoriously difficult to quantify, yet are essential in engineering many chemical systems, such as batteries and electrocatalysts. Experimental characterizations of such materials by operando microscopy produce rich image datasets, but data-driven methods to learn physics from these images are still lacking because of the complex coupling of reaction kinetics, surface chemistry and phase separation. Here we show that heterogeneous reaction kinetics can be learned from in situ scanning transmission X-ray microscopy (STXM) images of carbon-coated lithium iron phosphate (LFP) nanoparticles. Combining a large dataset of STXM images with a thermodynamically consistent electrochemical phase-field model, partial differential equation (PDE)-constrained optimization and uncertainty quantification, we extract the free-energy landscape and reaction kinetics and verify their consistency with theoretical models. We also simultaneously learn the spatial heterogeneity of the reaction rate, which closely matches the carbon-coating thickness profiles obtained through Auger electron microscopy (AEM). Across 180,000 image pixels, the mean discrepancy with the learned model is remarkably small (<7%) and comparable with experimental noise. Our results open the possibility of learning nonequilibrium material properties beyond the reach of traditional experimental methods and offer a new non-destructive technique for characterizing and optimizing heterogeneous reactive surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Learning heterogeneous reaction kinetics from X-ray movies pixel-by-pixel

Reaction rates at spatially heterogeneous, unstable interfaces are notoriously difficult to quantify, yet are essential in engineering many chemical systems, such as batteries 1 and electrocatalysts 2. Experimental characterizations of such materials by operando microscopy produce rich image datasets 3–6, but data-driven methods to learn physics from these images are still lacking because of the complex coupling of reaction kinetics, surface chemistry and phase separation 7. Here we show that heterogeneous reaction kinetics can be learned from in situ scanning transmission X-ray microscopy (STXM) images of carbon-coated lithium iron phosphate (LFP) nanoparticles. Combining a large dataset of STXM images with a thermodynamically consistent electrochemical phase-field model, partial differential equation (PDE)-constrained optimization and uncertainty quantification, we extract the free-energy landscape and reaction kinetics and verify their consistency with theoretical models. We also simultaneously learn the spatial heterogeneity of the reaction rate, which closely matches the carbon-coating thickness profiles obtained through Auger electron microscopy (AEM). Across 180,000 image pixels, the mean discrepancy with the learned model is remarkably small (<7%) and comparable with experimental noise. Our results open the possibility of learning nonequilibrium material properties beyond the reach of traditional experimental methods and offer a new non-destructive technique for characterizing and optimizing heterogeneous reactive surfaces.

Chueh, William↗

Nanometer Resolution Structure‐Emission Correlation of Individual Quantum Emitters via Enhanced Cathodoluminescence in Twisted Hexagonal Boron Nitride

Understanding the atomic structure of quantum emitters, often originating from point defects or impuritie, is essential for designing and optimizing materials for quantum technologies such as quantum computing, communication, and sensing. Despite the availability of atomic-resolution scanning transmission electron microscopy and nanoscale cathodoluminescence microscopy, experimentally determining the atomic structure of individual emitters is challenging due to the conflicting needs for thick samples to generate strong cathodoluminescence signals and thin samples for structural analysis. To overcome this challenge, significantly enhanced cathodoluminescence at twisted interfaces is leveraged to achieve sub-nanometer localization precision for the first time in mapping individual quantum emitters in carbon-implanted hexagonal boron nitride. This unprecedent spatial sensitivity, together with correlative electron energy loss spectroscopy quantitative scanning transmission electron microscopy imaging, and first principles density functional theory calculations, enables the identification of the atomic structure of the 440 nm blue emitter in hexagonal boron nitride as a substituted vertical carbon dimer. Building on the atomic structure insights, nanoscale spatially precise creation of blue emitters is demonstrated by electron beam irradiation of carbon-coated hexagonal boron nitride. This advancement in correlating atomic structures with optical properties lays the foundation for a deeper understanding and precise engineering of quantum emitters, significantly advancing the development of cutting-edge quantum information technologies.

2D material↗

Mechanistic Insights into the Surface Instabilities of TiNb 2 O 7, a High‐Power Li‐Ion Anode

TiNb 2 O 7 (TNO) is a promising Li-ion battery anode for high-power applications, such as implantable medical devices and heavy-duty equipment. Hailed as being safe due to its elevated operating potential near 1.6 V, TNO has long been assumed to be highly stable in the carbonate-based electrolytes used in Li-ion batteries. Herein, all mechanisms occurring at the surface of both TNO and Nd-doped TNO are identified, and both materials in fact show significant gassing. CO 2 is even released at open circuit conditions, demonstrating the poor chemical stability of the material in the electrolyte even prior to battery operation. Such extreme instability is a critical safety concern. In addition, it was found that Ti dissolves from the surface of TNO particles at low voltage (below 1.4 V vs Li), and in fact deposits on the counter electrode. Ti further inside TNO particles then diffuses to the Ti-poor surface during discharge. Partial carbon-coating as a mitigating measure has also been tested and found to exacerbate these processes. The findings identify novel reactions occurring within TNO, and clearly highlight the need to stabilize the surfaces of TNO in order to prevent such aggressive deterioration at the surface of the particles.

25 ENERGY STORAGE↗

Operando NMR characterization of cycled and calendar aged nanoparticulate silicon anodes for Li-ion batteries

Replacing graphite anodes with Si anodes can greatly increase the energy of current Li-ion batteries. Detailed characterization of Si lithiation reactions, SEI formation, and reversibility are therefore active areas of research. Solid-state 7 Li nuclear magnetic resonance (NMR) spectroscopy is useful for characterizing different lithium local environments within Si anodes. Here, we developed an operando NMR methodology to characterize aging of carbon-coated nanoparticulate Si anodes in pouch cells paired with Ni-rich cathodes. We observed a new lithiation mechanism in the Si nanoparticles: direct formation of over-lithiated Li 15+x Si 4 (x<0.6) phase. Furthermore, our novel operando cells maintained good performance with long-term cycle and calendar aging. Here we identified trapped lithium silicides as a major contributor to capacity fade with aging. Finally, we determined that the addition of Mg (TFSI) 2 to the electrolyte decreased the amount of trapped lithium silicides and therefore increased the capacity and capacity retention for the nanoparticulate Si used.

25 ENERGY STORAGE↗

Nanostructured C@CuS Core–Shell Framework with High Lithium-Ion Storage Performance

In this study, we have synthesized a nanostructured core–shell framework of carbon-coated copper sulfide (C@CuS) through a one-step precipitation technique. The carbon sphere template facilitated the nucleation of CuS nanostructures. The synthesized nanocomposites have demonstrated remarkable lithium-ion storage capabilities when utilized as an anode in lithium-ion batteries. Notably, they exhibit an impressive rate capability of 314 mAh g -1 at a high current density of 5000 mA g -1 , along with excellent long-term cycle stability, maintaining 463 mAh g -1 at 1000 mA g -1 after 800 cycles. This superior performance is due to the core–shell architecture of the composite, where the carbon core enhances the conductivity of CuS nanoparticles and mitigates volume expansion, thus preventing capacity loss. Our study not only elucidates the significance of carbon in the construction of nano-heterojunctions or composite electrodes but also presents a practical approach to significantly boost the electrochemical performance of CuS and other metal sulfides.

25 ENERGY STORAGE↗

Top-Coating Silicon Onto Ceramic

Polycrystalline silicon for solar cells produced at low cost. Molten silicon poured from quartz trough onto moving carbon-coated ceramic substrate. Doctor blade spreads liquid silicon evenly over substrate. Molten material solidifies to form sheet of polycrystalline silicon having photovoltaic conversion efficiency greater than 10 percent. Method produces 100-um-thick silicon coatings at speed 0.15 centimeter per second.

Heaps, J. D.↗

Performance of textured carbon on copper electrode multistage depressed collectors with medium-power traveling wave tubes

Performance of multistage depressed collectors (MDCs) using textured carbon on copper substrate electrode surfaces was evaluated in conjunction with medium-power traveling wave tubes (TWTs). The MDC and TWT overall efficiencies for these electrodes were measured and compared with those obtained with the same TWT and a copper electrode MDC of identical design. Long-term stability of the carbon-coated copper electrode surfaces was investigated by periodic evaluation of TWT-MDC performance over an extended period of continuous wave (CW) operation. Application of textured carbon coating on copper MDC electrode surfaces produced a 13% improvement in both MDC and TWT overall efficiencies for the TWT-MDC tests. During 1600 hr of CW operation with a medium power TWT, no significant changes in MDC performance were noted. This indicated good stability of the textured carbon electrode surfaces. This stability was confirmed by scanning electron microscope examinations of the electrode surfaces before assembly of the MDC and after completion of the test program.

Ramins, Peter↗

TWT efficiency improvement by a low-cost technique for deposition of carbon on MDC electrodes

A simple method of improving the TWT and multistage depressed collector (MDC) efficiency has been demonstrated. The efficiency improvement was produced by the application of a thin layer of carbon to the copper electrodes of the MDC by means of a rapid low-cost technique involving the pyrolysis of hydrocarbon oil in electric arc discharges. Experimental results with a representative TWT and MDC showed an 11 percent improvement in both the TWT and MDC efficiencies as compared to those of the same TWT and MDC with machined copper electrode surfaces. An extended test with a 550-W CW TWT indicated good durability of the carbon-coated electrode surfaces.

Ebihara, Ben T.↗

Antarctic polar stratospheric aerosols: The roles of nitrates, chlorides and sulfates

Nitric and hydrochloric acids have been postulated to condense in the winter polar stratosphere to become an important component of polar stratospheric clouds. One implication is that the removal of NO(y) from the gas phase by this mechanism allows high Cl(x) concentrations to react with O3, because the formation of ClNO3 is inhibited. Contributions of NO3 and Cl to the stratospheric aerosol were determined during the 1987 Airborne Antarctic Ozone Experiment by testing for the presence of nitrates and chlorides in the condensed phase. Aerosol particles were collected on four 500 micron diameter gold wires, each pretreated differently to give results that were specific to certain physical and chemical aerosol properties. One wire was carbon-coated for concentration and size analyses by scanning electron microscopy; X-ray energy dispersive analyses permitted the detection of S and Cl in individual particles. Three more wires were coated with Nitron, barium chloride and silver nitrate, respectively, to detect nitrate, sulfate and chloride in aerosol particles. All three ions, viz., sulfates, nitrates and chlorides were detected in the Antarctic stratospheric aerosol. In terms of number concentrations, the aerosol was dominated by sulfates, followed by chlorides and nitrates. An inverse linear regression can be established between nitrate concentrations and ozone mixing ratio, and between temperature and nitrates.

Pueschel, R. F.↗

Role of the interfacial thermal barrier in the effective thermal diffusivity/conductivity of SiC-fiber-reinforced reaction-bonded silicon nitride

Experimental thermal diffusivity data transverse to the fiber direction for composites composed of a reaction bonded silicon nitride matrix reinforced with uniaxially aligned carbon-coated silicon carbide fibers indicate the existence of a significant thermal barrier at the matrix-fiber interface. Calculations of the interfacial thermal conductances indicate that at 300 C and 1-atm N2, more than 90 percent of the heat conduction across the interface occurs by gaseous conduction. Good agreement is obtained between thermal conductance values for the oxidized composite at 1 atm calculated from the thermal conductivity of the N2 gas and those inferred from the data for the effective composite thermal conductivity.

Bhatt, Hemanshu↗

Grain growth, optical polarisation, and extinction in interstellar clouds

Increases in the wavelength of maximum polarization and the ratio of total to selective extinction are generally assumed to be the result of grain growth in interstellar clouds. Using a grain model in which the interstellar extinction is explained by amorphous carbon (a-C) and hydrogenated amorphous carbon (a-C:H) mantles on silicate cores the effects of these absorbing carbonaceous mantles on the polarizing properties of large (500 to 2500 A radius) silicate grains were theoretically studied. The polarization model of Mathis was adopted and it was shown that carbon-coated silicate grains can explain the relationship between the wavelength of maximum polarization and R observed toward dark clouds.

Jones, A. P.↗

Black Carbon (Soot) Aerosol in the Lower Stratosphere and Upper Troposphere

We have used two approaches to measure BCA in the stratosphere. The first method consists of collecting aerosols by impaction on quartz rods, upon which are mounted strips of polystyrene filter material. Each 25 mm by 0.5 mm filter strip is alternately masked and exposed in 5 mm long sections. After sampling, the optical density of the exposed sections is measured and compared with the optical density of the masked (unexposed) sections. The filter strip is a Lambertian collector, the scattering property of which is not affected by the deposition of liquid sulfuric acid droplets which dominate the stratospheric aerosol. Hence, all attenuation greater in the exposed than in the non-exposed sections is due to absorption by BCA or rare opaque materials such as meteoritic iron. In a second approach we expose carbon-coated gold or palladium wires to air outside the aircraft boundary layer [Farlow et al., 1979; Pueschel et al., 1989]. With a field emission scanning electron microscope we are able to characterize BCA particles in addition to the dominant sulfuric acid droplets. Typically, soot is comprised of 20 nm diameter spheres linked together as branching chains or loosely packed aggregates (Figure 1a). The microscope has a lateral image resolution of 1.5 nm and can clearly resolve individual spheres making up BCA aggregates. Their morphology is uniquely different from that of the liquid sulfuric acid-water aerosol (Figure 1b). We approximate the size of each BCA particle by that of a sphere of equivalent volume and fit a lognormal size distribution to both the BCA and H2SO4/H2O aerosols. Both sampler types have been mounted on NASA's ER-2 high-altitude research aircraft (altitude ceiling of 70,000 feet), and on NASA's DC-8 (40,000 feet ceiling) aircraft to sample aerosols from a significant portion of the atmosphere.

Pueschel, R. F.↗

Composite Cathodes for Dual-Rate Li-Ion Batteries

Composite-material cathodes that enable Li-ion electrochemical cells and batteries to function at both high energy densities and high discharge rates are undergoing development. Until now, using commercially available cathode materials, it has been possible to construct cells that have either capability for high-rate discharge or capability to store energy at average or high density, but not both capabilities. However, both capabilities are needed in robotic, standby-power, and other applications that involve duty cycles that include long-duration, low-power portions and short-duration, high-power portions. The electrochemically active ingredients of the present developmental composite cathode materials are: carbon-coated LiFePO4, which has a specific charge capacity of about 160 mA h/g and has been used as a high-discharge-rate cathode material and Li[Li(0.17)Mn(0.58)Ni(0.25)]O2, which has a specific charge capacity of about 240 mA h/g and has been used as a high-energy-density cathode material. In preparation for fabricating the composite material cathode described, these electrochemically active ingredients are incorporated into two sub-composites: a mixture comprising 10 weight percent of poly(vinylidine fluoride); 10 weight percent of carbon and 80 weight percent of carbon coated LiFePO4; and, a mixture comprising 10 weight percent of PVDF, and 80 weight percent of Li[Li(0.17)Mn(0.58)Ni(0.25)]O2. In the fabrication process, these mixtures are spray-deposited onto an aluminum current collector. Electrochemical tests performed thus far have shown that better charge/discharge performance is obtained when either 1) each mixture is sprayed on a separate area of the current collector or (2) the mixtures are deposited sequentially (in contradistinction to simultaneously) on the same current-collector area so that the resulting composite cathode material consists of two different sub-composite layers.

Whitacre, Jay↗

Olivine Dissolution and Formation of Secondary phases in Ultramafic Soils

Introduction: Olivine has been proposed as an indicator for the duration of water-rock interaction within Martian rocks and sediments [1-3]. The use of olivine as a mineralogical indicator for past aqueous alteration on Mars requires interpretation of a complex combination of factors including pH, temperature, and composition [5,6]. Here, we examine the persistence of natural olivine within terrestrial ultramafic soils (Fe/Mg-rich, Al-poor) developing under different climatic conditions and the incipient dissolution of emplaced forsterite (Fo) and fayalite (Fa) surfaces to investigate environmental effects on incipient olivine dissolution, olivine persistence in soils, and formation of secondary phases. Methods: Field Sites. We examined olivine weathering and secondary material formation in ultramafic soils at 6 sites in the Klamath Mountains (KM) of northern California with a mean annual temperature of ~12.8℃ and precipitation of ~55.7-95.4 cm/year [7], and soil pH of ~6.5-7.3; 4 sites in the Tablelands (TB) of Newfoundland, Canada with a mean annual temperature of <3.9℃ and precipitation of ~120.0 cm/year [8], and soil pH of ~7.7; and at 3 sites at Pickhandle Gulch (PG), Nevada with a mean annual temperature of ~14.4℃ and precipitation of ~14.1 cm/year [7], and soil pH of ~8.5. Sampling sites span an age range of ~12.1-50+ kya in the Klamath Mountains [9,10] and ~13-30 kya in the Tablelands [11]. Pickhandle Gulch sites are undated. Parent Material and Soil Analyses. Polished thin sections of bulk soil prepared by Wagner Petrographic, Inc were carbon-coated and analyzed on a JEOL 2100 SEM in back-scattered electron mode in the EMIL lab at UNLV and at the 13-ID-E synchrotron beamline at Argonne National Laboratory using µXRF, µXRD, and XAS. Soil and parent material samples were powdered in a Fritsch pulverisette and analyzed by XRD and soil by VNIR. Soil preparation is further described in [12]. Disk Preparation, Burial, and Collection. Fo disks were cut from a column prepared via hot-pressing and Fa disks by sintering synthetic fayalite powder, see [13] for detail. Disks were polished to a 0.25-micron level with diamond grit. Disks were buried in 3 KM soils, 4 TB soils, and 3 PG soils, collected after exactly 365 days, and washed gently with 100% reagent grade ethanol to remove potential adhered soil material. Weathered disks and soil samples were stored in a -20℃ freezer until analysis. Unaltered control disks prepared identically to the buried disks were stored at -20℃ for the duration of the experiment. Disk Analyses. One Fo and Fa disk from each climate zone was analyzed on a variable pressure Zeiss Supra 40VP SEM at Northern Arizona University. A separate Fo and Fa disk from each climate zone was analyzed by XPS using a Physical Electronics VersaProbe II at the Penn State Univ. Materials Characterization Lab after a Na-dodecyl sulfate wash and ozonation to remove carbon contamination as in [14]. VNIR measurements were conducted at Johnson Space Center using an ASD FieldSpec3 under ambient lab conditions on a separate Fo and Fa disk from each climate zone. One separate Fo and Fa control sample was analyzed for each technique for comparison with weathered samples. XPS uncertainty was determined from 5 repeat measurements on controls. Results: Bedrock and Soil Results Olivine is present in the parent material in the KM and TB. Olivine is found in ~12.1 ka KM soils but is absent from all older soils, while persisting into the oldest (>20 ka) TB soil (Figure 1). In both locations, olivine is found as cores surrounded by a serpentine rind (Figure 2). VNIR spectra from the analyzed soils possess strong OH-associated spectral features at ~2.33 µm indicating the presence of Mg-rich phyllosilicates as well as ferric-oxide features at ~0.92 µm in the KM (Figure 3). Primary crystalline silicate grains mostly incorporate Fe2+, while poorly crystalline weathering rinds are best fit by ferric oxide XAS standards (Figure 4). µXRF also shows that Fe and Ni concentrate in weathering rinds and Cr remains within interior silicate grains (Figure 4). Buried Sample Results All Fo surfaces exhibited formation of dissolution features including shallow pitting not observed on controls. Dissolution features were most visually widespread on the KM disk (Figure 5). Leaching of Mg from KM and TB Fo disks was evident from <1.6 Mg/Si ratios measured by XPS (Figure 6). Fe-rich precipitates in SEM (Figure 5) and Fe presence in XPS scans (Figure 6) indicate Fe deposition onto KM and TB Fo disk surfaces. The appearance of a spectral feature at 0.55 µm in the VNIR spectra from the TB Fo suggests this Fe is ferric (Figure 7). The PG Fo appears least altered, with minimal formation of dissolution features in SEM (Figure 5), a Mg/Si ratio inconsistent with leaching (~2) (Figure 6), and VNIR spectra almost identical to the control sample. Analysis of Fa surfaces is ongoing. The higher temperatures and more acidic pH in the KM soils likely drive the faster dissolution of the Fo disks described above. While the TB soils experience greater precipitation than in the KM, the cooler temperatures and more basic soil pH facilitate observable but more limited alteration. The dry climate and basic soil pH at PG lead to minimal dissolution of the PG disk surfaces.

A D Feldman↗