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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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All sourcesNASA NTRSDOE OSTI
NASA NTRS2013

Properties and Performance Attributes of Novel Co-extruded Polyolefin Battery Separator Materials: Electrical Properties - Part 2

As NASA prepares for its next era of manned spaceflight missions, advanced energy storage technologies are being developed and evaluated to address and enhance future mission needs and technical requirements. Cell-level components for advanced lithium-ion batteries possessing higher energy, more reliable performance and enhanced, inherent safety characteristics have been under development within the NASA infrastructure. A key component for safe and reliable cell performance is the cell separator, which separates the two energetic electrodes and functions to inhibit the occurrence of an internal short circuit but preserves an ionic current. Recently, a new generation of co-extruded separator films has been developed by ExxonMobil Chemical and introduced into their battery separator product portfolio. Several grades of this new separator material were evaluated with respect to dynamic mechanical properties and safety-related performance attributes, and the results of these evaluations were previously reported in "Part 1: Mechanical Properties" of this publication. This current paper presents safety-related performance results for these novel materials obtained by employing a complementary experimental methodology, which involved the analysis of separator impedance characteristics as a function of temperature. The experimental results from this study are discussed with respect to potential cell safety enhancement for future aerospace as well as for terrestrial energy storage needs, and they are compared with pertinent mechanical properties of these materials, as well as with current state-of-the practice separator materials.

Baldwin, Richard S.↗
DOE OSTI2020

Direct Evidence of Charge Transfer upon Anion Intercalation in Graphite Cathodes through New Electronic States: An Experimental and Theoretical Study of Hexafluorophosphate

Graphite intercalation compounds continue to be central to technologies for electrochemical energy storage from anodes in established Li-ion batteries to cathodes in beyond Li-ion concepts paired with multivalent anodes. When used as a cathode, graphite intercalates a variety of anions with PF 6 - being among the most common. Paired with Li intercalation at the anode, the corresponding dual carbon battery yields high energy and power densities. Given the available choice of anions as intercalants, it is important to elucidate how the graphite structure accommodates them in order to tailor the molecular species to maximize charge and reversibility. However, the changes in electronic structure of the host graphite lattice upon anion intercalation are poorly understood compared to cations, which represent a fundamentally different reaction. Herein, PF 6 -intercalated graphite has been studied using techniques sensitive to electronic structure, namely, X-ray Raman spectroscopy (XRS), X-ray absorption near-edge spectroscopy (XANES), and X-ray emission spectroscopy (XES). Complementary full-potential, all-electron density functional theory calculations yielded excellent agreement with the spectra, thus providing insight into charge compensation in the graphite lattice. In particular, a pre-$π^*$ feature emerged in XRS/XANES, which is direct evidence of the removal of charge from the host lattice to compensate the intercalated anions, leading to an overall lowering of the Fermi energy level. This is expected to be characteristic of many intercalants in anion-intercalated graphite. The unambiguous identification of the origin of the pre-$π^*$ spectral feature, which is frequently seen in graphitic systems, is of broad interest to the spectroscopy of graphitic systems beyond the practical implications of anion-induced changes in the electronic properties for real devices.

36 MATERIALS SCIENCE↗
NASA NTRS2009

NASA Tech Briefs, October 2009

Topics covered include: Light-Driven Polymeric Bimorph Actuators; Guaranteeing Failsafe Operation of Extended-Scene Shack-Hartmann Wavefront Sensor Algorithm; Cloud Water Content Sensor for Sounding Balloons and Small UAVs; Pixelized Device Control Actuators for Large Adaptive Optics; T-Slide Linear Actuators; G4FET Implementations of Some Logic Circuits; Electrically Variable or Programmable Nonvolatile Capacitors; System for Automated Calibration of Vector Modulators; Complementary Paired G4FETs as Voltage-Controlled NDR Device; Three MMIC Amplifiers for the 120-to-200 GHz Frequency Band; Low-Noise MMIC Amplifiers for 120 to 180 GHz; Using Ozone To Clean and Passivate Oxygen-Handling Hardware; Metal Standards for Waveguide Characterization of Materials; Two-Piece Screens for Decontaminating Granular Material; Mercuric Iodide Anticoincidence Shield for Gamma-Ray Spectrometer; Improved Method of Design for Folding Inflatable Shells; Ultra-Large Solar Sail; Cooperative Three-Robot System for Traversing Steep Slopes; Assemblies of Conformal Tanks; Microfluidic Pumps Containing Teflon[Trademark] AF Diaphragms; Transparent Conveyor of Dielectric Liquids or Particles; Multi-Cone Model for Estimating GPS Ionospheric Delays; High-Sensitivity GaN Microchemical Sensors; On the Divergence of the Velocity Vector in Real-Gas Flow; Progress Toward a Compact, Highly Stable Ion Clock; Instruments for Imaging from Far to Near; Reflectors Made from Membranes Stretched Between Beams; Integrated Risk and Knowledge Management Program -- IRKM-P; LDPC Codes with Minimum Distance Proportional to Block Size; Constructing LDPC Codes from Loop-Free Encoding Modules; MMICs with Radial Probe Transitions to Waveguides; Tests of Low-Noise MMIC Amplifier Module at 290 to 340 GHz; and Extending Newtonian Dynamics to Include Stochastic Processes.

Source record↗
DOE OSTI2021

Anharmonicity in partially filled skutterudites Yb x Co 4 Sb 12

Here, we report an experimental investigation of Yb filler ion dynamics in partially filled skutterudite samples Yb x Co 4 Sb 12 ( x = 0.26 and x = 0.4). From extended x-ray absorption fine structure (EXAFS) measurements at the Yb L 2 -edge, the mean-square displacements of the Yb fillers were extracted over a wide temperature range from 10 to 500 K. We found that the low-temperature dynamics of Yb fillers are described well using a harmonic oscillator approximation with Einstein temperatures of 70 ± 5 K for both samples. This finding is consistent with the observed low-energy phonon mode at 5.3(5) meV in the inelastic x-ray scattering (IXS) data. However, the temperature dependence deviates from the harmonic approximation at high temperatures due to significant cubic anharmonicity, which was revealed in the EXAFS cumulant analysis. Our study also demonstrates that complementary information on filler dynamics in skutterudites can be acquired using EXAFS and IXS.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Microstructurally informed synchrotron x-ray analysis revealing helium defect transitions in ultrafine grained tungsten

The formation of insoluble gaseous defects in materials due to nuclear transmutation or ion implantation involves the diffusion of impurity atoms to form atomic defect clusters that coalesce into bubbles or cavities and ultimately degrade the material properties. Transmission electron microscopy (TEM) is limited in its ability to resolve sub-nanometer gas clusters whereas X-ray diffraction (XRD) provides information pertaining to local atomic changes. Here, in this study, helium (He) implanted ultrafine grained tungsten is explored through a multimodal defect characterization campaign combining TEM-informed Small Angle X-ray Scattering (SAXS) analysis, XRD lattice parameter measurements, and nanoscale He cluster quantification from a region of reciprocal space accessible via Wide Angle X-ray Scattering (WAXS). Moderate elevated temperature implantations are shown to produce high concentrations of sub-nanoscale He clusters and small, homogeneously distributed cavities, which collectively are linked to lattice expansion and further substantiated through complementary atomistic simulations. Increased implantation temperatures encourage the diffusion of these defects to the grain boundaries (GBs), leading to lattice relaxation and the growth of large GB cavities manifesting as bimodal size distributions in the SAXS analysis. Overall, our results demonstrate the utility of multimodal synchrotron X-ray analysis in bridging the gap between microscale He cavity quantification and atomic-scale defect analysis.

36 MATERIALS SCIENCE↗
NASA NTRS1993

Orthopyroxenes as recorders of diogenite petrogenesis: Trace element systematics

Eucrite, howardite, and diogenite members of the achondrites are considered, by many, to be genetically related. Therefore, each provide a piece of the puzzle for reconstructing magmatic processes on the eucrite parent body (EPB). The relationship between eucrites and diogenites can be viewed within the context of two distinctly different models: (1) fractional crystallization; and (2) partial melting. In fractional crystallization models, eucrites and diogenites represent a complementary continuum of planetary fractional crystallization products in which the diogenites represent crystal accumulations during the crystallization of eucritic magmas at shallow to deep levels in the EPB. Alternatively, experimental studies may be interpreted as indicating eucrites represent peritectic partial melts of a primitive, chondritic EPB mantle. Within this type of model, the diogenites are also generally considered to be cumulates; however, their petrogenetic relationship to the eucrites is less clear. Sack et al. proposed that the olivine diogenites represent residua from the partial melting events that produced eucritic liquids. Initial trace element studies of orthopyroxene (OPX) are consistent with this model. However, this trace element modeling of the olivine diogenites is nonunique. As a further test of these models, we did the following three things: (1) analyzed OPX from cumulate diogenites to compare with the olibine diogenite data; (2) improved ion microprobe analytical techniques for the analysis of elements critical to our interpretations; and (3) selected more relevant Kd's for OPX-eucritic melt.

Shearer, C. K.↗
NASA NTRS1992

Global and local current sheet thickness estimates during the late growth phase

The thinning and intensification of the cross tail current sheet during the substorm growth phase are analyzed during the CDAW 6 substorm (22 Mar. 1979) using two complementary methods. The magnetic field and current sheet development are determined using data from two spacecraft and a global magnetic field model with several free parameters. These results are compared with the local calculation of the current sheet location and structure previously done by McPherron et al. Both methods lead to the conclusion that an extremely thin current sheet existed prior to the substorm onset, and the thicknesses estimated by the two methods at substorm onset agree relatively well. The plasma data from the ISEE 1 spacecraft at 13 R(sub E) show an anisotropy in the low energy electrons during the growth phase which disappears just before the substorm onset. The global magnetic model results suggest that the field is sufficiently stretched to scatter such low energy electrons. The strong stretching may improve the conditions for the growth of the ion tearing instability in the near Earth tail at substorm onset.

Pulkkinen, T. I.↗
NASA NTRS2014

Connecting Lunar Meteorites to Source Terrains on the Moon

The number of named stones found on Earth that have proven to be meteorites from the Moon is approx. 180 so far. Since the Moon has been mapped globally in composition and mineralogy from orbit, it has become possible to speculate broadly on the region of origin on the basis of distinctive compositional characteristics of some of the lunar meteorites. In particular, Lunar Prospector in 1998 [1,2] mapped Fe and Th at 0.5 degree/pixel and major elements at 5 degree/pixel using gamma ray spectroscopy. Also, various multispectral datasets have been used to derive FeO and TiO2 concentrations at 100 m/pixel spatial resolution or better using UV-VIS spectral features [e.g., 3]. Using these data, several lunar meteorite bulk compositions can be related to regions of the Moon that share their distinctive compositional characteristics. We then use EPMA to characterize the petrographic characteristics, including lithic clast components of the meteorites, which typically are breccias. In this way, we can extend knowledge of the Moon's crust to regions beyond the Apollo and Luna sample-return sites, including sites on the lunar farside. Feldspathic Regolith Breccias. One of the most distinctive general characteristics of many lunar meteorites is that they have highly feldspathic compositions (Al2O3 approx. 28% wt.%, FeO <5 wt.%, Th <1 ppm). These compositions are significant because they are similar to a vast region of the Moon's farside highlands, the Feldspathic Highlands Terrane, which are characterized by low Fe and Th in remotely sensed data [4]. The meteorites provide a perspective on the lithologic makeup of this part of the Moon, specifically, how anorthositic is the surface and what, if any, are the mafic lithic components? These meteorites are mostly regolith breccias dominated by anorthositic lithic clasts and feldspathic glasses, but they do also contain a variety of more mafic clasts. On the basis of textures, we infer these clasts to have formed by large impacts that excavated and mixed rocks from depth within the lunar crust and possibly the upper mantle. One of the key questions is whether the mafic materials are ferroan or magnesian, which remote sensing does not clearly distinguish, and if mafic, whether they might contain mantlederived components such as olivine (dunite). Many but not all have mainly ferroan mafic components, consistent with a ferroan crustal source that is complementary to the ferroan anorthositic suite and that represents primary magma-ocean-derived feldspathic crust. Meteorites such as ALH 81005 [5] and Shişr 161 [6], however, contain coarse-grained magnesian mafic clasts (Fig. 1a) derived from deeply seated and melted material associated with impact basins. Comparison to LP gamma-ray data [2] supports an origin for magnesian feldspathic meteorites such as these (e.g., Shişr 161) as shown in Fig. 1b. Sayh al Uhaymir (SaU) 169. Another distinctive but much less common composition is represented by relatively mafic impact-melt breccia that is rich in incompatible elements known as KREEP. These meteorites can be related to the western nearside Procellarum KREEP Terrane, especially through a combination of Fe and Th contents. Among the most enriched is SaU 169, which has been related to high- Th impact-melt breccia found at the Apollo 12 site [7]. Through detailed EPMA and ion microprobe analysis we have shown that these two rock types are related in age and origin.

Jolliff, B. L.↗
DOE OSTI2021

Constraining the hadronic spectrum and repulsive interactions in a hadron resonance gas via fluctuations of conserved charges

We simultaneously incorporate two common extensions of the hadron resonance gas model, namely the addition of extra, unconfirmed resonances to the particle list and the excluded volume repulsive interactions. We emphasize the complementary nature of these two extensions and identify combinations of conserved charge susceptibilities that allow to constrain them separately. In particular, ratios of second-order susceptibilities like $\chi_{11}^{BQ}/\chi_2^B$ and $\chi_{11}^{BS}/\chi_2^B$ are sensitive only to the baryon spectrum, while fourth-to-second order ratios like $\chi_4^B/\chi_2^B$, $\chi_{31}^{BS}/\chi_{11}^{BS}$, or $\chi_{31}^{BQ}/\chi_{11}^{BQ}$ are mainly determined by repulsive interactions. Analysis of the available lattice results suggests the presence of both the extra states in the baryon-strangeness sector and the repulsive baryonic interaction, with indications that hyperons have a smaller repulsive core than non-strange baryons. Furthermore, the modified hadron resonance gas model presented here significantly improves the description of lattice QCD susceptibilities at chemical freeze-out and can be used for the analysis of event-by-event fluctuations in heavy-ion collisions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS1996

Far-Infrared Water Emissions from Magnetohydrodynamic Shock Waves

Nondissociative, magnetohydrodynamic, C-type shock waves are expected to be a prodigious source of far-infrared water emissions in dense interstellar regions. We have constructed a model to calculate the farinfrared H20 line spectra that emerge from such shocks. Using the best estimates currently available for the radiative cooling rate and the degree of ion-neutral coupling within the shocked gas, we modeled the temperature structure of MHD shocks using standard methods in which the charged and neutral particles are treated separately as two weakly coupled, interpenetrating fluids. Then we solved the equations of statistical equilibrium to find the populations of the lowest 179 and 170 rotational states of ortho- and para-H2O We have completed an extensive parameter study to determine the emergent H2O line luminosities as a function of preshock density in the range n(H2) equals 10(exp 4) - 10(sup 6.5)/cc and shock velocity in the range upsilon(sub s) = 5 - 40 km/ s. We find that numerous rotational transitions of water are potentially observable using the Infrared Space Observatory and the Submillimeter Wave Astronomy Satellite and may be used as diagnostics of the shocked gas. We have also computed the rotational and ro-vibrational emissions expected from H2, CO, and OH, and we discuss how complementary observations of such emissions may be used to further constrain the shock conditions. In common with previous studies, we come close to matching the observed H2, and high-J CO emissions from the Orion-KL star-forming region on the basis of a single shock model. We present our predictions for the strengths of H2O line emission from the Orion shock, and we show how our results may be scaled to other regions where molecular shocks are likely to be present.

Kaufman, Michael J.↗
DOE OSTI2026

Neutrino oscillation prospects with a dual-baseline beam from BNL to SNOLAB and SURF

The Electron-Ion Collider (EIC) is a next-generation accelerator primarily designed to study the internal structure of nucleons through high-precision electron-hadron collisions. In this work, we explore the feasibility of employing a 1 MW fraction of the EIC proton beam to generate a high-intensity GeV-scale neutrino beam for long-baseline oscillation studies. We have simulated proton-target interactions and optimize the resulting neutrino fluxes for water-based liquid scintillator (WbLS) detectors located at distinct baselines of 900 km and at 2900 km. Oscillation analyses performed with GLoBES show that extended baselines allow access to multiple oscillation maxima, significantly enhancing sensitivity to leptonic CP violation. The study also examines the interplay between matter effects and the intrinsic CP violating phase in shaping observable asymmetries. We note that simplified systematics and no backgrounds are used in this analysis to establish the baseline physics potential. These results suggest that the EIC proton beam could provide a novel and complementary source for precision neutrino physics, extending the scientific reach of the EIC program.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS1993

The abundance of CH(+) in translucent molecular clouds - Further tests of shock models

Observations of interstellar absorption lines of CH(+) in the (0, 0) and (1, 0) bands of the A 1Pi - X 1Sigma(+) system are presented for 17 stars with reddenings up to E(B-V) about 1.5 mag. Complementary data on interstellar CH in the (0, 0) bands of the A 2Delta - X 2Pi and B 2Sigma(-) - X 2Pi systems and C2 in the A 1Pi(u) - X 1Sigma(g)(+) red system have been obtained as well. The derived CH(+) column densities continue to increase with total column density, and values up to 10 exp 14/sq cm are reported for highly-reddened lines of sight. In most cases, the CH(+) and CH absorptions are dominated by a single strong component, with weaker features displaced by a few km/s. No significant velocity difference is found between CH(+) and neutral species such as CH and CN for this sample of randomly oriented lines of sight. In contrast with CN, the CH(+) abundance does not increase with the density in the cloud as derived from the observed C2 excitation. For the two clouds with the largest density, HD 62542 and HD 94413, no CH(+) absorption is found with CH(+)/CH less than 0.03 and 0.14, respectively. The CH(+) findings do not support a single-shock origin for the formation of the ion.

Gredel, R.↗
NASA NTRS2003

Unified Models of Turbulence and Nonlinear Wave Evolution in the Extended Solar Corona and Solar Wind

The PI (Cranmer) and Co-I (A. van Ballegooijen) made significant progress toward the goal of building a "unified model" of the dominant physical processes responsible for the acceleration of the solar wind. The approach outlined in the original proposal comprised two complementary pieces: (1) to further investigate individual physical processes under realistic coronal and solar wind conditions, and (2) to extract the dominant physical effects from simulations and apply them to a one-dimensional and time-independent model of plasma heating and acceleration. The accomplishments in the report period are thus divided into these two categories: 1a. Focused Study of Kinetic MHD Turbulence. We have developed a model of magnetohydrodynamic (MHD) turbulence in the extended solar corona that contains the effects of collisionless dissipation and anisotropic particle heating. A turbulent cascade is one possible way of generating small-scale fluctuations (easy to dissipate/heat) from a pre-existing population of low-frequency Alfven waves (difficult to dissipate/heat). We modeled the cascade as a combination of advection and diffusion in wavenumber space. The dominant spectral transfer occurs in the direction perpendicular to the background magnetic field. As expected from earlier models, this leads to a highly anisotropic fluctuation spectrum with a rapidly decaying tail in the parallel wavenumber direction. The wave power that decays to high enough frequencies to become ion cyclotron resonant depends on the relative strengths of advection and diffusion in the cascade. For the most realistic values of these parameters, though, there is insufficient power to heat protons and heavy ions. The dominant oblique waves undergo Landau damping, which implies strong parallel electron heating. We thus investigated the nonlinear evolution of the electron velocity distributions (VDFs) into parallel beams and discrete phase-space holes (similar to those seen in the terrestrial magnetosphere) which are an alternate means of heating protons via stochastic interactions similar to particle-particle collisions. 1b. Focused Study of the Multi-Mode Detailed Balance Formalism. The PI began to explore the feasibility of using the "weak turbulence," or detailed-balance theory of Tsytovich, Melrose, and others to encompass the relevant physics of the solar wind. This study did not go far, however, because if the "strong" MHD turbulence discussed above is a dominant player in the wind's acceleration region, this formalism is inherently not applicable to the corona. We will continue to study the various published approaches to the weak turbulence formalism, especially with an eye on ways to parameterize nonlinear wave reflection rates. 2. Building the Unified Model Code Architecture. We have begun developing the computational model of a time-steady open flux tube in the extended corona. The model will be "unified" in the sense that it will include (simultaneously for the first time) as many of the various proposed physical processes as possible, all on equal footing. To retain this generality, we have formulated the problem in two interconnected parts: a completely kinetic model for the particles, using the Monte Carlo approach, and a finite-difference approach for the self-consistent fluctuation spectra. The two codes are run sequentially and iteratively until complete consistency is achieved. The current version of the Monte Carlo code incorporates gravity, the zero-current electric field, magnetic mirroring, and collisions. The fluctuation code incorporates WKJ3 wave action conservation and the cascade/dissipation processes discussed above. The codes are being run for various test problems with known solutions. Planned additions to the codes include prescriptions for nonlinear wave steepening, kinetic velocity-space diffusion, and multi-mode coupling (including reflection and refraction).

Cranmer, Steven R.↗
NASA NTRS1994

Particle/fluid simulations of an eruptive flare: Identifying the field-aligned currents responsible for the hard x-rays

While magnetohydrodynamics (MHD) can provide a reasonable description of the overall magnetic reconnection that is believed to drive flares, additional, and often separate processes have to be envoked to in order to explain the electron acceleration that is responsible for many of the observed flare emissions. A new model that incorporates the dynamic coronal current sheets, the reconnection site, and possible electron acceleration processes is developed through the use of two-dimensional particle and modified two-fluid simulations. The specific example of an eruptive flare driven by the coalescence of flux tubes supported by prescribed photospheric current elements is evaluated. It is shown that the electrons and ions have differential trajectories through the coronal current sheet which leads to the development of additonal plasma currents that flow around the surface of the current sheet. These surface currents are explicitly neglected in MHD but they are vital to the flare dynamics because they divert current from the coronal current sheet into the chromosphere, producing an effective resistivity that aids the development of fast reconnection. Because the surface currents are in the plane of the magnetic field, electrons in them experience strong acceleration and can account for the observed hard X-ray emissions. Model predictions are compared with observed time profiles of hard X-ray emissions and Doppler shifts seen in soft X-ray line emissions and are able to account for such features as (1) the asymmetry in the rise and decay time of the hard X-rays, (2) the apparent delay between the largest Doppler shifts and the hard X-ray peak, and (3) the relatively low intensity of the blue-shifted component. The use of particle and fluid simulations is important because it provides different, but complementary treatments of the electron acceleration, the global magnetic morphology, and the flare current system.

Winglee, R. M.↗
DOE OSTI2020

4D imaging of lithium-batteries using correlative neutron and X-ray tomography with a virtual unrolling technique

The temporally and spatially resolved tracking of lithium intercalation and electrode degradation processes are crucial for detecting and understanding performance losses during the operation of lithium-batteries. Here, high-throughput X-ray computed tomography has enabled the identification of mechanical degradation processes in a commercial Li/MnO 2 primary battery and the indirect tracking of lithium diffusion; furthermore, complementary neutron computed tomography has identified the direct lithium diffusion process and the electrode wetting by the electrolyte. Virtual electrode unrolling techniques provide a deeper view inside the electrode layers and are used to detect minor fluctuations which are difficult to observe using conventional three dimensional rendering tools. Moreover, the 'unrolling' provides a platform for correlating multi-modal image data which is expected to find wider application in battery science and engineering to study diverse effects e.g. electrode degradation or lithium diffusion blocking during battery cycling.

25 ENERGY STORAGE↗
DOE OSTI2023

Cation-Driven Assembly of Bilayered Vanadium Oxide and Graphene Oxide Nanoflakes to Form Two-Dimensional Heterostructure Electrodes for Li-Ion Batteries

Lithium preintercalated bilayered vanadium oxide (LVO or δ-Li x V 2 O 5 ·nH 2 O) and graphene oxide (GO) nanoflakes were assembled using a concentrated lithium chloride solution and annealed under vacuum at 200 °C to form two-dimensional (2D) δ-Li x V 2 O 5 ·nH 2 O and reduced GO (rGO) heterostructures. Here we found that the Li + ions from LiCl enhanced the oxide/carbon heterointerface formation and served as stabilizing ions to improve structural and electrochemical stability. The graphitic content of the heterostructure could be easily controlled by changing the initial GO concentration prior to assembly. We found that increasing the GO content in our heterostructure composition helped inhibit the electrochemical degradation of LVO during cycling and improved the rate capability of the heterostructure. A combination of scanning electron microscopy and X-ray diffraction was used to help confirm that a 2D heterointerface formed between LVO and GO, and the final phase composition was determined using energy-dispersive X-ray spectroscopy and thermogravimetric analysis. Scanning transmission electron microscopy and electron energy-loss spectroscopy were additionally used to examine the heterostructures at high resolution, mapping the orientations of rGO and LVO layers and locally imaging their interlayer spacings. Further, electrochemical cycling of the cation-assembled LVO/rGO heterostructures in Li-ion cells with a non-aqueous electrolyte revealed that increasing the rGO content led to improved cycling stability and rate performance, despite slightly decreased charge storage capacity. The heterostructures with 0, 10, 20, and 35 wt % rGO exhibited capacities of 237, 216, 174, and 150 mAh g –1 , respectively. Moreover, the LVO/rGO-35 wt % and LVO/rGO-20 wt % heterostructures retained 75% (110 mAh g–1) and 67% (120 mAh g –1 ) of their initial capacities after increasing the specific current from 20 to 200 mA g –1 , while the LVO/rGO-10 wt % sample retained only 48% (107 mAh g –1 ) of its initial capacity under the same cycling conditions. In addition, the cation-assembled LVO/rGO electrodes exhibited enhanced electrochemical stability compared to electrodes prepared through physical mixing of LVO and GO nanoflakes in the same ratios as the heterostructure electrodes, further revealing the stabilizing effect of a 2D heterointerface. The cation-driven assembly approach, explored in this work using Li + cations, was found to induce and stabilize the formation of stacked 2D layers of rGO and exfoliated LVO. The reported assembly methodology can be applied for a variety of systems utilizing 2D materials with complementary properties for applications as electrodes in energy storage devices.

25 ENERGY STORAGE↗
DOE OSTI2021

Coexistence and Coupling of Multiple Charge Orderings and Spin States in Hexagonal Ferrite

The coupling between charge and spin orderings in strongly correlated systems plays a crucial role in fundamental physics and device applications. As a candidate of multiferroic materials, LuFe 2 O 4 with a nominal Fe 2.5+ valence state has the potential for strong charge–spin interactions; however, these interactions have not been fully understood until now. Here, combining complementary characterization methods with theoretical calculations, two types of charge orderings with distinct magnetic properties are revealed. The ground states of LuFe 2 O 4 are decided by the parallel/antiparallel coupling of both charge and spin orderings in the adjacent FeO double layers. Whereas the ferroelectric charge ordering remains ferrimagnetic below 230 K, the antiferroelectric ordering undergoes antiferromagnetic–ferrimagnetic–paramagnetic transitions from 2 K to room temperature. This study demonstrates the unique aspects of strong spin-charge coupling within LuFe 2 O 4 . Our results shed light on the coexistence and competing nature of orderings in quantum materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS2015

Compositional and Microstructural Evolution of Olivine During Pulsed Laser Irradiation: Insights Based on a FIB/Field-Emission TEM Study

Introduction: The use of pulsed laser irradiation to simulate the short duration, high-energy conditions characteristic of micrometeorite impacts is now an established approach in experimental space weathering studies. The laser generates both melt and vapor deposits that contain nanophase metallic Fe (npFe(sup 0)) grains with size distributions and optical properties similar to those in natural impact-generated melt and vapor deposits. There remains uncertainty, however, about how well lasers simulate the mechanical work and internal (thermal) energy partitioning that occurs in actual impacts. We are currently engaged in making a direct comparison between the products of laser irradiation and experimental/natural hypervelocity impacts. An initial step reported here is to use analytical TEM is to attain a better understanding of how the microstructure and composition of laser deposits evolve over multiple cycles of pulsed laser irradiation. Experimental Methods: We irradiated pressed-powder pellets of San Carlos olivine (Fo(sub 90)) with up to 99 rastered pulses of a GAM ArF excimer laser. The irradiated surface of the sample were characterized by SEM imaging and areas were selected for FIB cross sectioning for TEM study using an FEI Quanta dual-beam electron/focused ion beam instrument. FIB sections were characterized using a JEOL2500SE analytical field-emission scanning transmission electron microscope (FE-STEM) optimized for quantitative element mapping at less than 10 nm spatial resolutions. Results: In the SEM the 99 pulse pressed pellet sample shows a complex, inhomogeneous, distribution of laser-generated material, largely concentrated in narrow gaps and larger depressions between grains. Local concentrations of npFe0 spherules 0.1 to 1 micrometers in size are visible within these deposits in SEM back-scatter images. Fig. 1 shows bright-field STEM images of a FIB cross-section of a one of these deposits that continuously covers the top and sloping side of an olivine grain. The deposit has 3 microstructurally distinct sub-layers composed of silicate glass with varying modal fractions and size distributions of npFe( sup 0) spherules, along with nanocrystalline silicate material. A relatively thin (50-300 nm) topmost surface layer has a high-concentration of npFe0 spherules 5-20 nm in size. Element mapping shows the layer to be enriched in Fe by a factor of 2.5 relative to the olivine substrate, with Mg and Si depleted by 20% and 10% respectively. This is compositionally complementary to the underlying, middle layer of the deposit that is depleted in Fe, enriched in Mg and has a much lower npFe0 concentration. A third layer of nanocrystalline olivine occurs at the substrate interface. Discussion: The FE-STEM results suggest the topmost layer is a vapor deposit, underlain by a thicker microstructurally complex melt-generated layer. The compositional relations suggest the melt layer was partially vaporized, preferentially losing more volatile elements (e.g., Fe). The vaporized material re-condensed to form the thin, npFe(sup 0)-rich surface deposit during or immediately after the scan cycle. Nanocrystalline olivine that grew within the melt layer as it formed and cooled is similar in volume and microstructure to what we have observed in the impact melt lining of a micrometeorite impact crater in olivine. This suggest the time-temperature relations attained in the laser sample may not be too different from a micrometeorite impact. Our TEM observations, however, do not show evidence for the same level of mechanical dam-age (e.g., fracturing) seen around the natural micrometeorite crater.

Christoffersen, R.↗