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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 181 records · Page 10

New promising lithium malonatoborate salts for high voltage lithium ion batteries

Here, three new lithium salts, lithium difluoro-2-methyl-2-fluoromalonaoborate (LiDFMFMB), lithium difluoro-2-ethyl-2-fluoromalonaoborate (LiDFEFMB), and lithium difluoro-2-propyl-2-fluoro malonaoborate (LiDFPFMB), have been synthesized and evaluated for application in lithium ion batteries. These new salts are soluble in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (1:2 by wt.) and 1.0 M salt solutions can be easily prepared. The ionic conductivities of these new salts are close to those of LiBF 4 and LiPF 6 . Cyclic voltammograms reveal that these new salt based electrolytes can passivate both natural graphite and high voltage spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) to form effective solid electrolyte interphases (SEIs). In addition, these new salts based electrolytes exhibit good cycling stability with high coulombic efficiencies in both LiNi 0.5 Mn 1.5 O 4 and graphite based half-cells and full cells.

25 ENERGY STORAGE↗

Electrolytes for Li-Ion Cells in Low Temperature Applications

Prototype AA-size lithium-ion cells have been demonstrated to operate effectively at temperatures as low as -30 to -40 C. These improvements in low temperature cell performance have been realized by the incorporation of ethylene carbonate-based electrolytes which possess low melting, low viscosity cosolvents, such as methyl acetate, ethyl acetate, gamma-butyrolactone, and ethyl methyl carbonate. The cells containing a 0.75M LiPF6 EC+DEC+DMC+EMC (1:1:1:1) electrolyte displayed the best performance at -30 C (> 90% of the room temperature capacity at approximately C/15 rate), whereas, at -40 C the cells with the 0.75M LiPF6 EC+DEC+DMC+MA (1:1:1:1) and 0.75M LiPF6 EC+DEC+DMC+EA (1:1:1:1) electrolytes showed superior performance.

Smart, M. C.↗

Field of View Analysis of SeaWinds Reflector Antenna

Antennas are often mounted among many other instruments on the spacecraft platform. The electromagnetic interference (EMI) and compatibility (EMC) issues are of great concern to the antenna and spacecraft system design engineers. Considering the rotating reflector antenna of the NASA SeaWinds Scatterometer on the Japanes ADEOS II spacecraft, it is desirable to determine the antenna's field of view (FOV) performance. In other words, how far should the other boxes be kept away from the reflector antenna to minimize the blockage/diffraction effects on the antenna's performance requirements.

electromagnetic interference EMI↗

Determination of crystallographic intensities from sparse data

X-ray serial microcrystallography involves the collection and merging of frames of diffraction data from randomly oriented protein microcrystals. The number of diffracted X-rays in each frame is limited by radiation damage, and this number decreases with crystal size. The data in the frame are said to be sparse if too few X-rays are collected to determine the orientation of the microcrystal. It is commonly assumed that sparse crystal diffraction frames cannot be merged, thereby setting a lower limit to the size of microcrystals that may be merged with a given source fluence. The EMC algorithm [Loh & Elser (2009), Phys. Rev. E , 80 , 026705] has previously been applied to reconstruct structures from sparse noncrystalline data of objects with unknown orientations [Philipp et al. (2012), Opt. Express , 20 , 13129–13137; Ayyer et al. (2014), Opt. Express , 22 , 2403–2413]. Here, it is shown that sparse data which cannot be oriented on a per-frame basis can be used effectively as crystallographic data. As a proof-of-principle, reconstruction of the three-dimensional diffraction intensity using sparse data frames from a 1.35 kDa molecule crystal is demonstrated. The results suggest that serial microcrystallography is, in principle, not limited by the fluence of the X-ray source, and collection of complete data sets should be feasible at, for instance, storage-ring X-ray sources.

Chemistry↗

Designing Li 4 Ti 5 O 12 /LiMn 2 O 4 Cells: Negative-to-Positive Ratio and Electrolyte

Li 4 Ti 5 O12/LiMn2O 4 (LTO/LMO) system is a promising candidate for behind-the-meter storage (BTMS) applications due to its critical-material-free chemistry exhibiting good safety and long lifetime. In this paper we design LTO/LMO cells to mitigate their major degradation mechanism, loss of Li inventory, and improve their long-term cyclability. First, LMO electrodes with different loadings (2.61, 3.29, and 4.26 mAh cm -2 ) are paired with an LTO electrode (3.35 mAh cm -2 ) to create varying negative-to-positive ratios (N/P>1, =1, and <1). Additionally, conventional ethylene carbonate (EC)/ethyl methyl carbonate (EMC) mixture electrolyte and safety enhanced EC-only electrolyte are examined. We show that storing additional Li inventory in the cathode (i.e., using a thicker electrode and having N/P<1) is a convenient method to enhance the capacity retention of LTO/LMO cells, but only if the electrode utilization is not limited by the Li + ion transport. For systems that suffer from limited transport properties, prelithiating the anode will be more effective since LTO (~165 mAh g -1 LTO ) can store the same amount of capacity using less material compared to LMO (~100 mAh g -1 LMO ). In this work, we demonstrate how the electrolyte properties and the electrode thickness of LTO/LMO cells can be designed to enhance their performance.

25 ENERGY STORAGE↗

End-to-End Trajectory for Conjunction Class Mars Missions Using Hybrid Solar-Electric/Chemical Transportation System

NASA's Human Spaceflight Architecture Team is developing a reusable hybrid transportation architecture in which both chemical and solar-electric propulsion systems are used to deliver crew and cargo to exploration destinations. By combining chemical and solar-electric propulsion into a single spacecraft and applying each where it is most effective, the hybrid architecture enables a series of Mars trajectories that are more fuel efficient than an all chemical propulsion architecture without significant increases to trip time. The architecture calls for the aggregation of exploration assets in cislunar space prior to departure for Mars and utilizes high energy lunar-distant high Earth orbits for the final staging prior to departure. This paper presents the detailed analysis of various cislunar operations for the EMC Hybrid architecture as well as the result of the higher fidelity end-to-end trajectory analysis to understand the implications of the design choices on the Mars exploration campaign.

Chai, Patrick R.↗

Protein crystal structure from non-oriented, single-axis sparse X-ray data

X-ray free-electron lasers (XFELs) have inspired the development of serial femtosecond crystallography (SFX) as a method to solve the structure of proteins. SFX datasets are collected from a sequence of protein microcrystals injected across ultrashort X-ray pulses. The idea behind SFX is that diffraction from the intense, ultrashort X-ray pulses leaves the crystal before the crystal is obliterated by the effects of the X-ray pulse. The success of SFX at XFELs has catalyzed interest in analogous experiments at synchrotron-radiation (SR) sources, where data are collected from many small crystals and the ultrashort pulses are replaced by exposure times that are kept short enough to avoid significant crystal damage. The diffraction signal from each short exposure is so `sparse' in recorded photons that the process of recording the crystal intensity is itself a reconstruction problem. Using the EMC algorithm, a successful reconstruction is demonstrated here in a sparsity regime where there are no Bragg peaks that conventionally would serve to determine the orientation of the crystal in each exposure. In this proof-of-principle experiment, a hen egg-white lysozyme (HEWL) crystal rotating about a single axis was illuminated by an X-ray beam from an X-ray generator to simulate the diffraction patterns of microcrystals from synchrotron radiation. Millions of these sparse frames, typically containing only ~200 photons per frame, were recorded using a fast-framing detector. It is shown that reconstruction of three-dimensional diffraction intensity is possible using the EMC algorithm, even with these extremely sparse frames and without knowledge of the rotation angle. Further, the reconstructed intensity can be phased and refined to solve the protein structure using traditional crystallographic software. In conclusion, this suggests that synchrotron-based serial crystallography of micrometre-sized crystals can be practical with the aid of the EMC algorithm even in cases where the data are sparse.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

The Effect of Electrolyte Additives upon the Lithium Kinetics of Li-Ion Cells Containing MCMB and LiNi(x)Co(1-x)O2 Electrodes and Exposed to High Temperatures

With the intent of improving the performance of lithium-ion cells at high temperatures, we have investigated the use of a number of electrolyte additives in experimental MCMB- Li(x)Ni(y)Co(1-y)O2 cells, which were exposed to temperatures as high as 80 C. In the present work, we have evaluated the use of a number of additives, namely vinylene carbonate (VC), dimethyl acetamide (DMAc), and mono-fluoroethylene carbonate (FEC), in an electrolyte solution anticipated to perform well at warm temperature (i.e., 1.0M LiPF6 in EC+EMC (50:50 v/v %). In addition, we have explored the use of novel electrolyte additives, namely lithium oxalate and lithium tetraborate. In addition to determining the capacity and power losses at various temperatures sustained as a result of high temperature cycling (cycling performed at 60 and 80 C), the three-electrode MCMB-Li(x)Ni(y)Co(1-y)O2 cells (lithium reference) enabled us to study the impact of high temperature storage upon the solid electrolyte interphase (SEI) film characteristics on carbon anodes (MCMB-based materials), metal oxide cathodes, and the subsequent impact upon electrode kinetics.

High Temperture Resilience↗

Using the Charge-Discharge Cycling of Positive Electrode Symmetric Cells to Find Electrolyte/Electrode Combinations with Minimum Reactivity

The effects of solvents, salts, electrolyte additives and surface coatings on LiNi 0.4 Mn 0.4 Co 0.2 O 2 (NMC442) or LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) have been probed using positive electrode Li-ion symmetric cells coupled with dV/dQ analysis. A robust symmetric cell design is presented which prevents hardware corrosion for over at least 800 hours of testing to 4.5 V vs. Li/Li + at 40°C. Positive electrode symmetric cells using uncoated positive electrode materials and 1M LiPF 6 EC:EMC 3:7 or 1M LiPF 6 EMC electrolyte rapidly developed high impedance and showed poor capacity retention. However, if 1% pyridine boron trifluoride (PBF) was added to these electrolytes, cell performance was dramatically improved. Replacing LiPF 6 by LiBF 4 in the electrolytes above, with or without PBF, yielded positive electrode symmetric cells with good capacity retention. Two types of surface coatings were explored on NMC622 positive electrodes. Cells using surface-coated positive electrodes demonstrated better capacity retention for all electrolytes compared to cells without surface coatings. Finally, this work can be used as a guide by those attempting to find electrolyte/electrode pairs suitable for use in NMC/graphite cells that can operate with long lifetime to 4.5 V.

25 ENERGY STORAGE↗

Interfacial Effects on Transport Coefficient Measurements in Li-ion Battery Electrolytes

Development of Li + -containing electrolytes with improved transport properties requires reliable, reproducible, and ideally low volume techniques to rigorously understand ion-transport with varying composition. Precisely measuring the complete set of transport coefficients in liquid electrolytes under battery-relevant operating conditions is difficult and the reliability of these methods are sparsely described in electrolyte transport literature. In this work, we apply a potentiostatic polarization-based transport characterization approach typically used for polymer electrolytes to liquid electrolyte systems in an attempt to fully measure all transport coefficients (conductivity, total salt diffusion coefficient, thermodynamic factor and transference number) for the model system of LiPF 6 in an ethylene carbonate—ethyl methyl carbonate (EC:EMC) mixture. Using systematic timescale and statistical analyses, we find that transport coefficients measured using potentiostatic polarization of Li-Li symmetric cells exhibit strong correlation to Li electrode interfacial resistance, indicating that such methods are probing both bulk and interfacial phenomena. This reveals a major roadblock in characterizing electrolyte systems where the interfacial resistance is significantly larger than ohmic electrolyte resistance. As a result, we find that methods that rely on potentiostatic Li metal stripping/plating do not readily result in reliable liquid electrolyte transport coefficients, unlike similar methods for solid polymer electrolytes, where interfacial resistances are typically smaller than electrolyte resistances at the elevated temperatures typically of interest for such electrolytes.

25 ENERGY STORAGE↗

NASAs Evolvable Mars Campaign: Mars Moons Robotic Precursor

Human exploration missions to the moons of Mars are being considered within NASA's Evolvable Mars Campaign (EMC) as an intermediate step for eventual human exploration and pioneering of the surface of Mars. A range of mission architectures is being evaluated in which human crews would explore one or both moons for as little as 14 days or for as long as 500 days with a variety of orbital and surface habitation and mobility options being considered. Relatively little is known about the orbital, surface, or subsurface characteristics of either moon. This makes them interesting but challenging destinations for human exploration missions during which crewmembers must be able to effectively conduct scientific exploration without being exposed to undue risks due to radiation, dust, micrometeoroids, or other hazards. A robotic precursor mission to one or both moons will be required to provide data necessary for the design and operation of subsequent human systems and for the identification and prioritization of scientific exploration objectives. This paper identifies and discusses considerations for the design of such a precursor mission based on current human mission architectures. Objectives of a Mars' moon precursor in support of human missions are expected to include: 1) identifying hazards on the surface and the orbital environment at up to 50-km distant retrograde orbits; 2) collecting data on physical characteristics for planning of detailed human proximity and surface operations; 3) performing remote sensing and in situ science investigations to refine and focus future human scientific activities; and 4) prospecting for in situ resource utilization. These precursor objectives can be met through a combination or remote sensing (orbital) and in-situ (surface) measurements. Analysis of spacecraft downlink signals using radio science techniques would measure the moon's mass, mass distribution, and gravity field, which will be necessary to enable trajectory planning. Laser altimetry would precisely measure the moon's shape and improve the accuracy of radio science measurements. A telescopic imaging camera would map the moon at submeter resolution and photograph selected areas of interest at subcentimeter resolution and a visible and near-infrared (0.4-3.0 mm) imaging spectrograph would produce a global map of mineral composition variations at a resolution of tens of meters and maps of selected areas of interest at meter resolution. Additional remote sensing capabilities could include a thermal infrared imager (heat flow, thermal inertia, and grain size distributions), a gamma-ray and neutron detector (atomic composition), a ground-penetrating radar (internal structure), and a magnetometer and Langmuir probe (magnetic properties and plasma field). Once on the surface of Phobos or Deimos, necessary instrumentation would include a penetrometer (regolith compressive strength), a motion-imagery camera (to observe the penetrometer tests before, during, and after contact), a dust-adhesion witness plate and camera (dust levitation), a microimager (dust particle sizes and shapes), and an alpha-proton-X-ray, X-ray fluorescence, Mossbauer, or Raman spectrometer (atomic and mineral composition of surface materials) and an optional temperature probe (regolith thermal properties). A variety of robotic mission design options to enable both orbital and surface measurements are being considered that include fully integrated and modular approaches. In-situ measurements from at least one surface location would be required, with additional measurement locations possible through use of multiple landers, through propulsive relocation of a single lander, or through electromechanical surface translation by a walking or hopping lander vehicle, which could also serve to evaluate such mobility capabilities for subsequent human missions. Preliminary orbital analysis suggests that remote sensing would likely be performed while in a distant retrograde orbit around the target moon. Mission design options to enable characterization of both Mars’ moons in a single mission are also being studied.

Gernhardt, Michael L.↗

Effect of Vinylene Carbonate and Fluoroethylene Carbonate on SEI Formation on Graphitic Anodes in Li-Ion Batteries

Binder free (BF) graphite electrodes were utilized to investigate the effect of electrolyte additives fluoroethylene carbonate (FEC) and vinylene carbonate (VC) on the structure of the solid electrolyte interface (SEI). The structure of the SEI has been investigated via ex-situ surface analysis including X-ray Photoelectron spectroscopy (XPS), Hard XPS (HAXPES), Infrared spectroscopy (IR) and transmission electron microscopy (TEM). The components of the SEI have been further investigated via nuclear magnetic resonance (NMR) spectroscopy of D2O extractions. The SEI generated on the BF-graphite anode with a standard electrolyte (1.2 M LiPF6 in ethylene carbonate (EC) / ethyl methyl carbonate (EMC), 3/7 (v/v)) is composed primarily of lithium alkyl carbonates (LAC) and LiF. Incorporation of VC (3% wt) results in the generation of a thinner SEI composed of Li2CO3, poly(VC), LAC, and LiF. Incorporation of VC inhibits the generation of LAC and LiF. Incorporation of FEC (3% wt) also results in the generation of a thinner SEI composed of Li2CO3, poly(FEC), LAC, and LiF. The concentration of poly(FEC) is lower than the concentration of poly(VC) and the generation of LAC is inhibited in the presence of FEC. The SEI appears to be a homogeneous film for all electrolytes investigated.

25 ENERGY STORAGE↗

Damage of Elastomeric Matrix Composites (EMC-rubbers) Under Static Loading Conditions: Experimental and Numerical Study

Elastomeric matrix composites (EMC-rubbers) are considered as isotropic hyper elastic incompressible materials under static loading conditions. As a rubber material element cannot be extended to an infinite stretch ratio, a damage mechanism at large strain is considered. The phenomenon of cavitation plays an important role in the damage of EMCs and influences the toughening mechanism of rubber-modified plastics. Indeed, cavitation in elastomers is thought to be initiated from flaws, which grow primarily due to a hydrostatic tensile stress and ahead of the crack; there will not only be a high stress perpendicular to the plane of the crack but also significant stress components in the other direction. However, there exists historically much discussion on the evolution of the cavitation in elastomers under monotonic and/or static solicitation. Mainly, cavitation instability occurs when the stress levels are sufficiently high so that the void expansion rate becomes infinitely large. Many research works have been performed to understand the effects of rubber cavitation on toughening of plastics. In fact, the cavitation phenomenon is not well known in detail. The most popular idea states that the cavitation is related to the existence of the gas bubbles trapped in the material during the production stage and the growing of the cavities would then be the result of the growing gas bubbles. Further, instable failure mechanism at the end of the cavitation is not well known too.

36 MATERIALS SCIENCE↗

Isolation and conversion of electrolyte components into a value-added product

The overall objective of this work was to develop a process for effectively (i) recycling the electrolyte components from the end-of-life batteries and reduce the environmental hazard, (ii) understand the fundamental differences between pristine and recycled electrolyte components, (iii) electrochemically and analytically evaluate the recycled electrolyte components and (iv) establish deviations from the pristine electrolyte, and effectively separation of value-added product. We focused on determining scaling up the electrolyte recovery process by distillation of end-of-life batteries to get yield enough to use it for electrolyte formulation of reuse in the battery cell. The used cells from the ORNL battery manufacture facility (BMF)as well as received from the industry partner, Austin Elements Inc., was scaled to 10 used multilayered pouch cells in each batch of distillation and systematically separated and identified the electrolyte components of the used cells with FTIR and NMR studies. We were able to recovery 10g of solvent mass from the used pouch cells. NMR spectroscopy showed that the solvent was pure EMC,DMC and the sample was used to make a new battery cell. The end-of-life battery, it was noted that some cells were visually drier than the other cells and were more advanced in aged. In that case, even though the same distillation conditions were utilized, no usable mass of electrolyte solvent was recovered. It is expected that most of the solvent was decomposed during the battery charge-discharge cycling. The solid salt residue was separated by chemical and water treatment processes. Components of resulting solid product was analyzed by XRD and XPS measurements. The solid products are very much related to the salts used in the electrolyte solution.

25 ENERGY STORAGE↗

Isolation and Conversion of Electrolyte Components into a Value-Added Product

The overall objective of this work was to develop a process for effectively (i) recycling the electrolyte components from the end-of-life batteries and reduce the environmental hazard, (ii) understand the fundamental differences between pristine and recycled electrolyte components, (iii) electrochemically and analytically evaluate the recycled electrolyte components and (iv) establish deviations from the pristine electrolyte, and effectively separation of value-added product. We focused on determining scaling up the electrolyte recovery process by distillation of end-of-life batteries to get yield enough to use it for electrolyte formulation of reuse in the battery cell. The used cells from the ORNL battery manufacture facility (BMF) as well as received from the industry partner, Austin Elements Inc., was scaled to 10 used multilayered pouch cells in each batch of distillation and systematically separated and identified the electrolyte components of the used cells with FTIR and NMR studies. We were able to recovery 10g of solvent mass from the used pouch cells. NMR spectroscopy showed that the solvent was pure EMC, DMC and the sample was used to make a new battery cell. The end-of-life battery, it was noted that some cells were visually drier than the other cells and were more advanced in aged. In that case, even though the same distillation conditions were utilized, no usable mass of electrolyte solvent was recovered. It is expected that most of the solvent was decomposed during the battery charge-discharge cycling. The solid salt residue was separated by chemical and water treatment processes. Components of resulting solid product was analyzed by XRD and XPS measurements. The solid products are very much related to the salts used in the electrolyte solution.

25 ENERGY STORAGE↗

Conceptual Model of Autonomous Seed Germination Habitat for Mars Mission

As human space exploration extends to Mars, the ability to germinate seeds in extraterrestrial environments is becoming a necessity. Recent technological feats such as the development of the European Modular Cultivation System (EMCS) have made botany experiments possible on the International Space Station (ISS). Despite preliminary designs, a biocompatible plant life support system capable of traveling to Mars has yet to be developed. This study focuses on two preparatory measures regarding seed germination in spaceflight: analysis of seed dormancy protocols and compact autonomous habitat development.The objective of this project is to conceptualize a habitat capable of preserving arabidopsis plant seeds on a long duration spaceflight for the purpose of germinating the first plants on Mars. The proposed container will require a compact, low wattage system to provide gas ventilation, artificial light, and water. A visualization system will also need to be developed in order to monitor seed germination remotely. In order to test the effects of dormancy durations on plant viability, we will conduct a ground study to monitor seed germination in seeds which have been dormant for three, six, nine, and twelve months. We will also compare the effects of different sterilization procedures. The results of this study will be instrumental in developing a viable procedure for transferring the first living plants to Mars.

Peter, Jonah↗

Theory of Cation Solvation in the Helmholtz Layer of Li-Ion Battery Electrolytes

The solvation environments of Li + in conventional nonaqueous battery electrolytes, such as LiPF 6 in mixtures of ethylene carbaronate (EC) and ethyl methyl carbonate (EMC), are often used to rationalize transport properties and solid electrolyte interphase (SEI) formation. Solvation environments in the compact electrical double layer (EDL) next to the electrode, also known as the Helmholtz layer, determine (partially) what species can react to form the SEI, with bulk solvation environments often being used as a proxy. Here, we develop and test a theory of cation solvation in the Helmholtz layer of nonaqueous Li-ion battery electrolytes. First, we validate the theory against bulk and diffuse EDL atomistic molecular dynamics (MD) simulations of LiPF 6 EC/EMC mixtures as a function of surface charge, where we find the theory can qualitatively capture the solvation environments. Next, we turn to the Helmholtz layer, where we find the main effect of the solvation structures next to the electrode is an apparent reduction in the number of binding sites between Li + and the solvents, again where we find reasonable agreement with our developed theory. Finally, by solving a simplified version of the theory, we find that the probability of Li + binding to each solvent remains equal to the bulk probability, suggesting that the bulk solvation environments are a reasonable place to start when understanding battery electrolytes. Our developed formalism can be parametrized from bulk MD simulations and used to predict the solvation environments in the Helmholtz layer through reducing the number of available coordination sites, which can be used to determine what could react and form the SEI.

Helmholtz↗

Mid-Lift-to-Drag Ratio Rigid Vehicle 6-DOF EDL Performance Using Tunable Apollo Powered Guidance

The Mid-Lift-to-Drag ratio Rigid Vehicle (MRV) is a candidate in the NASA multi-center effort to determine the most cost effective vehicle to deliver a large-mass payload to the surface of Mars for a human mission. Products of this effort include six-degree-of-freedom (6DoF) entry-to-descent trajectory performance studies for each candidate vehicle. These high fidelity analyses help determine the best guidance and control (G&C) strategies for a feasible, robust trajectory. This paper presents an analysis of the MRV's G&C design by applying common entry and descent associated uncertainties using a Fully Numerical Predictor-corrector Entry Guidance (FNPEG) and tunable Apollo powered descent guidance.

human↗