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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 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

The Effect of the CO32- to Ca2+ Ion activity ratio on calcite precipitation kinetics and Sr2+ partitioning

Engineering the precipitation of calcium carbonate, which can co-precipitate trace metal contaminants, is a proposed strategy for remediating toxic or radioactive metals in subsurface environments. Engineering precipitation of multi-component minerals will involve injection of chemical amendments that must be mixed at a molecular level to supersaturated conditions that are sufficient to promote rapid mineral precipitation relative to natural systems. In subsurface systems this often means reactant mixing zones will be formed that are characterized by gradients in solute concentrations, saturation state, and solute activity ratios. To better understand the effect of ion activity ratios on CaCO{sub 3} precipitation kinetics and Sr{sup 2+} co-precipitation we experiments were conducted under constant composition conditions where the supersaturation state ({Omega}) with respect to calcite was held constant at 9.4, but the ion activity ratio (r = a{sub co{sub 3}{sup 2-}}/a{sub Ca{sup 2+}}) ranged from 0.003 to 4.15. Results: Under the chosen experimental conditions the CaCO{sub 3} phase formed was calcite and initial precipitation rates varied from a maximum rate of 84.7 {mu}mol/ m{sup 2}/min for a carbonate to calcium activity ratio of (0.21). However, precipitation rates were found to vary with time which could be indicative of variations in precipitation mechanisms that are related to the ion activity ratio. The observed trends in the distribution coefficients for co-precipitated Sr2+ (D{sup P}{sub Sr}{sup 2+}) relative to the calcite precipitation rate (i.e. a positive correlation) indicate that increasing calcite precipitation rates increase the incorporation of Sr{sup 2+}. Conclusion: The observed variation between the rate maxima and minima based on the ion activity ratio could have great deal of implication for sequestering radionuclides (e.g. {sup 90}Sr) and other toxic metals in engineered systems at contaminated sites. Extending our data plot range allowed us to have clues about the differences in mechanism calcite precipitation, which would have significance in our understanding of mineral precipitation modes in subsurface remediation strategies. The positive correlation between D{sup P}{sub Sr}{sup 2+} and calcite precipitation rate could be indicative of the impact calcite precipitation would have on sequestering toxic metals in subsurface environment.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Disintegration of Meatball Electrodes for LiNi x Mn y Co z O 2 Cathode Materials

Mechanical degradation of Li-ion batteries caused by the repetitive swelling and shrinking of electrodes upon electrochemical cycles is now well recognized. Structural disintegration of the state-of-art cathode materials of a hierarchical structure is relatively less studied. In this paper, we track the microstructural evolution of different marked regimes in LiNi x Mn y Co z O 2 (NMC) electrodes after lithiation cycles. Decohesion of primary particles constitutes the major mechanical degradation in the NMC materials, which results in the loss of connectivity of the conductive network and impedance increase. We find that the structural disintegration is largely dependent on the charging rate – slow charging causes more damage, and is relatively insensitive to the cyclic voltage window. We use finite element modeling to study the evolution of Li concentration and stresses in a NMC secondary particle and employ the cohesive zone model to simulate the interfacial fracture between primary particles. Finally, we reveal that microcracks accumulate and propagate during the cyclic lithiation and delithiation at a slow charging rate.

25 ENERGY STORAGE↗
DOE OSTI2025

Temperature and dose effects on dislocation loops in self-ion irradiated high-purity iron

Body-centered cubic (BCC) Fe-based alloys are promising candidate materials for advanced nuclear reactors. However, a detailed understanding of irradiation induced dislocation loop microstructure development remains unresolved. It is a widespread belief that 〈001〉 loops become increasingly favorable over ½〈111〉 loops as irradiation temperature rises above ∼300 C. Unfortunately, the temperature effects on 〈001〉 loop have been primarily examined in in-situ irradiation on TEM thin foils but poorly explored on bulk Fe due to exceedingly limited experimental studies on bulk specimens, raising concerns about the potential influence of TEM thin foil artifacts on observed results. Here, in this study, we conducted experiments on ultra-high purity BCC Fe specimens irradiated with 6.7–8 MeV Fe ions over a wide temperature range on bulk samples. We investigated the effects of temperature (T irr = 250–500 °C), dose rate (10⁻⁵ to 10⁻³ dpa/s), and dose (0.35 to 3.5 dpa) on the formation and evolution of 〈001〉 and ½〈111〉 loops as well as cavity (void) formation. Post-irradiation Burgers vector analysis via g•b method on dislocation segments and loops revealed that 〈001〉 loop fraction does not show a monotonic positive correlation with irradiation temperature. Combined with previous and current theoretical as well as experimental findings, we explore the temperature effects on all existing models of 〈001〉 loop formation. We conclude that the prevailing reports regarding the dominance of 〈001〉 loops in Fe at elevated temperatures are mainly attributable to the loss of glissile ½〈111〉 clusters in TEM thin foil experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Identifying the Cause of Rupture of Li-Ion Batteries during Thermal Runaway

As the energy density of lithium-ion cells and batteries increases, controlling the outcomes of thermal runaway becomes more challenging. If the high rate of gas generation during thermal runaway is not adequately vented, commercial cell designs can rupture and explode, presenting serious safety concerns. Here, ultra-high-speed synchrotron X-ray imaging is used at >20 000 frames per second to characterize the venting processes of six different 18650 cell designs undergoing thermal runaway. For the first time, the mechanisms that lead to the most catastrophic type of cell failure, rupture, and explosion are identified and elucidated in detail. The practical application of the technique is highlighted by evaluating a novel 18650 cell design with a second vent at the base, which is shown to avoid the critical stages that lead to rupture. The insights yielded in this study shed new light on battery failure and are expected to guide the development of safer commercial cell designs.

25 ENERGY STORAGE↗
DOE OSTI2018

Crystalline Silicotitanate ion exchange media long-term storage evaluation

Crystalline Silicotitanate a (CST) ion exchange media is produced in an engineered form, known as IONSIV™ IE-911. This material has been tested extensively for use in removing 137 Cs from Savannah River Site (SRS) and Hanford site tank waste. This inorganic material is highly selective for removing cesium ions, even in the presence of high concentrations of sodium and potassium ions and is tolerant of the harsh conditions of the varying tank chemistries. A batch of caustic washed IE-911 that had been produced by the supplier and received at SRS in 2001 was tested to verify that it was still in good condition after the extended storage. This testing involved standard batch contacts to measure the removal of Cs from simulated tank waste. This report describes the results of testing performed to verify that the IE-911 matches the performance of previous batches of this media. To confirm that the performance of IE-911 is similar to previous batches and that no degradation had occurred during storage, batch contact testing was performed using SRNL’s standard methodology using a non-radioactive SRS Average Waste Simulant composition utilized in previous studies. Batch contact kinetics testing was also conducted to determine cesium loading on this batch versus time. The cesium equilibrium loading isotherm in SRS simulant at 23°C was compared to ZAM isotherm model predictions and previous test results with IE-911 media. The measured and predicted distribution coefficients and cesium loading (“Q”) are shown in Table ES-1. The physical properties of the material were also determined, including density, moisture content, and particle size.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Towards Understanding of Cracking during Drying of Thick Aqueous-Processed LiNi 0.8 Mn 0.1 Co 0.1 O 2 Cathodes

Replacing N-methyl-2-pyrrolidone (NMP) with water for processing of lithium-ion battery (LIB) electrodes has both cost and environmental benefits, which include reduced drying time, lower dryer capital cost, elimination of NMP recovery capital equipment, and no release of volatile organic compounds (VOCs) into the environment. However, aqueous-processed thick cathodes (≳4 mAh/cm 2 ) typically exhibit detrimental cracking during drying that is not observed for the NMP-based counterpart. The reasons for cracking of these water-based thick electrodes are still not well understood due to the complex nature of the colloidal dispersions used in the LIB electrode processing steps. In this work, the contributions of various factors responsible for cracking are discussed. We show that eliminating hydrogen evolution due to corrosion of the aluminum current collector eliminated the majority of the cracks regardless of the coating thickness, identifying the gas evolution as the primary reason for electrode cracking. Some secondary cracks and pinhole-type defects remained after addressing the aluminum current collector corrosion, which are thought to be caused by an inferior binding network formed by carbon black and binder in aqueous-processed cathodes compared to those processed with NMP. The thick aqueous processed cathodes are not able to sufficiently withstand the drying stresses without crack formation. We demonstrate reduction of these secondary defects by either improving the binding network or by reducing the drying stress. The former was achieved by replacing carbon black with vapor grown graphite tubes (VGGTs) that caused a more efficient utilization of the emulsion binder. Here, the latter was achieved by adding a small amount of IPA as a co-solvent that has been shown to reduce capillary stresses.

25 ENERGY STORAGE↗
DOE OSTI2012

ADVANCES IN HEXAVALENT CHROMIUM REMOVAL AT HANFORD

At the Hanford Site, chromium was used as a corrosion inhibitor in the reactor cooling water and was introduced into the groundwater as a result of planned and unplanned discharges from reactors during plutonium production since 1944. Beginning in 1995, groundwater treatment methods were evaluated leading to the use of pump and treat facilities with ion exchange using Dowex 21 K, a regenerable strong base anion exchange resin. This required regeneration of the resin, which is currently performed offsite. Resin was installed in a 4 vessel train, with resin removal required from the lead vessel approximately once a month. In 2007, there were 8 trains (32 vessels) in operation. In 2008, DOE recognized that regulatory agreements would require significant expansion in the groundwater chromium treatment capacity. Previous experience from one of the DOE project managers led to identification of a possible alternative resin, and the contractor was requested to evaluate alternative resins for both cost and programmatic risk reductions. Testing was performed onsite in 2009 and 2010, using a variety of potential resins in two separate facilities with groundwater from specific remediation sites to demonstrate resin performance in the specific groundwater chemistry at each site. The testing demonstrated that a weak base anion single-use resin, ResinTech SIR-700, was effective at removing chromium, had a significantly higher capacity, could be disposed of efficiently on site, and would eliminate the complexities and programmatic risks from sampling, packaging, transportation and return of resin for regeneration. This resin was installed in Hanford's newest groundwater treatment facility, called 100-DX, which began operations in November, 2010, and used in a sister facility, 100-HX, which started up in September of 2011. This increased chromium treatment capacity to 25 trains (100 vessels). The resin is also being tested in existing facilities that utilize Dowex 21 K for conversion to the new resin. This paper will describe the results of the testing, performance in the facilities, continued optimization in the pump and treat facilities, and the estimated savings and non-tangible benefits of the conversion.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2025

Anion Vacancies Coupling with Heterostructures Enable Advanced Aerogel Cathode for Ultrafast Aqueous Zinc‐Ion Storage

As a potential cathode material, manganese-based sulfide has recently attracted increasing interest due to its many advantages in aqueous zinc-ion storage. Unfortunately, some challenges such as sluggish kinetics, unstable structure, and controversial phase transition mechanism during the energy storage process hinder its practical application. Herein, inspired by density functional theory (DFT) calculations, a novel 3D sulfur vacancy-rich and heterostructured MnS/MXene aerogel is designed, and used as a cathode for aqueous Zn-ion batteries/hybrid capacitors (ZIBs/ZICs) for the first time. Thanks to the synergistic modification strategy of sulfur vacancies and heterostructures, the as-constructed MnS/MXene//Zn ZIBs exhibit significantly enhanced electrochemical properties, especially outstanding rate capability and cyclic stability. More encouragingly, the as-assembled MnS/MXene//porous carbon (PC) ZICs exhibit an ultrahigh energy density, a high power density, and a splendid cycling lifespan. Most notably, systematic kinetic analyses, ex situ characterizations, and DFT calculations illustrate that MnS/MXene first irreversibly converts into MnO x @ZnMnO 3 /MXene, and then undergoes a reversible conversion from MnO x @ZnMnO 3 /MXene to MnOOH@ZnMn 2 O 4 /MXene, accompanied by the co-insertion/extraction of H + and Zn 2+ . Further, the synergistic modification strategy of sulfur vacancies and heterostructures and the thorough mechanistic study proposed in this work offer valuable guidance for designing and exploiting high-performance cathodes in aqueous zinc-based energy storage devices.

25 ENERGY STORAGE↗
DOE OSTI2025

Tailoring P2/P3‐Intergrowth in Manganese‐Based Layered Transition Metal Oxide Positive Electrodes via Sodium Content for Na‐Ion Batteries

High-manganese content sodium-ion positive electrodes have received heightened interest as an alternative to contemporary Li-ion chemistries due to their high abundance, low toxicity, and even geographical distribution. However, these materials typically suffer from poor capacity, unstable cycling performance, and sluggish Na + kinetics. Herein, we explore a manganese-based layered transition metal oxide (Na x N 0.25 Mn 0.75 O 2 ) and show by X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) that careful variation of the sodium content can instigate the formation of a biphasic intergrowth. This intergrown P2/P3 material offered a higher capacity than its monophasic P2 counterpart due to the P3 structure having greater low-voltage Mn 3+/4+ redox. Further, the intergrowth material offers greatly enhanced kinetics and cycling stability when compared to single-phase P3 material, due to the stabilizing nature of the P2 structure, elucidated by galvanostatic intermittent titration technique (GITT) and operando synchrotron X-ray diffraction. These results highlight the beneficial effect that the intergrowth structure has on the electrochemical performance of high-manganese content positive electrode for future sodium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2019

Effect of wind pressure and modulation schemes on rain interrupted optical wireless links under tropical climates

Tropical and subtropical regions experience heavy rain intensities often accompanied with medium to strong winds. In this work, the effect of perpendicular wind flow and various modulation formats on a rain interrupted optical wireless link is investigated experimentally under controlled laboratory conditions. Attenuation as a function of rain rate is observed at different wind pressure. It is found that rain induced scattering dominates the rain specific attenuation however significant attenuation is expected at much higher wind pressure which normally increases with altitudes. A comparative performance of modulation formats like direct intensity modulation (D-IM), pulse width modulation (PWM) and various subcarrier intensity modulated (SIM) signals under heavy rain conditions is reported. It is found that SIM-FSK and SIM-AM offer better signal to noise performance (approximately two times) followed by subcarrier phase (SIM-PM) and frequency (SIM-FM) respectively. Also, SIM-FSK and PWM are least attenuated in heavy precipitation.

42 ENGINEERING↗
DOE OSTI2019

Stability and Compressibility of Cation-Doped High-Entropy Oxide MgCoNiCuZnO 5

High-entropy oxides (HEOx) are multicomponent (≥5) complex oxides that possess material properties and functions unexpected from their constituent simple oxides. Previous studies demonstrated that a cation-doped HEOx, MgCoNiCuZnO 5 , shows good catalytic activity, excellent ionic conductivity, and high energy storage. The structural and mechanical stabilities of materials are pivotal to their applications. However, how temperature and pressure influence the structural stability of cation-doped HEOx and how doping affects the mechanical properties are yet to be understood. In this work, we investigated the structural stabilities of undoped and Li/Mn-doped MgCoNiCuZnO 5 in heating or under compression using in situ synchrotron X-ray diffraction (XRD), and determined their elastic moduli using high-pressure XRD. Our results show that the HEOx compounds are structurally stable at temperatures up to ~450 °C or at pressures up to ~50 GPa, and that Li/Mn doping makes the HEOx more compressible. Our molecular static (MS) calculations predicted that the formation reaction of a HEOx is endothermic, consistent with the fact that a single-phase HEOx can only be produced at high temperatures. The MS calculations also revealed that the observed doping-induced elastic softening stems from the introduction of the Li-O/Mn-O ionic bonds in the HEOx compound, which are weaker than other cation-oxygen ionic bonds in the undoped HEOx. These findings will be indispensable to engineer HEOx materials for use in ion batteries, catalysis, and other fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Abnormal Current–Voltage Hysteresis Induced by Reverse Bias in Organic–Inorganic Hybrid Perovskite Photovoltaics

In this study, reverse bias (RB)-induced abnormal hysteresis is investigated in perovskite solar cells (PVSCs) with nickel oxide (NiOx)/methylammonium lead iodide (CH 3 NH 3 PbI 3 ) interfaces. Through comprehensive current-voltage (I-V) characterization and bias-dependent external quantum efficiency (EQE) measurements, we demonstrate that this phenomenon is caused by the interfacial ion accumulation intrinsic to CH 3 NH 3 PbI 3 . Subsequently, via systematic analysis we discover that the abnormal I-V behavior is remarkably similar to tunnel diode I-V characteristics and is due to the formation of a transient tunnel junction at NiO x /CH 3 NH 3 PbI 3 interfaces under RB. The detailed analysis navigating the complexities of I-V behavior in CH 3 NH 3 PbI 3 -based solar cells provided here ultimately illuminates possibilities in modulating ion motion and hysteresis via interfacial engineering in PVSCs. Moreover, this work shows that RB can alter how CH 3 NH 3 PbI 3 contributes to the functional nature of devices and provides the first steps toward approaching functional perovskite interfaces in new ways for metrology and analysis of complex transient processes.

14 SOLAR ENERGY↗
DOE OSTI2017

LiMn 2 O 4 Surface Chemistry Evolution during Cycling Revealed by in Situ Auger Electron Spectroscopy and X-ray Photoelectron Spectroscopy

This work utilizes in situ electrochemical and analytical characterization during cycling of LiMn 2 O 4 (LMO) equilibrated at different potentials in an ultrahigh vacuum (UHV) environment. The LMO reacts with organic molecules in the vacuum to form a high surface concentration of Li 2 CO 3 (≈50% C) during initial charging to 4.05 V. Charging to higher potentials reduces the overall Li 2 CO 3 concentration (≈15% C). Discharging to 3.0 V increases the Li 2 CO 3 concentration (≈30% C) and over discharging to 0.1 V again reduces its concentration (≈15% C). This behavior is reproducible over 5 cycles. The model geometry utilized suggests that oxygen from LMO can participate in redox of carbon, where LMO contributes oxygen to form the carbonate in the solid electrolyte interphase (SEI). Similar results were obtained from samples cycled ex situ , suggesting that the model in situ geometry provides reasonably representative information about surface chemistry evolution. Finally, carbon redox at LMO and the inherent voltage instability of the Li 2 CO 3 likely contributes significantly to its capacity fade.

25 ENERGY STORAGE↗
DOE OSTI2024

Fracture Dynamics in Silicon Anode Solid-State Batteries

Solid-state batteries (SSBs) with silicon anodes could enable improved safety and energy density compared to lithium-ion batteries. However, degradation arising from the massive volumetric changes of silicon anodes during cycling is not well understood in solid-state systems. Here, we use operando X-ray computed microtomography to reveal micro- to macro-scale chemo-mechanical degradation processes of silicon anodes in SSBs. Mud-type channel cracks driven by biaxial tensile stress form across the electrode during delithiation. We also find detrimental cracks at the silicon/ solid electrolyte interface that form due to local reaction competition between neighboring domains of different sizes. Continuum phase-field damage modeling quantifies stress-driven channel cracking and shows that the lithiated silicon stress state is critical for determining the extent of interfacial fracture. This work reveals the mechanisms that govern SSBs compared to conventional lithium-ion batteries and provides guidelines for engineering chemomechanically resilient electrodes for high-energy batteries.

25 ENERGY STORAGE↗
DOE OSTI2016

Phase restructuring in transition metal dichalcogenides for highly stable energy storage

Achieving homogeneous phase transition and uniform charge distribution is essential for good cycle stability and high capacity when phase conversion materials are used as electrodes. Herein, we show that chemical lithiation of bulk 2H-MoS 2 distorts its crystalline domains in three primary directions to produce mosaic-like 1T' nanocrystalline domains, which improve phase and charge uniformity during subsequent electrochemical phase conversion. 1T'-Li x MoS 2 , a macroscopic dense material with interconnected nanoscale grains, shows excellent cycle stability and rate capability in a lithium rechargeable battery compared to bulk or exfoliated-restacked MoS 2 . Transmission electron microscopy studies reveal that the interconnected MoS 2 nanocrystals created during the phase change process are reformable even after multiple cycles of galvanostatic charging/discharging, which allows them to play important roles in the long term cycling performance of the chemically intercalated TMD materials. Finally, these studies shed light on how bulk TMDs can be processed into quasi-2D nanophase material for stable energy storage.

25 ENERGY STORAGE↗
DOE OSTI2011

Experimental Investigation of the Reflection Mode Micro Laser Propulsion under Highly Frequent and Multi Pulse Laser

Micro laser propulsion used for some space tasks of micro-satellites are preferred to providing small thrust and high specific impulse while keeping power consumption low. Most previous work on micro laser propulsion are about transmission mode (T-mode) using a CW laser. In this article, a pulsed fiber laser is used to study the micro laser propulsion performance under reflection mode. Multi pulse (ranged from 100 to 2000) tests are conducted on a double base propellant with the vacuum less than 10 Pa. The laser frequency is 20 kHz and two kinds of instantaneous power density 4.77x10{sup 6} W/cm{sup 2} and 2.39x10{sup 7} W/cm{sup 2} are used. It is found that the momentum coupling coefficient C{sub m} and the mean thrust F increases with the increasing pulse numbers, which is different to the previous work. By adjusting the irradiation time T, it is easy to get a large mean thrust, up to mN. When the energy density is the same, C{sub m}, I{sub sp}, F and {eta} increase with the increasing power density. Also I{sub sp} and {eta} are very low, laser ablation is insufficiently under the current condition. 3D Morphology of the ablation hole is obtained by confocal microscope for the first time.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Beyond ITER: Neutral beams for a demonstration fusion reactor (DEMO) (invited)

In the development of magnetically confined fusion as an economically sustainable power source, International Tokamak Experimental Reactor (ITER) is currently under construction. Beyond ITER is the demonstration fusion reactor (DEMO) programme in which the physics and engineering aspects of a future fusion power plant will be demonstrated. DEMO will produce net electrical power. The DEMO programme will be outlined and the role of neutral beams for heating and current drive will be described. In particular, the importance of the efficiency of neutral beam systems in terms of injected neutral beam power compared to wallplug power will be discussed. Options for improving this efficiency including advanced neutralisers and energy recovery are discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2015

Fabrication of polylactide nanocomposite scaffolds for bone tissue engineering applications

Highly porous three-dimensional polylactide (PLA) scaffolds were obtained from PLA incorporated with different amounts of chitosan-modified montmorillonite (CS-MMT), through solvent casting and particulate leaching method. The processed scaffolds were tested in vitro for their possible application in bone tissue engineering. Scaffolds were characterized by Focused Ion Beam Scanning Electron Microscopy (FIB SEM), Fourier Transform Infra-Red (FTIR), and X-Ray Diffraction (XRD) to study their structure and intermolecular interactions. Bioresorbability tests in simulated body fluid (pH 7.4) were conducted to assess the response of the scaffolds in a simulated physiological condition. The FIB SEM images of the scaffolds showed a porous architecture with gradual change in morphology with increasing CS-MMT concentration. FTIR analysis revealed the presence of both PLA and CS-MMT particles on the surface of the scaffolds. XRD showed that the crystalline unit cell type was the same for all the scaffolds, and crystallinity decreased with an increase in CS-MMT concentration. The scaffolds were found to be bioresorbable, with rapid bioresorbability on the scaffolds with a high CS-MMT concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗