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At least 1,207 records · Page 67
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Model of the Plasma Potential Distribution in the Plume of a Hollow Cathode

In this paper we present results from a new model of the plasma potentials in the plume just downstream of the hollow cathode keeper. We examine the electron drift velocity as the hollow cathode plasma and neutral gas expand downstream of the keeper. If the drift velocity exceeds the thermal velocity a double layer potential structure develops that is the source of hot electrons. Ions are accelerated upstream through the double layer. The locations of the double layers are calculated using a simple model. It is shown that as the cathode gas flow increases, the location of the double layer moves farther downstream.

ion propulsion↗
NASA NTRS2008

Wear Mechanisms in Electron Sources for Ion Propulsion, 2: Discharge Hollow Cathode

The wear of the keeper electrode in discharge hollow cathodes is a major impediment to the implementation of ion propulsion onboard long-duration space science missions. The development of a predictive theoretical model for hollow cathode keeper life has long been sought, but its realization has been hindered by the complexities associated with the physics of the partially ionized gas and the associated erosion mechanisms in these devices. Thus, although several wear mechanisms have been hypothesized, a quantitative explanation of life test erosion profiles has remained incomplete. A two-dimensional model of the partially ionized gas in a discharge cathode has been developed and applied to understand the mechanisms that drove the erosion of the keeper in two long-duration life tests of a 30-cm ion thruster. An extensive set of comparisons between predictions by the numerical simulations and measurements of the plasma properties and of the erosion patterns is presented. It is found that the near-plume plasma oscillations, predicted by theory and observed by experiment, effectively enhance the resistivity of the plasma as well as the energy of ions striking the keeper.

hollow cathode↗
NASA NTRS2014

Operational Status of the International Space Station Plasma Contactor Hollow Cathode Assemblies from July 2011 to May 2013

The International Space Station has onboard two Aerojet Rocketdyne developed plasma contactor units that perform the function of charge control. The plasma contactor units contain NASA Glenn Research Center developed hollow cathode assemblies. NASA Glenn Research Center monitors the onorbit operation of the flight hollow cathode assemblies. As of May 31, 2013, HCA.001-F has been ignited and operated 123 times and has accumulated 8072 hours of operation, whereas, HCA.003-F has been ignited and operated 112 times and has accumulated 9664 hours of operation. Monitored hollow cathode ignition times and anode voltage magnitudes indicate that they continue to operate nominally.

International Space Station↗
NASA NTRS2013

Temporal Fluctuations in a 100-A LaB6 Hollow Cathode

The temporal fluctuations in the near plume of a 100-Amperes LaB6 (Lanthanum hexaboride) hollow cathode are experimentally investigated. At high currents, turbulent oscillations may contribute to two of the anomalous processes of hollow cathode operation - anomalous resistivity and the production of energetic ions. A detailed study of the properties of the oscillations in a high current cathode is necessary to determine the impact of the fluctuation spectrum on these two effects. In this investigation, a probe array is employed to measure the amplitude and dispersion of axial modes in the plume while a retarding potential analyzer yields estimates of the radial ion energy distribution. The onset of the ion acoustic turbulence (IAT) is observed at high current values, and the character of the turbulent spectrum is shown to agree with weak turbulent theory: the amplitude of the spectrum decreases with flow rate but increases with discharge current. Estimates of the anomalous collision frequency based on experimental observations indicate that the IAT collision frequency can exceed the classical collision frequency at sufficiently high discharge current densities. Additionally, the onset of the IAT is shown to be correlated with the appearance of a high energy ion tail and that the energy in this tail is comparable to the energy in the experimentally-observed IAT.

production of ions↗
NASA NTRS2008

Tungsten and Barium Transport in the Internal Plasma of Hollow Cathodes

The effect of tungsten erosion, transport and redeposition on the operation of dispenser hollow cathodes was investigated in detailed examinations of the discharge cathode inserts from an 8200 hour and a 30,352 hour ion engine wear test. Erosion and subsequent re-deposition of tungsten in the electron emission zone at the downstream end of the insert reduces the porosity of the tungsten matrix, preventing the flow of barium from the interior. This inhibits the interfacial reactions of the barium-calcium-aluminate impregnant with the tungsten in the pores. A numerical model of barium transport in the internal xenon discharge plasma shows that the barium required to reduce the work function in the emission zone can be supplied from upstream through the gas phase. Barium that flows out of the pores of the tungsten insert is rapidly ionized in the xenon discharge and pushedback to the emitter surface by the electric field and drag from the xenon ion flow. Thisbarium ion flux is sufficient to maintain a barium surface coverage at the downstream endgreater than 0.6, even if local barium production at that point is inhibited by tungsten deposits. The model also shows that the neutral barium pressure exceeds the equilibrium vapor pressure of the impregnant decomposition reaction over much of the insert length,so the reactions are suppressed. Only a small region upstream of the zone blocked by tungsten deposits is active and supplies the required barium. These results indicate that hollowcathode failure models based on barium depletion rates in vacuum dispenser cathodes are very conservative.

Hollow cathodes↗
NASA NTRS2010

Barium Depletion in the NSTAR Discharge Cathode After 30,000 Hours of Operation

Dispenser hollow cathodes rely on a consumable supply of barium released by impregnant materials in the pores of a tungsten matrix to maintain a low work function surface. Examinations of cathode inserts from long duration ion engine tests show deposits of tungsten at the downstream end that appear to block the flow of barium from the interior. In addition, a numerical model of barium transport in the insert plasma indicates that the barium partial pressure in the insert may exceed the equilibrium vapor pressure of the dominant barium-producing reaction, and it was postulated previously that this would suppress barium loss in the upstream part of the insert. New measurements of the depth of barium depletion from a cathode insert operated for 30,352 hours reveal that barium loss is confined to a narrow region near the downstream end, confirming this hypothesis.

plasma transport↗
NASA NTRSDate not supplied

Effects of Environmental Exposure on Barium Oxide Cathode Operation

Hollow cathode assemblies (HCA) are typically designed around a cylindrical emitter for the electron source. Barium oxide (BaO) emitters are one type of emitter commonly used, which consists of a porous tungsten matrix impregnated with a mixture of barium oxide, calcium oxide, and alumina. Barium oxide emitters are susceptible to poisoning by a variety of substances, including oxygen, water vapor, carbon dioxide, and air. Poisoning can occur both during operation and exposure during storage. Water vapor is the primary contaminant of concern with ground exposure, and has been historically controlled by appropriate storage and handling procedures. Over the past several years, NASA Glenn Research Center (GRC)has been testing BaO cathodes to observe the effects on cathode operation after extended environmental exposures

electric propulsion↗
DOE OSTI2018

Thick Co-Extruded Cathode Electrodes for High Energy Lithium-Ion Batteries

Co-Extrusion (CoEx) is a high speed, scalable deposition process for creating finely patterned, interdigitated thick films. Our CoEx printhead is designed to be a drop-in replacement for slot-die heads on web coaters, enabling novel geometric structuring of electrodes with minor changes to existing battery electrode processing lines. Here, we present the use of CoEx to prepare thick (~ 120 µm) NMC cathode electrodes consisting of alternating regions of high lithium-ion transport and high lithium-ion storage capacity. By structuring the cathode electrode, we enable full lithium utilization at C/2, despite near doubling of the electrode thickness compared to conventional baseline electrodes. CoEx cathode electrodes are paired with thick, graded graphite anode electrodes and assembled into 1 Ah pouch cells for electrochemical testing. CoEx pouch cells demonstrate 10 – 20% improved energy density with respect to conventional electrodes and > 30% improved power density with respect to thick conventional (unstructured) electrodes at high discharge rates,

25 ENERGY STORAGE↗
DOE OSTI2022

Modeling Chemo-Mechanics with Electrolyte Infiltration to Quantify Degradation of Cathode Particles

One of the main goals in modeling lithium-ion batteries is to improve/predict longevity and resilience of new chemistries. To that end, this talk investigates the formation of stress-induced fracture within polycrystalline cathode particles and the impact on capacity loss. Physically based cathode aging dynamics is simulated in a 3D, continuum-level chemo-mechanical model. The model captures anisotropic Li diffusion within a single polycrystalline particle comprised of hundreds to thousands of randomly oriented grains. A recent addition to this model includes electrolyte infiltration, which occurs when the electrolyte seeps into surface cracks within the particle. The model predicts that particle fracture is primarily due to non-ideal grain interactions with slight dependence on high-rate charge demands. Essentially, when neighboring grains are misaligned, they expand a different rates relative to one another leading to high stresses and ultimately the formation of intraparticle cracks. The model predicts that small particles with large grains develop significantly less damage than larger particles with small grains. Finally, the model predicts most of the chemo-mechanical damage accumulates in the first charge after formation. This chemo-mechanical "damage saturation" effect indicates that initial particle fracture occurs within the first few cycles, while long-term cathode degradation is not solely chemo-mechanically induced. The principle contribution of this research is the use of an anisotropic chemo-mechanical model to test how particle geometry affect capacity fade, which predicts that particle size has a stronger effect on capacity fade than grain size and ultimately that small particles with large grains have the least capacity fade.

cathode↗
DOE OSTI2022

Meshfree Methods for Modeling Chemo-Mechanical Cathode Cracking in Li-Ion Batteries

Through repeated charging and discharging, the electrodes of a Li-ion battery experience cyclic loading causing swelling and contraction due to the movement of lithium, also known as intercalation. This research focuses specifically on the chemo-mechanical cracking in the cathode. Because cathode particles are comprised of many randomly-oriented grains, which have highly anisotropic material properties, the expansion and contraction is very non-uniform. As a result, stress concentrations tend to form between grains, which necessitates the modeling of crack propagation largely along grain boundaries. Chemo-mechanical models are simulated mainly by two methods: the cohesive zone model (CZM) and the continuous damage model (CDM). The CZM is more accurate at capturing the sharp discontinuities of a crack but is very computationally expensive and intractable for large-scale models as a result. Conversely, the CDM is easily computed but not well-suited to easily allow for discontinuous field variables, which are inherent across a crack. This study aims to improve the CDM's ability to capture discontinuous cracks. Current versions of the CDM use the finite element method (FEM), which is one of the most widely used approaches for spatial discretization. This research investigates the use of the Reproducing Kernel Particle Method (RKPM), a meshfree method, for spatial discretization and aims to achieve a chemo-mechanical crack propagation model that achieves both intermediate accuracy and computational time between a CDM and CZM. To gain a better understanding of how the meshfree model compares to the current FEM model in capturing cathode crack propagation, further investigation is needed.

cathode cracking↗
DOE OSTI2019

Simultaneously Dual Modification of Ni-Rich Layered Oxide Cathode for High-Energy Lithium-Ion Batteries

A critical challenge in the commercialization of layer-structured Ni-rich materials is the fast capacity drop and voltage fading due to the interfacial instability and bulk structural degradation of the cathodes during battery operation. Herein, with the guidance of theoretical calculations of migration energy difference between La and Ti from the surface to the inside of LiNi 0.8 Co 0.1 Mn 0.1 O 2 , for the first time, Ti-doped and La 4 NiLiO 8 -coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathodes are rationally designed and prepared, via a simple and convenient dual-modification strategy of synchronous synthesis and in situ modification. Impressively, the dual modified materials show remarkably improved electrochemical performance and largely suppressed voltage fading, even under exertive operational conditions at elevated temperature and under extended cutoff voltage. Further studies reveal that the nanoscale structural degradation on material surfaces and the appearance of intergranular cracks associated with the inconsistent evolution of structural degradation at the particle level can be effectively suppressed by the synergetic effect of the conductive La 4 NiLiO 8 coating layer and the strong Ti—O bond. The present work demonstrates that our strategy can simultaneously address the two issues with respect to interfacial instability and bulk structural degradation, and it represents a significant progress in the development of advanced cathode materials for high-performance lithium-ion batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Ultralow-Strain Zn-Substituted Layered Oxide Cathode with Suppressed P2–O2 Transition for Stable Sodium Ion Storage

Layered transition metal oxides have drawn much attention as a promising candidate cathode material for sodium-ion batteries. However, their performance degradation originating from strains and lattice phase transitions remains a critical challenge. Herein, a high-concentration Zn-substituted Na x MnO 2 cathode with strongly suppressed P2–O2 transition is investigated, which exhibits a volume change as low as 1.0% in the charge/discharge process. Additionally, such ultralow strain characteristics ensure a stable host for sodium ion storage, which significantly improves the cycling stability and rate capability of the cathode material. Also, the strong coupling between the highly reversible capacity and the doping content of Zn in Na x MnO 2 is investigated. It is suggested that a reversible anionic redox reaction can be effectively triggered by Zn ions and is also highly dependent on the Zn content. Such an ion doping strategy could shed light on the design and construction of stable and high-capacity sodium ion host.

25 ENERGY STORAGE↗
DOE OSTI2024

Cationic and Anionic Redox of Battery Cathodes Investigated by Advanced Synchrotron‐Based Mapping of Resonant Inelastic X‐ray Scattering

Abstract Redox reaction builds the foundation stone for the energy density of rechargeable battery cathodes. Probing and understanding the redox reaction behavior is crucial, but also extremely formidable, which requires individual and reliable detection of cationic and anionic redox states. Fortunately, the recently developed ultra‐high‐efficiency mapping of resonant inelastic X‐ray scattering (mRIXS) has emerged as a powerful tool to probe the battery chemistry states. Here, the latest advances of employing advanced mRIXS is summarized to investigate the cationic and anionic redox mechanism of battery cathodes during electrochemical operation. Owing to the new dimension of information along the emission energy and high sensitivity to valence 3d states, 3d transition‐metal L ‐edge (TM‐ L ) mRIXS can eliminate the lineshape distortion in conventional 3d TM‐ L fluorescence X‐ray absorption spectra and investigate the cationic redox quantitatively. Moreover, O‐ K mRIXS could fingerprint the intrinsic oxidized lattice oxygen states and quantify the oxygen redox (OR) reversibility, thus demystifying the controversy in traditional wisdom. In addition, different modification strategies coupled with underlying mechanisms for regulating the activity and reversibility of OR utilizing mRIXS are also summarized. This review provides valuable guidance for further exploration of underlying reaction mechanisms of battery cathodes by mRIXS, along with both technological and scientific improvements.

Cheng, Chen↗
DOE OSTI2023

Stabilizing the Deep Sodiation Process in Layered Sodium Manganese Cathodes by Anchoring Boron Ions

Advanced high-energy-density sodium-ion batteries (SIBs) are inseparable from cathode materials with high specific capacities. Layered manganese-rich oxides (Na x MnO 2 , 0.6 ≤ x ≤1) are promising cathode materials owing to their ease of intercalation and extraction of a considerable amount of sodium ions. However, lattice interactions, especially electrostatic repulsive forces and anisotropic stresses, are usually caused by deep desodiatin/sodiation process, resulting in intragranular cracks and capacity degradation in SIBs. Here, boron ions are introduced into the layered structure to build up B-O-Mn bonds. Further, the regulated electronic structure in Na 0.637 B 0.038 MnO 2 (B-NMO) materials inhibits the deformation of MnO 6 octahedra, which finally achieves a gentle structural transition during the deep sodiation process. B-NMO electrode exhibits a high capacity (141 mAh g –1 ) at 1 C with a capacity retention of 81% after 100 cycles. Therefore, anchoring boron to manganese-rich materials inhibits the detrimental structural evolution of deep sodiation and can be used to obtain excellent cathode materials for SIBs.

25 ENERGY STORAGE↗
DOE OSTI2024

Freestanding Ammonium Vanadate Composite Cathodes with Lattice Self-Regulation and Ion Exchange for Long-Lasting Ca-Ion Batteries

Calcium-ion batteries (CIBs) have emerged as a promising alternative for electrochemical energy storage. The lack of high-performance cathode materials severely limits the development of CIBs. Vanadium oxides are particularly attractive as cathode materials for CIBs, and preinsertion chemistry is often used to improve their calcium storage performance. However, the room temperature cycling lifespan of vanadium oxides in organic electrolytes still falls short of 1000 cycles. Here, based on preinsertion chemistry, the cycling life of vanadium oxides is further improved by integrated electrode and electrolyte engineering. Utilizing a tailored Ca electrolyte, the constructed freestanding (NH 4 ) 2 V 6 O 16 ·1.35H 2 O@graphene oxide@carbon nanotube (NHVO-H@GO@CNT) composite cathode achieves a 305 mAh g -1 high capacity and 10 000 cycles record-long life. Additionally, for the first time, a Ca-ion hybrid capacitor full cell is assembled and delivers a capacity of 62.8 mAh g -1 . The calcium storage mechanism of NHVO-H@GO@CNT based on a two-phase reaction and the exchange of NH 4 + and Ca 2+ during cycling are revealed. The lattice self-regulation of V—O layers is observed and the layered vanadium oxides with Ca 2+ pillars formed by ion exchange exhibit higher capacity. This work provides novel strategies to enhance the calcium storage performance of vanadium oxides via integrated structural design of electrodes and electrolyte modification.

25 ENERGY STORAGE↗
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 OSTI2021

Achieving Stable Molybdenum Oxide Cathodes for Aqueous Zinc‐Ion Batteries in Water‐in‐Salt Electrolyte

Abstract Layered MoO 3 represents a promising cathode for aqueous rechargeable Zn‐ion batteries, but the implementation of this material is limited due to the low conductivity and poor structural stability. A 30 m ZnCl 2 water‐in‐salt electrolyte (WISE) is introduced to a MoO 3 nanobelt cathode for the first time, significantly increasing the stability of MoO 3 cathodes compared to those in 3 m ZnSO 4 and 3 m ZnCl 2 . The Zn/MoO 3 cell in WISE unambiguously demonstrate significantly improved rate performance delivering 349, 253, and 222 mAh g −1 at 100, 500, and 1000 mA g −1 , denoting a 12× capacity increase of those achieved in 3 m electrolytes at 1000 mA g −1 . A capacity retention rate of 73% is achieved after (dis)charging at 100 mA g −1 for 100 cycles, and no obvious capacity fading is observed at higher current densities of 500 mA g −1 and 2 A g −1 . Specifically, the data suggest that the drastic fading in 3 m electrolytes can be attributed to the parasitic surface deposits on Zn originated from Mo dissolution and H 2 formation due to Zn corrosion and hydrogen evolution reaction, which are significantly suppressed in the WISE. The direct visualization of these side reactions is achieved for the first time in the Zn‐MoO 3 system, using an in situ optoelectrochemical measurement.

Wang, Lei↗
DOE OSTI2023

Beneficial Effects of La 0.5 Sr 0.5 CoO 3 Coatings on Thin‐Film LiMn 2 O 4 Cathodes for Lithium Ion Batteries

Abstract The severe capacity loss of spinel LiMn 2 O 4 (LMO) limits the utility of this otherwise promising lithium ion battery cathode material. One of the strategies to mitigate capacity fade is applying a coating on LMO particle surfaces. While this approach yields promising results, there is limited understanding of mechanisms whereby coatings improve LMO capacity retention. Herein, the effects of a new protective coating material, La 0.5 Sr 0.5 CoO 3 (LSCO), in a thin‐film battery geometry that is amenable to fundamental studies of electrode processes, are reported. RF sputtering deposition is used to produce high quality 25–100 nm LMO cathodes on Al 2 O 3 substrates with an intervening Pt/Ti back‐side contact layer. Cycling of the un‐coated cathodes results in capacity loss of 18% over 300 cycles. Adding a 2 nm LSCO layer reduces the capacity loss to 3%. While this may be due in part to reduced Mn dissolution, scanning transmission electron microscopy results indicate that the coating helps to preserve crystallinity and reduce lattice structure distortion due to inhibited formation of defect tetragonal spinel. Three‐electrode electrochemical impedance spectroscopy results reveal that the LSCO coating increases charge transfer and ohmic resistances, but the increases are generally too small to significantly impact cell performance even at high C‐rates.

25 ENERGY STORAGE↗