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At least 379 records · Page 21

Towards the Identification of the Keeper Erosion Cause(s): Numerical Simulations of the Plasma and Neutral Gas Using the Global Cathode Model OrCa2D-II

Numerical simulations with the time-dependent Orificed Cathode (OrCa2D-II) computer code show that classical enhancements of the plasma resistivity can not account for the elevated electron temperatures and steep plasma potential gradients measured in the plume of a 25-27.5 A discharge hollow cathode. The cathode, which employs a 0.11-in diameter orifice, was operated at 5.5 sccm without an applied magnetic field using two different anode geometries. It is found that anomalous resistivity based on electron-driven instabilities improves the comparison between theory and experiment. It is also estimated that other effects such as the Hall-effect from the self-induced magnetic field, not presently included in OrCa2D-II, may contribute to the constriction of the current density streamlines thus explaining the higher plasma densities observed along the centerline.

plasma modeling↗

Model of a Hollow Cathode Insert Plasma

A 2-D axisymmetric fluid model of the plasma in the insert region of a hollow cathode is presented. The level of sophistication included in the model is motivated in part by the need to determine quantitatively plasma fluxes to the emitter surface. The ultimate goal is to assess whether plasma effects can degrade the life of impregnated inserts beyond those documented throughout the 30-50 year history of vacuum cathode technologies. Results from simulations of a 1.2-cm diameter cathode operating at a discharge current of 25 A, and a gas flow rate of 5 sccm, suggest that approximately 10 A of electron current, and 3.5 A of ion current return to the emitter surface. The total emitted electron current computed by the model is about 35 A. Comparisons with plasma measurements suggest that anomalous heating of the plasma due to two-stream instabilities is possible near the orifice region. Solution to the heavy species energy equation, with classical transport and no viscous effects, predicts heavy species temperatures as high as 2640 K.

hollow cathodes↗

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↗

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↗

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↗

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↗

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↗

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↗

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↗

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↗

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↗

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↗

Stable Cycling of Sodium All‐Solid‐State Batteries with High‐Capacity Cathode Presodiation

Sodium all-solid-state batteries (NaSSBs) with an alloy-type anode (e.g., Sn and Sb) offer superior capacity and energy density compared to hard carbon anode. However, the irreversible loss of Na + at the alloy anode during the initial cycle results in diminished capacity and stability, impairing full-cell performance. Here, this study presents an easy-to-implement cathode presodiation strategy by employing a Na-rich material to address these challenges. Leveraging the high theoretical capacity and suitable voltage window, Na 2 S is chosen as the Na donor, which is activated by creating a mixed electron-ion conducting network, delivering a high capacity of 511.7 mAh g −1 . By adding a small amount (i.e., 3 wt.%) of Na 2 S to the cathode composite, a NaCrO 2 || Sn full cell demonstrated capacity improvement from 90.8 to 118.2 mAh g −1 (based on cathode mass). The capacity-balanced full cell can thus cycle to more than 300 times with >90% capacity retention. This work provides a practical solution to enhance the full-cell performance and advance the transformation from half-cell to full-cell applications of NaSSBs.

25 - ENERGY STORAGE↗

Deciphering the Evolution of Current Distribution in Hybrid Silver Vanadium Oxide / Carbon Monofluoride Cathodes within Lithium Primary Batteries

For batteries to function effectively all active material must be accessible requiring both electron and ion transport to each particle. A common approach to generating the needed conductive network is the addition of carbon to create a composite electrode. An alternative approach is the electrochemically induced formation of conductive reaction products where the electrochemically generated materials are in intimate contact with the active material contributing to effective connection of each active particle. Furthermore, this study probes silver vanadium oxide (Ag 2 V 4 O 11 , SVO), carbon monofluoride (CF x ), and hybrid SVO/CF x electrodes in lithium batteries. Ex situ XRD identifies Ag 0 as a reduction product from SVO and LiF from CF x that can be followed as a function of depth-of-discharge (DOD). Spatially-resolved operando energy dispersive x-ray diffraction reveals that the presence of SVO alleviates reaction heterogeneity in the electrodes which are electron transfer limited in the absence of sufficient Ag 0 . Synchrotron X-ray tomography on discharged cathodes reveals the distribution of silver particles where the particles are more closely spaced near the current collector indicating multiple nucleation sites for their formation. Finally, operando isothermal microcalorimetry is used to determine the heat dissipation of the parent and hybrid battery types. Using material enthalpy potentials, we determine the current distribution between the two active materials for the discharging hybrid cathode adding further insight to the diffraction analysis. Taken together, these results provide a comprehensive understanding of hybrid SVO/CF x cathodes and give guidance on optimal compositions that balance power and energy density considerations.

36 MATERIALS SCIENCE↗

Air‐Stable High‐Voltage Li‐Ion Organic Cathode Enabled by Localized High‐Concentration Electrolyte

While lithium‐ion batteries have revolutionized the field of energy storage, their reliance on critical minerals such as cobalt and nickel raises significant concerns over resource availability and supply chain uncertainty. In this study, we revisit dithiin‐fused dilithium naphthazarin (5,8‐dihydroxy‐1,4‐naphthoquinone) (DNP‐Li) as a high‐voltage Li‐ion organic cathode and evaluate its performance in conjunction with localized high‐concentration electrolyte (LHCE). DNP‐Li exhibits remarkable air and thermal stability, a high operating potential of 3.55 V vs. Li + /Li, and a specific capacity of 232 mAh g −1 , positioning it as one of the most promising candidates among Li‐ion organic cathodes. Furthermore, the electrochemical behavior of DNP‐Li is strongly influenced by the electrolyte composition, giving distinct two‐plateau or four‐plateau voltage profiles accompanied by reversible or irreversible phase transitions in carbonate‐based or LHCE electrolyte formulations, respectively. The reduced solubility of DNP‐Li‐based redox intermediates in LHCE enhances cycling stability, achieving a capacity retention of 85% after 50 cycles at 0.1C and 75% after 160 cycles at 0.5C, demonstrating a significant improvement compared to the carbonate‐based electrolyte. This work highlights the critical role of solute–electrolyte interactions in modulating the electrochemical performance of multielectron small‐molecule organic cathodes, offering new pathways for advancing sustainable and high‐efficiency energy storage technologies.

Lakraychi, Alae Eddine [Department of Electrical a↗

Enhancing the Reaction Kinetics and Stability of Co‐Free Li‐Rich Cathode Materials via a Multifunctional Strategy

Co-free Li-rich layered oxides (CFLLOs) with anionic redox activity are among the most promising cathode materials for high-energy-density and low-cost lithium-ion batteries (LIBs). However, irreversible oxygen release often causes severe structural deterioration, electrolyte decomposition, and the formation of unstable cathode-electrolyte interface (CEI) film with high impedance. Additionally, the elimination of cobalt elements further deteriorates the reaction kinetics, leading to reduced capacity and poor rate performance. Here, in this study, a multifunctional strategy is proposed, incorporating Li 2 MnO 3 phase content regulation, micro-nano structure design, and heteroatom substitution. The increased content of Li 2 MnO 3 phase enhances the capacity through oxygen redox. The smaller nanoscale primary particles induce greater tensile strain and introduce more grain boundaries, thereby improving the reaction kinetics and reactivity, while the larger micron-sized secondary particles help to reduce interfacial side reactions. Furthermore, Na⁺ doping modulates the local coordination environment of oxygen, stabilizing both the anion framework and the crystal structure. As a result, the designed cathode exhibits enhanced rate performance, delivering a capacity of 158 mAh g⁻¹ at 5.0 C and improved cyclic stability, with a high capacity retention of 99% after 400 cycles at 1.0 C. This multifunctional strategy holds great promise for advancing the practical application of CFLLOs in next-generation LIBs.

Co-free Li-rich layered oxide↗

Microsphere LiMn 0.6 Fe 0.4 PO 4 /C cathode with unique rod-like secondary architecture for high energy lithium ion batteries

LiMn x Fe 1-x PO 4 /C is considered a promising next-generation cathode material with significant commercial potential, inheriting the safety of LiFePO 4 while offering higher energy densities. However, the extremely low conductivity and the Jahn-Teller effect induced by Mn 3+ limit its practical capacity and rate performance. Effective modifications can be achieved through particle nanonization and uniform carbon coating. Here, in this work, we synthesized microspherical LiMn 0.6 Fe 0.4 PO 4 /C cathode materials using a hydrothermal method combined with spray drying carbon coating. The cathode material exhibits a microsphere structure composed of aggregated nanorods with a uniform 3 nm carbon coating, showing good dispersibility, small specific surface area and high tap density. In-situ diffraction analysis showed that expanding the single-phase solid solution region during (de)lithiation can reduce the energy barrier for electron transport, improve the kinetics of the (dis)charge process, and enhance both cycling and rate performance. The initial capacity at 0.1C can reach 155 mAh/g, and the capacity remains at 133.5 mAh/g with a retention rate of 97.1 % after 300 cycles. The synergistic effect of particle nanonization and uniform carbon coating endows the LiMn x Fe 1-x PO 4 /C material with excellent electrochemical performance.

25 ENERGY STORAGE↗

Evaluating Material Design Principles for Calcium-Ion Mobility in Intercalation Cathodes

Multivalent-ion batteries offer an alternative to Li-based technologies, with the potential for greater sustainability, improved safety, and higher energy density, primarily due to their rechargeable system featuring a passivating metal anode. Although a system based on the Ca 2+ /Ca couple is particularly attractive given the low electrochemical plating potential of Ca 2+ , the remaining challenge for a viable rechargeable Ca battery is to identify Ca cathodes with fast ion transport. In this work, a high-throughput computational pipeline is adapted to (1) discover novel Ca cathodes in a largely unexplored space of empty intercalation hosts and (2) develop material design rules for Ca-ion mobility. One candidate from the screening, W 2 O 3 (PO 4 ) 2 , is confirmed to have a low Nudged Elastic Band (NEB) barrier of 168 meV within a one-dimensional (1D) ion percolation topology. This candidate is subsequently synthesized and electrochemically tested, achieving reversible Ca cycling with a capacity of 25 mA h/g. To further accelerate the screening for promising Ca intercalation electrodes, machine learning (ML) Random Forest (RF) and Extreme Gradient Boosting (XGB) classification models are created with local environment descriptors based on a large, structurally and chemically diverse dataset of minimum energy pathways, spanning over 5,000 density functional theory (DFT) site energy calculations. Accuracies of 92% are achieved, material design metrics are quantified, ML force-fields are leveraged in an accelerated iteration of the screening, and a total of 27 novel Ca cathode materials are highlighted for further investigation.

25 ENERGY STORAGE↗