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At least 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Mechanism of cathode spot splitting in vacuum arcs in an oblique magnetic field

Experiments in the last decade showed that for cathode spots in a magnetic field that obliquely intercepts the cathode surface, the current per spot increased with the transverse component of the magnetic field and decreased with the normal component. The present work analyzes the nature of cathode spot splitting in an oblique magnetic field. A physical model for cathode spot current splitting was developed, which considered the relation between the plasma kinetic pressure, self-magnetic pressure, and applied magnetic pressure in a current carrying cathode plasma jet. The current per spot was calculated, and it was found to increase with the tangential component of the magnetic field and to decrease with the normal component, which agrees well with the experimental dependence.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Experimental research of different plasma cathodes for generation of high-current electron beams

The results of experimental studies of different types of cathodes—carbon-epoxy rods, carbon-epoxy capillary, edged graphite, and metal-dielectric—under the application of high-voltage pulses with an amplitude of several hundreds of kV and pulse duration of several nanoseconds are presented. The best diode performance was achieved with the edged graphite and carbon-epoxy-based cathodes characterized by uniform and fast (<1 ns) formation of explosive emission plasma spots and quasi-constant diode impedance. This result was achieved for both annular cathodes in a strong magnetic field and planar cathodes of a similar diameter (∼2 cm) with no external magnetic field. The cathodes based on carbon-epoxy rods and carbon-epoxy capillaries operating with an average current density up to 1 kA/cm{sup 2} showed insignificant erosion along 10{sup 6} pulses of the generator and the generated electron beam current showed excellent reproducibility in terms of the amplitude and waveform.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

A multiple gap plasma cathode electron gun and its electron beam analysis in self and trigger breakdown modes

In the present paper, a pseudospark discharge based multiple gap plasma cathode electron gun is reported which has been operated separately in self and trigger breakdown modes using two different gases, namely, argon and hydrogen. The beam current and beam energy have been analyzed using a concentric ring diagnostic arrangement. Two distinct electron beams are clearly seen with hollow cathode and conductive phases. The hollow cathode phase has been observed for ∼50 ns where the obtained electron beam is having low beam current density and high energy. While in conductive phase it is high current density and low energy electron beam. It is inferred that in the hollow cathode phase the beam energy is more for the self breakdown case whereas the current density is more for the trigger breakdown case. The tailor made operation of the hollow cathode phase electron beam can play an important role in microwave generation. Up to 30% variation in the electron beam energy has been achieved keeping the same gas and by varying the breakdown mode operations. Also, up to 32% variation in the beam current density has been achieved for the trigger breakdown mode at optimized trigger position by varying the gas type.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2024

Direct evidence of low work function on SrVO 3 cathode using thermionic electron emission microscopy and high-field ultraviolet photoemission spectroscopy

Perovskite SrVO 3 has recently been proposed as a novel electron emission cathode material. Density functional theory (DFT) calculations suggest multiple low work function surfaces, and recent experimental efforts have consistently demonstrated effective work functions of ~2.7 eV for polycrystalline samples, both results suggesting, but not directly confirming, that some fraction of even lower work function surface is present. In this work, thermionic electron emission microscopy (ThEEM) and high-field ultraviolet photoemission spectroscopy (UPS) are used to study the local work function distribution and measure the work function of a partially oriented- (110)-SrVO 3 perovskite oxide cathode surface. Our results show direct evidence of low work function patches of about 2.0 eV on the cathode surface, with a corresponding onset of observable thermionic emission at 750 °C. We hypothesize that, in our ThEEM and UPS experiments, the high applied electric field suppresses the patch field effect, enabling the direct measurement of local work functions. This measured work function of 2.0 eV is comparable to the previous DFT-calculated work function values of the SrVO-terminated (110) SrVO 3 surface (2.3 eV) and SrO-terminated (100) surface (1.9 eV). The measured 2.0 eV value is also much lower than the work function for the (001) LaB 6 single crystal cathode (~2.7 eV) and comparable to the effective work function of B-type dispenser cathodes (~2.1 eV). If SrVO 3 thermionic emitters can be engineered to access domains of this low 2.0 eV work function, they have the potential to significantly improve thermionic emitter-based technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Atomic-scale constituting stable interface for improved LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathodes of lithium-ion batteries

Ascribed to their higher capacity and lower cost compared to conventional LiCoO 2 , the Ni-rich layered LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) is now considered as one promising cathode for lithium-ion batteries (LIBs). However, it still suffers from some evident performance degradation, especially under high cutoff voltages (i.e., >4.3 V versus Li/Li + ). The performance degradation typically is exhibited as capacity fading and voltage drop, mainly originating from an instable interface between the NMC622 and electrolyte as well as the evolution of the NMC structure. To improve the interfacial and structural stability of NMC cathodes, herein we deposited an ultrathin layer of Al 2 O 3 coatings (<5 nm) conformally over NMC622 composite electrodes directly using atomic layer deposition (ALD). It was found that, under different upper cutoff voltages (4.3, 4.5, and 4.7 V), the ALD Al 2 O 3 coatings enable enhanced performance of NMC622 cathodes with better cyclability and higher capacity. Particularly, the beneficial effects of the ALD Al 2 O 3 coatings are more remarkable at higher upper cutoff voltages (4.5 and 4.7 V). Furthermore, the ALD coatings can significantly improve the rate capability of NMC622. To this end, we utilized a suite of characterization tools and performed a series of electrochemical tests to clarify the effects of the ALD Al 2 O 3 coatings. This study revealed that the beneficial effects of the Al 2 O 3 ALD coatings are multiple: (i) serving as an artificial layer of solid electrolyte interphase to mitigate undesirable interfacial reactions; (ii) acting as a physical barrier to inhibit metal dissolution of NMC; and (iii) forming a reinforced networked overcoating to boost the mechanical integrity of NMC cathodes. This study is favorable for designing high-performance NMC cathodes.

25 ENERGY STORAGE↗
DOE OSTI2012

Effect of the cathode on the 3D plume distribution of a Hall thruster

A Hall thruster usually has a symmetric cylindrical structure with the cathode placed on the outlet along a particular radial direction. In order to evaluate the effect of the nonaxisymmetric location of the cathode on the plume distribution, the 3D ion current density distribution was measured and the plume deflection angles were defined. Experimental results show that high electron density near the cathode would cause plume deflection angles along a radial direction toward the cathode. The effect of the cathode's nonaxisymmetric location upon the discharge's axisymmetric characteristics is an important physical problem, which deserves emphasizing.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2011

Determination of the cathode and anode voltage drops in high power low-pressure amalgam lamps

For the first time, cathode and anode drops of powerful low-pressure amalgam lamps were measured. The lamp discharge current is 3.2 A, discharge current frequency is 43 kHz, linear electric power is 2.4 W/cm. The method of determination of a cathode drop is based on the change of a lamp operating voltage at variation of the electrode filament current at constant discharge current. The total (cathode plus anode) drop of voltage was measured by other, independent ways. The maximum cathode fall is 10.8 V; the anode fall corresponding to the maximal cathode fall is 2.4 V. It is shown that in powerful low pressure amalgam lamps the anode fall makes a considerable contribution (in certain cases, the basic one) to heating of electrodes. Therefore, the anode fall cannot be neglected, at design an electrode and ballast of amalgam lamps with operating discharge current frequency of tens of kHz.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2015

Vacuum arc with a distributed cathode spot as a plasma source for plasma separation of spent nuclear fuel and radioactive waste

Results from experimental studies of a vacuum arc with a distributed cathode spot on the heated cathode are presented. Such an arc can be used as a plasma source for plasma separation of spent nuclear fuel and radioactive waste. The experiments were performed with a gadolinium cathode, the properties of which are similar to those of an uranium arc cathode. The heat flux from the plasma to the cathode (and its volt equivalent) at discharge voltages of 4-15 V and discharge currents of 44-81 A, the radial distribution of the emission intensity of gadolinium atoms and singly charged ions in the arc channel at a voltage of 4.3 V, and the plasma electron temperature behind the anode were measured. The average charge of plasma ions at arc voltages of 3.5-8 V and a discharge current of 52 A and the average rate of gadolinium evaporation in the discharge were also determined.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2016

Auxiliary glow discharge in the trigger unit of a hollow-cathode thyratron

Results from studies of a low-current glow discharge with a hollow cathode are presented. A specific feature of the discharge conditions was that a highly emissive tablet containing cesium carbonate was placed in the cathode cavity. In the absence of a tablet, the discharge ignition voltage was typically ≥3.5 kV, while the burning voltage was in the range of 500–600 V. The use of the tablet made it possible to decrease the ignition voltage to 280 V and maintain the discharge burning voltage at a level of about 130 V. A model of the current sustainment in a hollow-cathode discharge is proposed. Instead of the conventional secondary emission yield, the model uses a generalized emission yield that takes into account not only ion bombardment of the cathode, but also the emission current from an external source. The model is used to interpret the observed current−voltage characteristics. The results of calculations agree well with the experimental data. It is shown that, in some discharge modes, the external emission current from the cathode can reach 25% of the total discharge current.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2015

Fundamental Impact of Humidity on SOFC Cathode ORR

Although solid oxide fuel cells (SOFC) have demonstrated excellent performance, the durability of SOFCs under real working conditions is still an issue for commercial deployment. In particular cathode exposure to atmospheric air contaminants, such as humidity, can result in long-term performance degradation issues. Therefore, a fundamental understanding of the interaction between water molecules and cathodes is essential to resolve this issue and further enhance cathode durability. In order to study the effects of humidity on the oxygen reduction reaction (ORR), we used in-situ 18 O isotope exchange techniques to probe the exchange of water with two of themost common SOFC cathode materials, (La 0.8 Sr 0.2 ) 0.95 MnO 3±δ (LSM) and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF). In this experiment, heavy water, D 2 O (with a mass/charge ratio of m/z = 20), is used to avoid the overlapping of H 2 O and the 18 O 2 cracking fraction, which both provide a peak at m/z = 18. A series of temperature programmed isotope exchange measurements were performed to comprehensively study the interaction of water with the cathode surface as a function of temperature, oxygen partial pressure, and water vapor concentration. The results suggest that water and O 2 share the same surface exchange sites, leading to competitive adsorption. Our findings show that water prefers to exchange with LSCF at lower temperatures, around 300–450°C. For LSM, O 2 is more favorable than water to be adsorbed on the surface and the presence of O 2 limits water exchange. The experimental data are summarized in a Temperature-PO 2 diagram to help visualize how the exchange of water on each material depends on the operating conditions.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2016

Relationships between PEMFC Cathode Kinetic Losses and Contaminants’ Dipole Moment and Adsorption Energy on Pt

A database summarizing the effects of 21 contaminants on the performance of proton exchange membrane fuel cells (PEMFCs) was used to examine relationships between cathode kinetic losses and contaminant physicochemical parameters. Impedance spectroscopy data were employed to obtain oxygen reduction kinetic resistances by fitting data in the 10-158 Hz range to a simplified equivalent circuit. The contaminant dipole moment and the adsorption energy of the contaminant on a Pt surface were chosen as parameters. Dipole moments did not correlate with dimensionless cathode kinetic resistances. In contrast, adsorption energies were quantitatively and linearly correlated with minimum dimensionless cathode kinetic resistances. Contaminants influence the oxygen reduction for contaminant adsorption energies smaller than -24.5 kJ mol -1 , a value near the high limit of the adsorption energy of O 2 on Pt. Dimensionless cathode kinetic resistances linearly increase with decreasing O 2 adsorption energies below -24.5 kJ mol -1 . Measured total cell voltage losses are mostly larger than the cathode kinetic losses calculated from kinetic resistance changes, which indicates the existence of other sources of performance degradation. Modifications to the experimental procedure are proposed to ensure that data are comparable on a similar basis and improve the correlation between contaminant adsorption energy and kinetic cell voltage losses.

25 ENERGY STORAGE↗
DOE OSTI2020

Long Term Degradation of LSM Based SOFC Cathodes: Use of a Proven Accelerated Test Regimen

The overall goals of the program were: • To understand the microstructural basis of long-term performance loss in solid oxide fuel cells (SOFCs) with cathodes based on lanthanum strontium manganite (LSM, (La 1–x Sr x ) 1–yM nO 3±z ); • To develop strategies for optimizing LSM–based cathodes that achieve improved long-term performance, while exhibiting microstructural and chemical stability, for commercial fuel cell systems. The research project carried out accelerated testing of SOFCs with LSM-based cathodes of selected compositions. After intervals of accelerated testing (and control tests using non-accelerated conditions), the cells underwent extensive microstructural characterization to determine the physical and chemical changes in the cells. By analysis of a) the results of the testing, b) the observed microstructural changes, and c) the differences in these correlations between different cathode compositions and test durations, the research: • Identified a correlation between microstructural change and performance loss: specifically, between decrease of three-phase boundary (TPB) density and increase of area specific re-sistance (ASR) during operation; • Identified a cathode composition parameter — Mn excess, defined as 1/(1–y) in (La 1–x Sr x ) 1–y MnO 3±z ) — and how it affects TPB density, ASR and change of cell performance over time.

08 HYDROGEN↗
DOE OSTI2019

Self-regulating surface chemistry for more robust highly durable solid oxide fuel cell cathodes

Solid oxide fuel cells (SOFCs) offer direct conversion of hydrogen or hydrocarbon fuels to electricity with high energy conversion efficiency (>50%). Impurities that block active reaction sites on the electrode surface can markedly degrade the oxygen exchange rate, and lead to a reduction in long term durability of such devices. In this work, we propose to develop electrodes that are tolerant to Si which is one of the most prevalent cathode impurities. This work draws on our recent method to fully recover oxygen exchange kinetics following Si induced aging of ceria containing cathodes. We take advantage of elements, which over time during SOFC operation, are released by exsolution to actively trap (i.e. getter) Si impurities in a self-regulating chemical fashion. The objective is to evaluate impurity scavenging by added reactive elements that are intentionally exsolved from the SOFC cathode electrode during operation. In this study, we chose to focus our effort on one cathode material: Pr doped ceria (PCO). This material has the advantage of not containing strontium, an element known to segregate to the surface of the well-known perovkite based cathodes materials, thereby degrading their performance. As for the Si getter, we choose to focus on lanthanum, which is added in PCO in solid solution.

03 NATURAL GAS↗
NASA NTRSDate not supplied

The Effect of Anode Configuration on the Plasma Plume of a 25-A class Hollow Cathode

The effect of anode configuration on the plasma plume properties of a 25-A class hollow cathode are experimentally characterized. At a nominal operating condition of 20.8 A and 14.7 sccm of xenon, the cathode was operated with two axially-segmented anodes of different diameters at varying distance from the cathode. A fast, reciprocating motion stage was used to rapidly insert an ion saturation probe and an emissive probe on cathode centerline, and from those measurements, spatial profiles of plasma density, plasma potential, and electron temperature were calculated. For both anode diameters, maximum plasma potential and electron temperature increased with increasing anode distance. However, the 64-mm diameter anode was found to be significantly more sensitive to position, with measurements indicating that parameters changed continuously with position instead of an instantaneous mode change at a certain critical distance. The 254-mm diameter, in contrast, showed much more similar plasma property profiles across the range of anode positions tested and much smaller changes per unit increase in distance. These results are discussed in the context of assessing anode design for component-level cathode tests.

Space propulsion↗
NASA NTRSDate not supplied

The Effect of Anode Configuration on the Plasma Plume of a 25-A class Hollow Cathode

The effect of anode configuration on the plasma plume properties of a 25-A class hollow cathode are experimentally characterized. At a nominal operating condition of 20.8 A and 14.7 sccm of xenon, the cathode was operated with two axially-segmented anodes of different diameters at varying distance from the cathode. A fast, reciprocating motion stage was used to rapidly insert an ion saturation probe and an emissive probe on cathode centerline, and from those measurements, spatial profiles of plasma density, plasma potential, and electron temperature were calculated. For both anode diameters, maximum plasma potential and electron temperature increased with increasing anode distance. However, the 64-mm diameter anode was found to be significantly more sensitive to position, with measurements indicating that parameters changed continuously with position instead of an instantaneous mode change at a certain critical distance. The 254-mm diameter, in contrast, showed much more similar plasma property profiles across the range of anode positions tested and much smaller changes per unit increase in distance. These results are discussed in the context of assessing anode design for component-level cathode tests.

space propulsion↗
DOE OSTI2024

High–Energy Earth–Abundant Cathodes with Enhanced Cationic/Anionic Redox for Sustainable and Long–Lasting Na–Ion Batteries

Layered iron/manganese-based oxides are a class of promising cathode materials for sustainable batteries due to their high energy densities and earth abundance. However, the stabilization of cationic and anionic redox reactions in these cathodes during cycling at high voltage remain elusive. Here, an electrochemically/thermally stable P2-Na 0.67 Fe 0.3 Mn 0.5 Mg 0.1 Ti 0.1 O 2 cathode material with zero critical elements is designed for sodium-ion batteries (NIBs) to realize a highly reversible capacity of ≈210 mAh g –1 at 20 mA g –1 and good cycling stability with a capacity retention of 74% after 300 cycles at 200 mA g –1 , even when operated with a high charge cut-off voltage of 4.5 V versus sodium metal. Combining a suite of cutting-edge characterizations and computational modeling, it is shown that Mg/Ti co-doping leads to stabilized surface/bulk structure at high voltage and high temperature, and more importantly, enhances cationic/anionic redox reaction reversibility over extended cycles with the suppression of other undesired oxygen activities. This work fundamentally deepens the failure mechanism of Fe/Mn-based layered cathodes and highlights the importance of dopant engineering to achieve high-energy and earth-abundant cathode material for sustainable and long-lasting NIBs.

25 ENERGY STORAGE↗
DOE OSTI2018

ZnNi x Mn x Co 2–2 x O 4 Spinel as a High‐Voltage and High‐Capacity Cathode Material for Nonaqueous Zn‐Ion Batteries

Abstract Nonaqueous Zn‐ion batteries are regarded as one alternative for Li‐ion batteries. Such batteries not only afford attractive attributes of cost, but also embody the advantages of the high‐specific capacities of Zn anodes, as well as the wide potential window of nonaqueous electrolytes. To fully exploit these advantages, improved cathode materials are highly desired. In this manuscript, a new series of spinels, ZnNi x Mn x Co 2–2 x O 4 , are reported as cathode materials for nonaqueous Zn‐ion batteries. Full cells constructed using this new spinel ( x = 1/2) as a cathode paired with a metal anode showed capacities over 200 cycles of 174 mAh g −1 and an open circuit potential of 2.05 V. The battery exhibits an energy density of 305 Wh kg −1 , which is the highest energy density yet reported for a Zn‐intercalation cathode. The data show that the Zn 2+ ions reversibly intercalate into the spinel structure during the charge/discharge processes, a compositional transformation directly correlated with a multiply reversible conversion between Co 4+ /Co 3+ , Ni 4+ /Ni 3+ /Ni 2+ , and Mn 4+ /Mn 3+ oxidation states within the lattice. The data suggest that Mn, Ni cosubstitution for Co in ZnCo 2 O 4 is an efficient method to facilitate Zn‐deintercalation and enhance discharge capacity, which may provide some guidelines for designing more attractive multivalent cathodes materials.

Pan, Chengsi↗
DOE OSTI2024

Effects of Calcination Conditions on the Structural and Electrochemical Behaviors of High‐Nickel, Cobalt‐Free LiNi 0.9 Mn 0.1 O 2 Cathode

Abstract Eliminating cobalt from high‐nickel layered oxide cathodes lowers the cost of lithium‐ion batteries for electric vehicles. However, cobalt‐free cathodes with high Mn 4+ and Ni 2+ contents are prone to Li/Ni mixing after synthesis, potentially compromising battery energy density, rate capability, and cycling stability. Without cobalt facilitating cation ordering in the layered structure, the degree of Li/Ni mixing in cobalt‐free cathodes depends heavily on the calcination conditions. In this study, a systematic exploration of calcination temperatures and LiOH ratio for LiNi 0.9 Mn 0.1 O 2 (NM‐90) provides detailed insights into the optimal synthesis conditions for high‐capacity cobalt‐free cathodes with extended cycle life. Surprisingly, high Li/Ni mixing does not necessarily lead to poor cycling stability whereas low Li/Ni mixing does not guarantee a long cycle life. More importantly, although excessive calcination temperature can further decrease Li/Ni mixing, it does not necessarily enhance capacity. Instead, the pernicious effects from the H2 → H3 phase transition are amplified due to a pronounced two‐phase reaction. An extensive suite of chemical and structural characterization methods uncovers a correlation between elevated calcination temperature, phase transformation, cation ordering, and capacity fading behavior: “overcooking” high‐nickel, cobalt‐free cathodes induce structural arrangement toward that of LiNiO 2 , with exacerbated lattice distortion and surface instability accelerating capacity fade.

Lee, Steven↗