Electrochemical Cycling and Lithium Insertion in Nanostructured FeF3 Cathodes
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Galvanostatic intermittent titration technique (GITT) - a popular method for characterizing kinetic and transport properties of battery electrodes - is predicated on the proper evaluation of electrode active area. LiNi 0.5044 Co 0.1986 Mn 0.2970 O 2 (NCM523) material exhibits a complex morphology in which sub-micron primary particles aggregate to form secondary particle agglomerates. Our work proposes a new active area formulation for primary/secondary particle agglomerate materials to better mimic the morphology of NCM532 electrodes. Furthermore, this formulation is then coupled with macro-homogeneous models to simulate GITT and half-cell performance of NCM523 electrodes. Subsequently, the model results are compared against the experimental results to refine the area formulation. A single parameter, the surface roughness factor, is proposed to mimic the change in interfacial area, diffusivity and exchange current density simultaneously and detailed modeling results are presented to provide valuable insights into the efficacy of the formulation.
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Changes to the LANL / BNL photocathode programs are a strategic response to evolving needs and opportunities within NNSA. The Materials by Design strategy engages the broader material science communities at both LANL and BNL. Progress has been non-linear with time and investment. Techniques honed for one application can be rapidly applied to many others. For example, Cs 2 Te following successes of smooth K 2 CsSb. We enter a cycle of using accelerator-based tools to improve accelerators. Providers of advanced tools of material science (accelerator based x-ray light sources) are now availing themselves of the same capabilities to improve the next-generation machines. We are looking to define future collaborations.
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Long DARHT II injector cathode operating lifetimes are desirable for flash radiography of hydrodynamic tests at the dual-axis radiographic hydrotest facility (DARHT). The specification for cathode operating lifetime given to Spectra-Mat in the purchase orders for the 311X-M cathodes is ≥ 1000 hours at full operating temperature (~1120 °C). Of the five most-recent cathodes operated on DARHT II, only two have met this specification. It is desirable to have cathodes lifetimes considerably longer than the specified 1000 hours. In this report we present the thermal and vacuum history of cathode 12 (serial no. [S/N] 15), a 311X-M cathode, as recorded in the historian database and the shot data database. The hope is that by examining this history we can identify the parameter (or parameters) that are limiting the DARHT II 311X-M cathode lifetimes. This is the first in a series of 5 DARHT Tech Notes in which recent cathode thermal and vacuum histories are examined. The other tech notes in this series are DARHT Tech Notes Nos. 502 (cathode 13, S/N 19), 503 (cathode 14, S/N 20), 504 (cathode 15, S/N 21), and 505 (cathode 16, S/N 22). In DARHT Tech Note No. 506 we will compare the recorded thermal and vacuum histories of cathodes 12-16 and attempt to understand the cathode lifetime limitations based on the stored cathode data presented in DARHT Tech Notes 501-505 and other relevant information.
Long DARHT II injector cathode operating lifetimes are desirable for flash radiography of hydrodynamic tests at the dual-axis radiographic hydrotest facility (DARHT). The specification for cathode operating lifetime given to Spectra-Mat in the purchase orders for the 311X-M cathodes is ≥ 1000 hours at full operating temperature (~1120 oC). Of the five most-recent cathodes operated on DARHT II, only two have met this specification. It is desirable to have cathodes lifetimes considerably longer than the specified 1000 hours. In this report we present the thermal and vacuum history of cathode 16 (serial no. [S/N] 22), a 311X-M cathode, as recorded in the historian database and the shot data database. The hope is that by examining this history we can identify the parameter (or parameters) that are limiting the DARHT II 311X-M cathode lifetimes. This is the fifth in a series of 5 DARHT Tech Notes in which recent cathode thermal and vacuum histories are examined. The other tech notes in this series are DARHT Tech Notes Nos. 501 (cathode 12, S/N 15), 502 (cathode 13, S/N 19), 503 (cathode 14, S/N 20), and 504 (cathode 15, S/N 21). In DARHT Tech Note No. 506 we will compare the recorded thermal and vacuum histories of cathodes 12-16 and attempt to understand the cathode lifetime limitations based on the stored cathode data presented in DARHT Tech Notes 501-505 and other relevant information.
DC arc plasma from Ti, Al, and Ti{sub 1-x}Al{sub x} (x = 0.16, 0.25, 0.50, and 0.70) compound cathodes was characterized with respect to plasma chemistry and charge-state-resolved ion energy. Scanning electron microscopy, X-ray diffraction, and Energy-dispersive X-ray spectroscopy of the deposited films and the cathode surfaces were used for exploring the correlation between cathode-, plasma-, and film composition. Experimental work was performed at a base pressure of 10{sup −6} Torr, to exclude plasma-gas interaction. The plasma ion composition showed a reduction of Al of approximately 5 at. % compared to the cathode composition, while deposited films were in accordance with the cathode stoichiometry. This may be explained by presence of neutrals in the plasma/vapour phase. The average ion charge states (Ti = 2.2, Al = 1.65) were consistent with reference data for elemental cathodes, and approximately independent on the cathode composition. On the contrary, the width of the ion energy distributions (IEDs) were drastically reduced when comparing the elemental Ti and Al cathodes with Ti{sub 0.5}Al{sub 0.5}, going from ∼150 and ∼175 eV to ∼100 and ∼75 eV for Ti and Al ions, respectively. This may be explained by a reduction in electron temperature, commonly associated with the high energy tail of the IED. The average Ti and Al ion energies ranged between ∼50 and ∼61 eV, and ∼30 and ∼50 eV, respectively, for different cathode compositions. The attained energy trends were explained by the velocity rule for compound cathodes, which states that the most likely velocities of ions of different mass are equal. Hence, compared to elemental cathodes, the faster Al ions will be decelerated, and the slower Ti ions will be accelerated when originating from compound cathodes. The intensity of the macroparticle generation and thickness of the deposited films were also found to be dependent on the cathode composition. The presented results may be of importance for choice of cathodes for thin film depositions involving compound cathodes.
The National Aeronautics and Space Administration (NASA) Science Mission Directorate In- Space Propulsion Technology office is sponsoring NASA Glenn Research Center (GRC) to develop a 4 kW-class Hall thruster propulsion system for implementation in NASA science missions. Tests were performed within NASA GRC Vacuum Facility 5 at background pressure levels that were six times lower than what has previously been attained in other vacuum facilities. A study was conducted to assess the impact of varying the cathode-to-anode flow fraction and cathode position on the performance and operational characteristics of the High Voltage Hall Accelerator (HiVHAc) thruster. In addition, the impact of injecting additional xenon propellant in the vicinity of the cathode was also assessed. Cathode-to-anode flow fraction sensitivity tests were performed for power levels between 1.0 and 3.9 kW. It was found that varying the cathode flow fraction from 5 to approximately 10% of the anode flow resulted in the cathode-to-ground voltage becoming more positive. For an operating condition of 3.8 kW and 500 V, varying the cathode position from a distance of closest approach to 600 mm away did not result in any substantial variation in thrust but resulted in the cathode-to-ground changing from -17 to -4 V. The change in the cathode-to-ground voltage along with visual observations indicated a change in how the cathode plume was coupling to the thruster discharge. Finally, the injection of secondary xenon flow in the vicinity of the cathode had an impact similar to increasing the cathode-to-anode flow fraction, where the cathode-to-ground voltage became more positive and discharge current and thrust increased slightly. Future tests of the HiVHAc thruster are planned with a centrally mounted cathode in order to further assess the impact of cathode position on thruster performance.
For this work, Fe-based platinum group metal (PGM)-free catalysts were incorporated into electrospun fiber mat or powder cathode membrane-electrode-assemblies (MEAs) with a Nafion 211 membrane and a Pt/C powder anode. Fabrication and characterization tests were performed on MEAs with: (1) a conventional powder cathode with a neat Nafion binder, (2) a fiber mat cathode with a Nafion/polyethylene oxide (PEO) binder, where PEO was extracted before MEA testing, (3) a powder cathode with a blended binder of Nafion and polyvinylidene fluoride (PVDF), and (4) a series of fiber mat cathodes with different Nafion/PVDF binder weight ratios. Cathode degradation occurred, with a loss in power output, in MEAs with a neat Nafion powder cathode or with a Nafion fiber cathode. In contrast, little or no power loss was observed for powder or fiber cathodes when the binder was a blend of Nafion and PVDF. The presence of hydrophobic PVDF drove water and electrogenerated peroxide out of the cathode, away from catalyst particles, which improved cathode durability, but PVDF also decreased the binder conductivity and slowed oxygen reduction kinetics, resulting in lower power densities. A 75:25 w:w Nafion:PVDF fiber cathode MEA was the best compromise for maximizing power and minimizing catalyst degradation. For such a cathode, with a PGM-free cathode catalyst loading of 3.0 mg cm –2 , a power density of 88 mW cm –2 at 0.5 V, 80 °C, and 200 kPa abs pressure was maintained for 80 h of continuous operation.
The main objective of this project is to unravel the degradation mechanism of LSCF cathodes under realistic operating conditions with different types of contaminants, aiming towards the rational design of cathodes with high-performance and enhanced durability by combining a porous backbone (such as LSCF) with a thin catalyst coating. The mechanistic understanding will help us to optimize the composition and morphology of the catalyst layer and microstructure of the LSCF backbone for better performance and durability. More specifically, the technical objectives include: (1) to unravel the degradation mechanism of LSCF cathodes under realistic operating conditions with different types of contaminants using in situ and ex situ measurements performed on specially-designed cathodes; (2) to examine the microstructural and compositional evolution of LSCF cathodes as well as the cathode/electrolyte interfaces under realistic operating conditions; (3) to correlate the fuel cell performance instability and degradation with the microstructural and morphological evolution and surface chemistry change of the cathode under realistic operating conditions; (4) to explore new catalyst materials and electrode structures to enhance the stability of the LSCF cathode under realistic operating conditions; and (5) to validate the long term stability of the modified LSCF cathode in commercially available cells under realistic operating conditions. We have systematically evaluated LSCF cathodes in symmetrical cells and anode supported cells under realistic conditions with different types of contaminants such as humidity, CO 2 , and Cr. Electrochemical models for the design of test cells and understanding of mechanisms have been developed for the exploration of fundamental properties of electrode materials. It is demonstrated that the activity and stability of LSCF cathodes can be degraded by the introduction of contaminants. The microstructural and compositional evolution of LSCF cathodes as well as the cathode/electrolyte interfaces under realistic operating conditions has been studied. It is found that SrO readily segregated/enriched on the LSCF surface. More severe contamination conditions cause more SrO on surface. Novel catalyst coatings through particle depositions (PrOx) or continuous thin films (PNM) were successfully developed to improve the activity and stability of LSCF cathodes. Finally, we have demonstrated enhanced activity and stability of LSCF cathodes over longer periods of time in homemade and commercially available cells by an optimized PNM (dense film and particles) infiltration process, under clean air and realistic operating conditions (3% H 2 O, 5% CO 2 and direct Crofer contact). Both performance and durability of single cells with PNM coating has been enhanced compared with those without coating. Raman analysis of cathodes surface indicated that the intensity of SrCrO 4 was significantly decreased.
A compact, high-current, hollow cathode utilizing a lanthanum hexaboride (LaB6) thermionic electron emitter has been developed for use with high-power Hall thrusters and ion thrusters. LaB6 cathodes are being investigated due to their long life, high current capabilities, and less stringent xenon purity and handling requirements compared to conventional barium oxide (BaO) dispenser cathodes. The new cathode features a much smaller diameter than previously developed versions that permit it to be mounted on axis of a Hall thruster ( internally mounted ), as opposed to the conventional side-mount position external to the outer magnetic circuit ("externally mounted"). The cathode has also been reconfigured to be capable of surviving vibrational loads during launch and is designed to solve the significant heater and materials compatibility problems associated with the use of this emitter material. This has been accomplished in a compact design with the capability of high-emission current (10 to 60 A). The compact, high-current design has a keeper diameter that allows the cathode to be mounted on the centerline of a 6- kW Hall thruster, inside the iron core of the inner electromagnetic coil. Although designed for electric propulsion thrusters in spacecraft station- keeping, orbit transfer, and interplanetary applications, the LaB6 cathodes are applicable to the plasma processing industry in applications such as optical coatings and semiconductor processing where reactive gases are used. Where current electrical propulsion thrusters with BaO emitters have limited life and need extremely clean propellant feed systems at a significant cost, these LaB6 cathodes can run on the crudest-grade xenon propellant available without impact. Moreover, in a laboratory environment, LaB6 cathodes reduce testing costs because they do not require extended conditioning periods under hard vacuum. Alternative rare earth emitters, such as cerium hexaboride (CeB6) can be used in this configuration with possibly an even longer emitter life. This cathode is specifically designed to integrate on the centerline of a high-power Hall thruster, thus eliminating the asymmetries in the plasma discharge common to cathodes previously mounted externally to the thruster s magnetic circuit. An alternative configuration for the cathode uses an external propellant feed. This diverts a fraction of the total cathode flow to an external feed, which can improve the cathode coupling efficiency at lower total mass flow rates. This can improve the overall thruster efficiency, thereby decreasing the required propellant loads for different missions. Depending on the particular mission, reductions in propellant loads can lead to mission enabling capabilities by allowing launch vehicle step-down, greater payload capability, or by extending the life of a spacecraft.
A hollow cathode-based plasma contactor has been baselined for use on the Space Station to reduce station charging. The plasma contactor provides a low impedance connection to space plasma via a plasma produced by an arc discharge. The hollow cathode of the plasma contactor is a refractory metal tube, through which xenon gas flows, which has a disk-shaped plate with a centered orifice at the downstream end of the tube. Within the cathode, arc attachment occurs primarily on a Type S low work function insert that is next to the orifice plate. This low work function insert is used to reduce cathode operating temperatures and energy requirements and, therefore, achieve increased efficiency and longevity. The operating characteristics and lifetime capabilities of this hollow cathode, however, are greatly reduced by oxygen bearing contaminants in the xenon gas. Furthermore, an optimized activation process, where the cathode is heated prior to ignition by an external heater to drive contaminants such as oxygen and moisture from the insert absorbed during exposure to ambient air, is necessary both for cathode longevity and a simplified power processor. In order to achieve the two year (approximately 17,500 hours) continuous operating lifetime requirement for the plasma contactor, a test program was initiated at NASA Lewis Research Center to demonstrate the extended lifetime capabilities of the hollow cathode. To date, xenon hollow cathodes have demonstrated extended lifetimes with one test having operated in excess of 8000 hours in an ongoing test utilizing contamination control protocols developed by Sarver-Verhey. The objectives of this study were to verify the transportability of the contamination control protocols developed by Sarver-Verhey and to evaluate cathode contamination control procedures, activation processes, and cathode-to-cathode dispersions in operating characteristics with time. These were accomplished by conducting a 2000 hour wear test of four hollow cathodes with different xenon gas purities and activation processes. The following will be presented: a description of the facility and test hardware, testing procedures and operating conditions, a discussion of test results, and conclusions.
The current design of the Nuclear Electric Xenon Ion System (NEXIS) employs a reservoir cathode as both the discharge and neutralizer cathode to meet the 10 yr thruster design life. The main difference between a reservoir cathode and a conventional discharge cathode is the source material (barium-containing compound) is contained within a reservoir instead of in an impregnated insert in the hollow tube. However, reservoir cathodes do not have much life test history associated with them. In order to demonstrate the feasibility of using a reservoir cathode as an integral part of the NEXIS ion thruster, a 2000 hr life test was performed. Several proof-of-concept (POC) reservoir cathodes were built early in the NEXIS program to conduct performance testing as well as life tests. One of the POC cathodes was sent to Marshall Space Flight Center (MSFC) where it was tested for 2000 hrs in a vacuum chamber. The cathode was operated at the NEXIS design point of 25 A discharge current and a xenon flow rate of 5.5 sccm during the 2000 hr test. The cathode performance parameters, including discharge current, discharge voltage, keeper current; keeper voltage, and flow rate were monitored throughout test. Also, the temperature upstream of cathode heater, the temperature downstream of the cathode heater, and the temperature of the orifice plate were monitored throughout the life of the test. The results of the 2000 hr test will be described in this paper. Included in the results will be time history of discharge current, discharge voltage, and flow rate. Also, a time history of the cathode temperature will be provided.