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At least 397 records · Page 22

Structural and chemical evolutions of a magnesium vanadium oxide cathode under electrochemical cycling in magnesium batteries

The design of cathode materials that remain chemically and structurally stable during repetitive ion insertion and extraction poses a significant challenge in developing multivalent batteries. The cycling stability of traditional metal oxide-based cathode is challenged by sluggish diffusion of multivalent cations and parasitic reactivity at interfacial regimes, including the cathode electrolyte interphase layer (CEI). Understanding the reactions at the cathode-electrolyte interface, particularly those induced by non-stoichiometric surface layers, is a crucial design parameter for both cathode materials and electrolytes. Here, in this study, we employed multimodal analysis, including in situ and ex situ X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (TEM) and electrochemical impedance spectroscopy (EIS) to examine the surface reactions and subsequent structural and chemical evolutions of the CEI on high voltage magnesium vanadium oxide (MgV 2 O 4 ) spinel cathode during the Mg 2+ insertion/extraction processes. The results revealed that the presence of non-stoichiometric surface layers in the magnesium vanadium oxide cathode drive the decomposition of bis(trifluoromethanesulfonyl)imide (TFSI - ) anion, leading to the formation of the CEI layer. The CEI layer could inhibit the Mg 2+ ion transfer processes. Accompanying this reactivity-driven degradation, the magnesium vanadium oxide cathode undergoes pulverization, forming clusters of nanosized particles. This process likely improves cycling ability by creating new intercalation sites and shortening the diffusion pathway for the Mg 2+ cations. This study demonstrates that controlling surface stoichiometry and engineering morphological properties are critical design parameters for high performance cathodes for multivalent batteries.

25 ENERGY STORAGE↗

Preliminary investigation of an improved metal-dielectric cathode for magnetically insulated transmission line oscillator

In order to explore the cathode with good repetition quality for the magnetically insulated transmission line oscillators, an improved metal-dielectric cathode is proposed and investigated experimentally. The cathode is designed to be step-like shape, and thin copper plated boards are periodically and compactly arrayed on the surface of the cathode base, which ensures the uniformity of the electrons emitted from the cusps of the copper plated boards. According to the numerical simulation results, the step-like shape is beneficial to convert the kinetic energy of the magnetic insulating current partially and enhance the beam-wave interaction efficiency. Finally, a preliminary experiment of an L-band magnetically insulated transmission line oscillator (MILO) with the improved metal-dielectric cathode is carried out. A high power microwave (HPM) with an average power of 1.95 GW is generated from the MILO, with an efficiency of 13.5%. Under the same experiment condition, the output power and main frequency with the presented cathode are almost the same to those with the velvet cathode. Apart from that, metal-dielectric cathode has the merits of small outgassing and long lifetime, and all of these make the improved metal-dielectric cathode significantly promising for the MILO repetition operation.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Characterization of Hollow Cathode Performance and Thermal Behavior

Hollow cathodes are one of the main life-limiting components in ion engines and Hall thrusters. Although state-of-the-art hollow cathodes have demonstrated up to 30,352 hours of operation in ground tests with careful handling, future missions are likely to require longer life, more margin and greater resistance to reactive contaminant gases. Three alternate hollow cathode technologies that exploit different emitter materials or geometries to address some of the limitations of state-of-the-art cathodes are being investigated. Performance measurements of impregnated tungsten-iridium dispenser cathodes at discharge currents of 4 to 15 A demonstrated that they have the same operating range and ion production efficiency as conventional tungsten dispenser cathodes. Temperature measurements indicated that tungsten-iridium cathodes also operate at the same emitter temperatures. They did not exhibit the expected reduction in work function at the current densities tested. Hollow cathodes with lanthanum hexaboride emitters operated over a wide current range, but suffered from lower ion production efficiency at currents below about 12.4 A because of higher insert heating requirements. Differences in operating voltages and ion production rates are explained with a simple model of the effect of cathode parameters on discharge behavior.

ion engines↗

High Current Cathode Thermal Behavior, Part II: Theory

Cathode erosion is one of the life limiting mechanisms for several classes of electric thrusters. Since cathode erosion is strongly dependent on the cathode temperature, a quantitative understanding of the effects of cathode operation on the cathode temperature is required. The development of a cathode/plasma interaction model for determining the heat loads to the cathode as function of the various free stream plasma parameters is presented. This model is combined with a cathode thermal model in order to provide a complete and integrated picture of high current cathode operation.

cathode erosion cathode temperature high current c↗

Regulation of Cathode Mass and Charge Transfer by Structural 3D Engineering for Protonic Ceramic Fuel Cell at 400 °C

Abstract Lowering the operating temperature (ideally below 400 °C) for solid oxide fuel cell (SOFC) technology deployment has been an important transition that introduces the benefit of reduced operational costs and system durability. However, the key technical issue limiting the transition is the sluggish cathodic performance, namely the oxygen reduction reaction (ORR) rate of the conventional sponge‐like cathode dramatically drops as the temperature reduces. In this paper, 3D engineering of a cathode is conducted on a protonic ceramic fuel cell to obtain an enhanced ORR between 400 and 600 °C. Compared with a cell using a conventional sponge‐like cathode, 3D engineering improves the cathode ORR by 41% at 400 °C with a peak power density of 0.410 W cm −2 . A phase field simulation is applied to assist the engineering by understanding the competition between the cathode mass and charge transfer with different cathode porosities. The results show that structural engineering of existing well‐developed cathodes is a simple and effective method to promote cathode ORR for low temperature SOFC by regulating the mass and charge transfer.

Bian, Wenjuan↗

A highly active hybrid catalyst modified (La 0.60 Sr 0.40 ) 0.95 Co 0.20 Fe 0.80 O 3-δ cathode for proton conducting solid oxide fuel cells

The sluggish reaction kinetics in the cathode usually leads to considerable cathode polarization resistance, hindering the development of proton conducting solid oxide fuel cells (H-SOFCs) operated at intermediate temperatures (400–650 °C). In this paper, to address this problem, for the first time, a novel hybrid catalyst consisting of PrNi 0.5 Mn 0.5 O 3 and PrOx is impregnated in the (La 0.60 Sr 0.40 ) 0.95 Co 0.20 Fe 0.80 O 3-δ (LSCF) cathode of H-SOFCs, resulting in significant enhancement of the cathode reaction kinetics. Single cells with impregnated LSCF cathode and BaZr 0.8 Y 0.2 O 3 (BZY) electrolyte yield a maximum power density (MPD) of 0.198 W cm -2 at 600 °C, more than doubled of that with blank LSCF cathode (0.083 W cm -2 ). ECR and EIS studies reveal that the hybrid catalyst can substantially accelerate the oxygen-ion transfer and oxygen dissociation-absorption processes in the cathode, resulting in significantly lower polarization resistance and higher MPD. In addition, the hybrid catalyst possesses good chemical and microstructural stability at 600 °C. Consequently, the single cells with impregnated LSCF cathode show excellent durability. Finally, this study shows that the impregnation of this novel hybrid catalyst in the cathode could be a promising approach to improve the performance and stability of H-SOFCs.

36 MATERIALS SCIENCE↗

Probing Operando Electrochemical Strain Generation in α-NaFeO 2 Composite Cathodes during Cycling of Na-Ion Batteries

The transition metal oxide (TMO) cathodes in Na-ion batteries suffer from low-capacity retention. Chemo-mechanical instabilities lead to the deterioration of the electrochemical performance of TMO cathodes in Li-ion batteries. However, there is not much known about the chemo-mechanical instabilities in the TMO cathodes for Na-ion batteries. Understanding the governing forces behind the interplay between the electrochemical performance and mechanical stability in TMO cathodes is critical for the development of Na-ion batteries. Here, we synchronize the digital image correlation (DIC) technique with electrochemical analysis to capture the real-time deformation behavior of the α-NaFeO 2 cathodes during cycling. When the charge cutoff voltage is 3.6 V, the cathode experiences reversible deformations (except for the first cycle). There is negative strain (shrinkage) generation during Na extraction and positive strain (expansion) generation during the subsequent Na insertion. A detailed analysis of the potential-dependent strain rate evolution points out complicated phase transformations and nonequilibrium conditions in the α-NaFeO 2 cathodes during cycling. When the charge cutoff voltage was increased to 4.2 V, there was a rapid capacity loss and large plastic deformations in the α-NaFeO 2 cathodes. We provide an in-depth discussion about the possible mechanisms behind the chemo-mechanical instabilities in the α-NaFeO 2 . In conclusion, the correlation is critical to develop material-based strategies to mitigate instability mechanisms in TMO cathodes for Na-ion batteries.

Wable, Minal [University of Maryland Baltimore Cou↗

Implications of Local Cathode Structure in Solid-State Batteries

Solid-state batteries (SSBs) are promising candidates for energy storage systems—specifically for automotive applications—owing to their higher energy density and supreme safety. SSBs currently must improve area-specific cathode loadings as well as the electro-chemo-mechanical stability at high voltages. Composite cathodes in SSBs are comprised of active material, ion and electronic conductors, binders, and electronic conducting materials. In addition to experimental limitations with engineering thick cathode architectures, low utilization and chemomechanical degradation of the cathodes limit the performance of composite cathodes. Composite cathodes must optimize several parameters simultaneously to achieve high performances that include loading, electrochemically active surface area, mechanical resilience, and porosity. This chapter summarizes the current state-of-the-art applications with regard to composite cathodes for SSBs and provides insights into cathode architectures using geometric packing models. Tailoring ion and electron transport pathways within the electrode while mitigating operational stresses is crucial for achieving energy-dense cathode structres for SSBs.

Dixit, Marm↗

Dissolution, migration, and deposition of transition metal ions in Li-ion batteries exemplified by Mn-based cathodes – a critical review

Unlike the revolutionary advances in the anodes of lithium-ion batteries from Li intercalation materials to Li alloy and/or conversion reaction materials, the development of the cathode is still dominated by the Li intercalation compounds. Transition metal ions are essential in these cathodes as the rapid redox reaction centers, and one of the biggest challenges for the TM-based cathodes is the capacity and power fading especially at an elevated temperature, which is directly associated with the dissolution–migration–deposition (DMD) process of TMs from the cathode materials. This process not only alters the surface structure of the cathode materials, but more importantly, changes the SEI composition at the anode side. There is no doubt that the TM-DMD issue should be addressed thoroughly to unlock the potential of these compounds to enable a prolonged battery lifetime. This review article mainly focuses on research activities with regard to the DMD process in TM-based cathode materials. In the first four sections, we choose Mn-based cathodes as an example to discuss how Mn DMD relates to the capacity fade of the cell, and what possible approaches might suppress the DMD process by modification of the electrode or electrolyte. In the fifth section, we discuss the TM DMD process in Ni-, Co-, Fe- and V-containing cathode materials. Furthermore, this article reviews the frontier electrochemical research on TM-based cathodes and summarizes the progress and challenges, thereby helping to advance future R&D of LIBs.

25 ENERGY STORAGE↗

Cathode Side-emission Mitigation for Linear Induction Accelerators

Linear induction accelerators (LIAs) are one of the main technologies used in creating flash x-rays used for diagnosing hydrodynamic experiments. The quality of the data produced in these experiments is dependent on the dose of x-rays generated via bremsstrahlung radiation. There are several electron beam quantities that effect the amount of dose extracted from the bremsstrahlung radiation, such as beam instabilities, corkscrew motion, and beam emittance. Injector design is key in delivering well-behaved electron beams to the accelerator, and design choices include components such as anode-cathode (AK) gap dimensions based on required voltage and current, shroud shaping, and cathode type and composition. Thermionic cathodes have shown reliable performance in electron emission, however, if enough of the cathode side is subject to high-enough electric field values, electrons can be emitted. This issue is more likely to happen when the cathode is treated with materials that have lower work functions, which is common for cathodes used in LIAs. These extra electrons can work their way through the rest of the beam, inducing high non-linearities in phase space which can increase the emittance of this beam. In this paper we outline conducted trade-space studies where we examined different shaping parameters of the cathode shroud design to decrease the effect side electrons may have on the beam emittance. Particle trajectories are determined by electric potential contours across the face of the cathode shroud component, and so we hypothesize that the proper shaping of the cathode-shroud interface can tune the electric field to mitigate the effect of side electrons. Electron beam transport is simulated down the length of the injector and the beam quality is diagnosed by studying the emittance as a function of position. Acceptable emittance increase is recorded and noted to meet radiographic requirements.

42 ENGINEERING↗

Tests of high current hollow cathodes for ion engines

The development of high power, high thrust ion engines requires the development of long life hollow cathodes capable of producing emission currents of hundreds of amperes. This paper describes results obtained through the extended testing of two 12.7 mm diameter hollow cathodes at high emission currents. The first cathode, operated on xenon for a total of 170 hours at an emission current of 100 A, sustained very little damage except for an increase in the cathode orifice diameter, from 0.953 to 1.71 mm. The second cathode was operated on xenon at 150 A emission current continuously for 24 hours, and for over 1000 hours at 100 A on argon with essentially no change in the cathode operating characteristics. Operation of this cathode was terminated due to severe erosion of several discharge chamber components located downstream of the cathode. The erosion of these components occurred despite operation at discharge voltages less than 24 volts, and poses a serious challenge to the sucessful implementation of multi-hundred ampere cathodes and high thrust ion engines.

Brophy, John R.↗

Extended testing of xenon ion thruster hollow cathodes

A hollow cathode wear-test of 508 hours was successfully completed at an emission current of 23.0 A and a xenon flow rate of 10 Pa-L/s. This test was the continuation of a hollow cathode contamination investigation. Discharge voltage was stable at 16.7 V. The cathode temperature averaged 1050 C with a 7 percent drop during the wear-test. Discharge ignition voltage was found to be approximately 20 V and was repeatable over four starts. Post-test analyses of the hollow cathode found a much improved internal cathode condition with respect to earlier wear-test cathodes. Negligible tungsten movement occurred and no formation of mono-barium tungstate was observed. These results correlated with an order-of-magnitude reduction in propellant feed-system leakage rate. Ba2CaWO6 and extensive calcium crystal formation occurred on the upstream end of the insert. Ba-Ca compound depositions were found on the Mo insert collar, on the Re electrical leads, and in the gap between the insert and cathode wall. This wear-test cathode was found to be in the best internal condition and had the most stable operating performance of any hollow cathode tested during this contamination investigation.

Sarver-Verhey, Timothy R.↗

Physical model and experimental results of cathode erosion related to power supply ripple

This paper discusses the physical effects of power supply ripple on cathode erosion and cathode arc attachment in a water-cooled, 30 kW nitrogen arcjet. Experimental results are presented for 2 percent thoriated tungsten, which show that the long-term cathode erosion rate is a decreasing function of current ripple over the range 1-13 percent. Above this range, the cathode discharge becomes unstable, and the erosion rate rapidly increases. A qualitative model of this effect is given in terms of a magnetically induced radial motion of the arc column, and an overall increase in the cathode spot radius due to the higher peak current associated with higher ripple. The most important effect of power supply ripple is therefore shown to be its ability to collectively drive the cathode attachment away from the cathode center. This leads to an increase in the cathode attachment area, and a subsequent decrease in the cathode erosion rate.

Harris, W. J.↗

Extended-testing of xenon ion thruster hollow cathodes

A hollow cathode wear-test of 508 hours was successfully completed at an emission current of 23.0 A and a xenon flow rate of 10 Pa-L/s. This test was the continuation of a hollow cathode contamination investigation. Discharge voltage was stable at 16.7 V. The cathode temperature averaged 1050 C with a 7 percent drop during the wear-test. Discharge ignition voltage was found to be approximately 20 V and was repeatable over four starts. Post-test analyses of the hollow cathode found a much improved internal cathode condition with respect to earlier wear-test cathodes. Negligible tungsten movement occurred and no formation of mono-barium tungsten was observed. These results correlated with an order-of-magnitude reduction in propellant feed-system leakage rate. Ba2CaWO6 and extensive calcium crystal formation occurred on the upstream end of the insert. Ba-Ca compound depositions were found on the Mo insert collar, on the Re electrical leads, and in the gap between the insert and cathode wall. This wear-test cathode was found to be in the best internal condition and had the most stable operating performance of any hollow cathode tested during this contamination investigation.

Sarver-Verhey, Timothy R.↗

Multiple Hollow Cathode Wear Testing for the Space Station Plasma Contactor

A wear test of four hollow cathodes was conducted to resolve issues associated with the Space Station plasma contactor. The objectives of this test were to evaluate unit-to-unit dispersions, verify the transportability of contamination control protocols developed by the project, and to evaluate cathode contamination control and activation procedures to enable simplification of the gas feed system and heater power processor. These objectives were achieved by wear testing four cathodes concurrently to 2000 hours. Test results showed maximum unit-to-unit deviations for discharge voltages and cathode tip temperatures to be +/-3 percent and +/-2 percent, respectively, of the nominal values. Cathodes utilizing contamination control procedures known to increase cathode lifetime showed no trends in their monitored parameters that would indicate a possible failure, demonstrating that contamination control procedures had been successfully transferred. Comparisons of cathodes utilizing and not utilizing a purifier or simplified activation procedure showed similar behavior during wear testing and pre- and post-test performance characterizations. This behavior indicates that use of simplified cathode systems and procedures is consistent with long cathode lifetimes.

Soulas, George C.↗

MoO3 Cathodes for High-Temperature Lithium Thin-Film Cells

MoO3 has shown promise as a cathode material that can extend the upper limit of operating temperature of rechargeable lithium thin-film electrochemical cells. Cells of this type are undergoing development for use as energy sources in cellular telephones, wireless medical sensors, and other, similarly sized portable electronic products. The LiCoO2 and LiMn2O4 cathodes heretofore used in these cells exhibit outstanding cycle lives (of the order of hundreds of thousands of cycles) at room temperature, but operation at higher temperatures reduces their cycle lives substantially: for example, at a temperature of 150 C, cells containing LiCoO2 cathodes lose half their capacities in 100 charge/discharge cycles. The superiority of MoO3 as a cathode material was demonstrated in experiments on lithium thin-film cells fabricated on glass slides. Each cell included a layer of Ti (for adhesion to the glass slide), a patterned layer of Pt that served as a cathode current collector, a cathode layer of MoO3, a solid electrolyte layer of Li3.3 PO3.8 N0.22 ("LiPON"), and an anode layer of Li. All the layers were deposited by magnetron sputtering except for the Li layer, which was deposited by thermal evaporation. These cells, along with similar ones containing LiCoO2 cathodes, were subjected to several tests, including measurements of specific capacity in charge/discharge cycling at a temperature of 150 C. The results of these measurements, plotted in the figure, showed that whereas specific capacity of the cells containing LiCoO2 cathodes faded to about half its initial value after only 100 cycles, the specific capacity of the cells containing the MoO3 cathodes faded only slightly during the first few hundred cycles and thereafter not only recovered to its initial value but continued to increase up to at least 5,500 cycles.

West, William↗

Numerical Simulations of the Partially-Ionized Gas in a 100-A LaB6 Hollow Cathode

Numerical simulations of a hollow cathode with a LaB6 emitter operating at 100 A have been performed for the first time using the 2-D Orificed Cathode (OrCa2D) code. Results for a variety of plasma properties are presented and compared with laboratory measurements. The large size of the device permits peak electron number densities in the cathode interior that are lower than those established in the NSTAR hollow cathode, which operates with a 7.3x lower discharge current and 3.2x lower mass flow rate. Also, despite the higher discharge current in the LaB6 cathode, the maximum electron current density is lower, by 4.2x, than that in the NSTAR cathode due to the larger orifice size. Simulations and direct measurements show that at 12 sccm of xenon flow the peak emitter temperature is in the range of 1594-1630 C. It is also found that the conditions for the excitement of current-driven streaming instabilities and ion-acoustic turbulence (IAT) are satisfied in this cathode, similarly to what was found in the past in its smaller counterparts like the NSTAR cathode. Based on numerical simulations, it has long been argued that these instabilities may be responsible for the anomalously large ion energies that have been measured in these discharges as well as for the enhancement of the plasma resistivity. Confirmation of the presence of IAT in this cathode is presented for the first time in a companion paper.

robotic exploration↗

Hollow Cathode Assembly Development for the HERMeS Hall Thruster

To support the operation of the HERMeS 12.5 kW Hall Thruster for NASA's Asteroid Redirect Robotic Mission, hollow cathodes using emitters based on barium oxide impregnate and lanthanum hexaboride are being evaluated through wear-testing, performance characterization, plasma modeling, and review of integration requirements. This presentation will present the development approach used to assess the cathode emitter options. A 2,000-hour wear-test of development model Barium Oxide (BaO) hollow cathode is being performed as part of the development plan. Specifically this test is to identify potential impacts cathode emitter life during operation in the HERMeS thruster. The cathode was operated with a magnetic field-equipped anode that simulates the HERMeS hall thruster operating environment. Cathode discharge performance has been stable with the device accumulating 743 hours at the time of this report. Observed voltage changes are attributed to keeper surface condition changes during testing. Cathode behavior during characterization sweeps exhibited stable behavior, including cathode temperature. The details of the cathode assembly operation of the wear-test will be presented.

Propulsion Technology↗