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At least 109 records · Page 6

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.↗

Fluid model of plasma outside a hollow cathode neutralizer

The present study analyzes the capability of a fluid model of electron transport to explain observed properties of the external plasma of a hollow cathode neutralizer used to neutralize beams emerging from ion thrusters. Calculations reported here show that when the effective collision frequency in such a model is near the plasma frequency, the resulting electric potential and electron temperature variations are in qualitative agreement with values measured in the plume mode of the hollow cathode. Both theory and experiment show strong variations of temperature and potential within a few centimeters of the cathode orifice.

Parks, D. E.↗

Three-Dimensional Reconstruction and Microstructure Modeling of Porosity-Graded Cathode Using Focused Ion Beam and Homogenization Techniques

In this study, microstructure of a porosity-graded lanthanum strontium manganite (LSM) cathode of solid oxide fuel cells (SOFCs) has been characterized using focused ion beam (FIB) and scanning electron microscopy(SEM) combined with image processing. Two-point correlation functions of the two-dimensional (2D) images taken along the direction of porosity gradient are used to reconstruct a three-dimensional (3D) microstructure. The effective elastic modulus of the two-phase porosity-graded cathode is predicted using strong contrast (SC) and composite inclusion (CI) homogenization techniques. The effectiveness of the two methods in predicting the effective elastic properties of the porositygraded LSM cathode is investigated in comparison with the results obtained from the finite element model (FEM).

25 ENERGY STORAGE↗

Modeling Planar Electrodes and Zero–Gap Membrane Electrode Assemblies for CO 2 Electrolysis

Multiphysics modeling enables probing of conditions inside a CO 2 electrolyzer that are difficult to measure, such as local concentrations and pH, as well as rapid testing of possible design changes. A one-dimensional model for a zero-gap membrane electrode assembly (MEA) CO 2 electrolyzer was developed with the assumption that catalyst layers interact with the membrane ionomer such that the ionomer affects the underlying kinetics. The kinetics for bicarbonate reacting to form hydrogen are fit using a planar electrode model for silver with an ionomer coating. The MEA model results are validated against experimental studies for current density and product selectivity. Flooding of the cathode is modeled using saturation curves, and results show that blocked pores in the microporous layer play a significant role in limiting the mass transport at high potentials (>2.8 V). Sensitivity studies showed that CO Faradaic efficiency can be increased by decreasing catalyst layer thickness and porosity, and decreasing KHCO 3 concentration.

30 DIRECT ENERGY CONVERSION↗

Editors’ Choice—Natural Convection Boundary Layer Thickness at Elevated Chloride Concentrations and Temperatures and the Effects on a Galvanic Couple

The natural convection boundary layer ( δ n c ) and its influence on cathodic current in a galvanic couple under varying electrolytes as a function of concentration (1 − 5.3 M NaCl) and temperature (25 °C−45 °C) were understood. Polarization scans were obtained under quiescent conditions and at defined boundary layer thicknesses using a rotating disk electrode on platinum and stainless steel 304L (SS304L); these were combined to determine δ n c . With increasing chloride concentration and temperature, δ n c decreased. Increased mass transport (Sherwood number) results in a decrease in δ n c , providing a means to predict this important boundary. Using Finite Element Modeling, the cathodic current was calculated for an aluminum alloy/SS304L galvanic couple as a function of water layer ( WL ) thickness and cathode length. Electrolyte domains were delineated, describing (i) dominance of ohmic resistance over mass transport under thin WL , (ii) the transition from thin film to bulk conditions at δ n c , and (iii) dominance of mass transport under thick WL . With increasing chloride concentration, cathodic current decreased due to decreases in mass transport. With increasing temperature, increased cathodic current was related to increases in mass transport and solution conductivity. This study has implications for sample sizing and corrosion prediction under changing environments.

25 ENERGY STORAGE↗

The swelling mechanism of cathodes in Li/(CFx)(sub n) cells

Active material particles spatial arrangement in combination with the nature of the electrochemical reduction mechanism were found to be the major cause of excessive swelling in cathodes in Li/(CF(x))n cells. A better understanding of the chemical reaction mechanism, a possible new role for the carbon, and a model for cathode growth are discussed.

Margalit, Nehemiah↗

Atmospheric pressure arc discharge with ablating graphite anode

The anodic carbon arc discharge is used to produce carbon nanoparticles. Recent experiments with the carbon arc at atmospheric pressure helium demonstrated the enhanced ablation rate for narrow graphite anodes resulting in high deposition rates of carbonaceous products on the copper cathode (Fetterman et al 2008 Carbon 46 1322–6). The proposed model explains these results with interconnected steady-state models of the cathode and the anode processes. When considering cathode functioning, the model predicts circulation of the particles in the near-cathode region: evaporation of the cathode material, ionization of evaporated atoms and molecules in the near-cathode plasma, return of the resulting ions to the cathode, surface recombination of ions and electrons followed again by cathode evaporation etc. In the case of the low anode ablation rate, the ion acceleration in the cathode sheath provides the major cathode heating mechanism. In the case of an intensive anode ablation, an additional cathode heating is due to latent fusion heat of the atomic species evaporated from the anode and depositing at the cathode. Using the experimental arc voltage as the only input discharge parameter, the model allows us to calculate the anode ablation rate. A comparison of the results of calculations with the available experimental data shows reasonable agreement.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Integration issues of a plasma contactor Power Electronics Unit

A hollow cathode-based plasma contactor is baselined on International Space Station Alpha (ISSA) for spacecraft charge control. The plasma contactor system consists of a hollow cathode assembly (HCA), a power electronics unit (PEU), and an expellant management unit (EMU). The plasma contactor has recently been required to operate in a cyclic mode to conserve xenon expellant and extend system life. Originally, a DC cathode heater converter was baselined for a continuous operation mode because only a few ignitions of the hollow cathode were expected. However, for cyclic operation, a DC heater supply can potentially result in hollow cathode heater component failure due to the DC electrostatic field. This can prevent the heater from attaining the proper cathode tip temperature for reliable ignition of the hollow cathode. To mitigate this problem, an AC cathode heater supply was therefore designed, fabricated, and installed into a modified PEU. The PEU was tested using resistive loads and then integrated with an engineering model hollow cathode to demonstrate stable steady-state operation. Integration issues such as the effect of line and load impedance on the output of the AC cathode heater supply and the characterization of the temperature profile of the heater under AC excitation were investigated.

Pinero, Luis R.↗

Temperature Distributions in Hollow Cathode Emitters

Life-limiting processes in hollow cathodes are determined largely by the temperature of the emitter. To support development of cathode life models we have developed a noncontact temperature measurement technique which employs a stepper motor-driven fiber optic probe. The probe is driven inside the hollow cathode and collects light radiated by the hot interior surface of the emitter. Ratio pyrometry is used determine the axial temperature profile. Thermocouples on the orifice plate provide measurements ofthe external temperature during cathode operation and are used to calibrate the pyrometer system in situ with a small oven enclosing the externally heated cathode. Initial measurements of the temperature distribution in a hollow cathode with the same geometry as a cathode that failed after operating at 12 A emission current for 27800 hours are discussed.

ratio pyrometer system↗

Two-dimensional model of orificed micro-hollow cathode discharge for space application

In this paper, we describe results of self-consistent two-dimensional (x-z) particle-in-cell simulations, with a Monte Carlo collision model, of an orificed micro-hollow cathode operating in a planar diode geometry. The model includes thermionic electron emission with Schottky effect, secondary electron emission due to cathode bombardment by the plasma ions, several different collision processes, and a non-uniform xenon background gas density in the cathode-anode gap. Simulated results showing behavior of the plasma density, potential distribution, and energy flux towards the hollow cathode and orifice walls, are discussed. In addition, results of simulations showing the effect of different Xe gas pressures, orifice size, and cathode voltage, on operation of the micro-hollow cathode are presented.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

The effect of cathode geometry on barium transport in hollow cathode plasmas

The effect of barium transport on the operation of dispenser hollow cathodes was investigated in numerical modeling of a cathode with two different orifice sizes. Despite large differences in cathode emitter temperature, emitted electron current density, internal xenon neutral and plasma densities, and size of the plasma-surface interaction region, the barium transport in the two geometries is qualitatively very similar. Barium is produced in the insert and flows to the surface through the porous structure. A buildup of neutral Ba pressure in the plasma over the emitter surface can suppress the reactions supplying the Ba, restricting the net production rate. Neutral Ba flows into the dense Xe plasma and has a high probability of being ionized at the periphery of this zone. The steady state neutral Ba density distribution is determined by a balance between pressure gradient forces and the drag force associated with collisions between neutral Ba and neutral Xe atoms. A small fraction of the neutral Ba is lost upstream. The majority of the neutral Ba is ionized in the high temperature Xe plasma and is pushed back to the emitter surface by the electric field. The steady state Ba{sup +} ion density distribution results from a balance between electrostatic and pressure forces, neutral Xe drag and Xe{sup +} ion drag with the dominant forces dependent on location in the discharge. These results indicate that hollow cathodes are very effective at recycling Ba within the discharge and therefore maintain a high coverage of Ba on the emitter surface, which reduces the work function and sustains high electron emission current densities at moderate temperatures. Barium recycling is more effective in the cathode with the smaller orifice because the Ba is ionized in the dense Xe plasma concentrated just upstream of the orifice and pushed back into the hollow cathode. Despite a lower emitter temperature, the large orifice cathode has a higher Ba loss rate through the orifice because the Xe plasma density peaks further upstream.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Role of Redox-Inactive Transition-Metals in the Behavior of Cation-Disordered Rocksalt Cathodes

Owing to the capacity boost from oxygen redox activities, Li-rich cation-disordered rocksalts (LRCDRS) represent a new class of promising high-energy Li-ion battery cathode materials. Redox-inactive transition-metal (TM) cations, typically d 0 TM, are essential in the formation of rocksalt phases, however, their role in electrochemical performance and cathode stability is largely unknown. In the present study, the effect of two d 0 TM (Nb 5+ and Ti 4+ ) is systematically compared on the redox chemistry of Mn-based model LRCDRS cathodes, namely Li 1.3 Nb 0.3 Mn 0.4 O 2 (LNMO), Li 1.25 Nb 0.15 Ti 0.2 Mn 0.4 O 2 (LNTMO), and Li 1.2 Ti 0.4 Mn 0.4 O 2 (LTMO). Although electrochemically inactive, d 0 TM serves as a modulator for oxygen redox, with Nb 5+ significantly enhancing initial charge storage contribution from oxygen redox. Further studies using differential electrochemical mass spectroscopy and resonant inelastic X-ray scattering reveal that Ti 4+ is better in stabilizing the oxidized oxygen anions (O n- , 0 < n < 2), leading to a more reversible O redox process with less oxygen gas release. As a result, much improved chemical, structural and cycling stabilities are achieved on LTMO. Detailed evaluation on the effect of d 0 TM on degradation mechanism further suggests that proper design of redox-inactive TM cations provides an important avenue to balanced capacity and stability in this newer class of cathode materials.

25 ENERGY STORAGE↗

Effect of crystallite geometries on electrochemical performance of porous intercalation electrodes by multiscale operando investigation

Lithium-ion batteries are yet to realize their full promise because of challenges in the design and construction of electrode architectures that allow for their entire interior volumes to be reversibly accessible for ion storage. Electrodes constructed from the same material and with the same specifications, which differ only in terms of dimensions and geometries of the constituent particles, can show surprising differences in polarization, stress accumulation and capacity fade. Here, using operando synchrotron X-ray diffraction and energy dispersive X-ray diffraction (EDXRD), we probe the mechanistic origins of the remarkable particle geometry-dependent modification of lithiation-induced phase transformations in V2O5 as a model phase-transforming cathode. A pronounced modulation of phase coexistence regimes is observed as a function of particle geometry. Specifically, a metastable phase is stabilized for nanometre-sized spherical V2O5 particles, to circumvent the formation of large misfit strains. Spatially resolved EDXRD measurements demonstrate that particle geometries strongly modify the tortuosity of the porous cathode architecture. Greater ion-transport limitations in electrode architectures comprising micrometre-sized platelets result in considerable lithiation heterogeneities across the thickness of the electrode. These insights establish particle geometry-dependent modification of metastable phase regimes and electrode tortuosity as key design principles for realizing the promise of intercalation cathodes. Designing electrode architectures for Li-ion batteries that can be reversibly accessible for ion storage can be challenging. Using operando techniques the mechanistic origin of lithiation-induced phase transformations in a V2O5 model cathode is now clarified.

Luo, Yuting↗

Mathematical model of a lithium/polypyrrole cell

A mathematical model to simulate the charge/discharge behavior of a lithium/lithium perchlorate-propylene carbonate/polypyrrole secondary battery cell is presented. The model can be used to gain a better understanding of the behavior of this cell and to provide guidance toward the design of new secondary batteries which utilize an electronically conductive polymer such as polypyrrole as the cathode. The model includes the capability of handling charge and discharge behavior and is used to study the effect of various design parameters on the performance of the cell.

Yeu, Taewhan↗

(Plenary) Electrochemical Diagnostics and Modeling in Developing the PEMFC Cathode

Reducing the use of precious metal in a proton exchange membrane fuel cell is a key challenge in mass commercialization of fuel cell electric vehicles. However, as Pt loadings are reduced, fuel cell performance losses due to mass transport phenomena become more localized to the Pt and ionomer interface. In this paper, we provide an overview of how we use in-situ electrochemical diagnostics and modeling to understand the performance of low-Pt electrodes, identify their key limiting factors, and guide our catalyst layer development. Furthermore, diagnostics used to quantify the local-Pt oxygen transport resistance and the ionomer adsorption on the Pt surface will be discussed.

25 ENERGY STORAGE↗