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At least 307 records · Page 17

A Solution-Processable High-Modulus Crystalline Artificial Solid Electrolyte Interphase for Practical Lithium Metal Batteries

The solid electrolyte interphase (SEI) has been identified as a key challenge for Li metal anodes. The brittle and inhomogeneous native SEI generated by parasitic reactions between Li and liquid electrolytes can devastate battery performance; therefore, artificial SEIs (ASEIs) have been proposed as an effective strategy to replace native SEIs. Herein, as a collaboration between academia and industrial R&D teams, a multifunctional (crystalline, high modulus, and robust, Li + ion conductive, electrolyte-blocking, and solution processable) ASEI material, LiAl-FBD (where “FBD” refers to 2,2,3,3-tetra-fluoro-1,4-butanediol), for improving Li metal battery performance is designed and synthesized. The LiAl-FBD crystal structure consists of Al 3+ ions bridged by FBD 2– ligands to form anion clusters while Li + ions are loosely bound at the periphery, enabling an Li + ion conductivity of 9.4 × 10 –6 S cm –1 . Further, the fluorinated, short ligands endow LiAl-FBD with electrolyte phobicity and high modulus. The ASEI is found to prevent side reactions and extend the cycle life of Li metal electrodes. Specifically, pairing LiAl-FBD coated 50 μm thick Li with industrial 3.5 mAh cm –2 NMC811 cathode and 2.8 μL mAh –1 lean elec-trolyte, the Li metal full cells show superior cycle life compared to bare ones, achieving 250 cycles at 1 mA cm –2 .

25 ENERGY STORAGE↗

Consequences of plane-strain and plane-stress assumptions in fully coupled chemo-mechanical Li-ion battery models

In Li-ion battery research, it is common to simulate chemo-mechanical phenomena in reduced dimensions (e.g., 2-D) as opposed to fully resolve these complex physics in 3-D. It is common to assume either (1) the out-of-plane strain is negligible (commonly referred to as plane-strain), or (2) the out-of-plane stress is negligible (commonly referred to as plane-stress). However, there is typically little consideration as to the quantitative consequences of these approximations. Furthermore, the influence of these out-of-plane assumptions can be compounded and convoluted when chemo-mechanics models implement so-called “fully coupled” formulations, where the local species concentrations influence the stress-state and the stress-state influences the local species fluxes. Here, the present manuscript explores the implications of using plane-stress and plane-strain assumptions in 2-D as compared to simulating a full 3-D electrode particle. This comparative study includes simulating both isotropic and anisotropic particle intercalation where the particles can be surrounded by either a liquid or solid electrolyte. Additionally, common Li-ion battery-model metrics such as the state-of-stress, intercalation fraction distribution, and specific capacity are compared, while also considering the effects of particle size and C-rate. As alternatives to the pure plane-strain and plane stress approximations, two modified plane-strain assumptions are found to better approximate the fully coupled chemo-mechanical 3-D behavior.

25 ENERGY STORAGE↗

Xerogel-Derived Ni Electrocatalysts for the Hydrogen Evolution Reaction in Alkaline Media

Anion exchange membrane water electrolyzers (AEMWEs) represent a promising technology for hydrogen production. The big advantage of the technology is that it allows for the use of platinum group metal-free (PGM-free) electrocatalysts at both electrodes, including catalysts for the hydrogen evolution reaction (HER) at the cathode. In addition to fulfilling the cost requirement, PGM-free HER catalysts need to meet the activity and durability targets of the AEMWEs. Here, in this work, we developed several carbon-supported, xerogel-derived nickel (Ni) HER electrocatalysts and evaluated the effect of various synthesis conditions, such as the type of carbon support, Ni-to-carbon ratio, and heat-treatment temperature and time, on their performance. Scanning transmission electron microscopy combined with energy-dispersive X-ray spectroscopy (STEM-EDS), X-ray diffraction spectroscopy (XRD), and X-ray photoelectron spectroscopy (XPS) revealed the formation of Ni nanoparticles with an oxygen-rich layer on the outside. Durability of the best-performing catalyst was assessed via a constant-current hold at 10 mA cm –2 over 100 h. This catalyst was found to be more active and durable than the reference PGM-free material, a commercial Ni catalyst supported on a Vulcan XC-72. The catalyst was also tested in the cathode of a fully PGM-free AEMWE, allowing to reach 1.90 V (1.84 V HFR-free) at 1 A cm –2 at 80 °C.

08 HYDROGEN↗

Multi-channel front-end ASIC for a 3D position-sensitive detector

Arrays of 3D position-sensitive detectors (3DPSD), operating at room temperature and using cadmium zinc telluride (CZT) and thallium bromide (TIBr) sensors, are suitable for gamma-ray spectrometry in many applications. One detector configuration, the 3D position-sensitive Virtual Frisch-Grid detector (VFG), is particularly advantageous for integrating into large area arrays. The signals generated inside each detector of the array are captured with the anode, cathode and four pads that enable the reconstruction of the position and energy of the ionizing interaction by measurements of amplitude and timing of the signals. For these applications, a low-noise front-end ASIC has been developed, capable of processing bipolar signals (needed because of AC-coupling of certain electrodes). The ASIC can be coupled to an ADC in order to form a compound “waveform digitizer” capable of post-processing the analog signals and determining amplitude and timing information. This paper describes a 32-channel front-end ASIC that is suitable for reading out a 3 × 3 or 4 × 4 element matrix in the VFG configuration. Each channel is composed of a low-noise charge amplifier with an adaptive continuous reset feedback circuit suitable for both positive and negative charge, a first order shaper and a single-to-differential converter output stage. Voltage and current references are all internally generated by 10-bit DACs and the chip is fully controllable with the I 2 C communication protocol. The readout channel response has been verified using the implemented injection circuit. Linear behavior up to ~75 ke ± with the gain of ~80 mV/fC, and up to ~200 ke ± with the gain of ~30 mV/fC was demonstrated. In conclusion, the first test result waveforms using a 137 Cs radioactive source on a 5 × 5 × 12 mm 3 TIBr crystal are reported.

47 OTHER INSTRUMENTATION↗

Influence of discharge polarity on streamer breakdown criterion of ambient air in a non-uniform electric field

Streamer breakdown of atmospheric air with non-uniform dc electric field in a needle-to-plate electrode configuration is studied using a semi-analytic model and experimental measurements. A high voltage (either positive or negative) is applied to a hollow needle with 0.51 mm outer diameter and 0.25 mm inner diameter separated from a planar ground electrode by a gap distance of 0.1–1.4 cm. Breakdown voltages are recorded for both positive and negative discharge polarities. Empirical relations between the critical avalanche size for streamer breakdown and the gap distance are proposed. Using these empirical relations, a semi-analytic model based on Meek's criterion for streamer breakdown is developed to accurately predict the measured breakdown voltages. It is found that for pd > 380 Torr cm (or d > 0.5 cm at one atmosphere) streamer breakdown of ambient air occurs at a lower applied voltage for a positively biased needle compared to that with a negatively biased needle, referred as the polarity effect. For pd < 380 Torr cm breakdown is attained at a lower applied voltage with a negatively biased needle compared to that with a positively biased needle, and breakdown mode transits from the polarity effect to the so called inverted polarity effect.

42 ENGINEERING↗

System Modeling of a Lunar Molten Regolith Electrolysis Plant

Introduction: In-Situ Resource Utilization (ISRU) is the process of extracting local resources to produce commodities for propulsion, life support systems, and off-planet construction rather than transporting consumables from Earth. Molten Regolith Electrolysis (MRE) is a novel ISRU method of extracting oxygen gas and metal alloy from lunar regolith. The MRE process involves placing lunar regolith between two electrodes, through which current is passed, to melt the regolith and reduce the metal oxide constituents by direct electrolysis (e.g. FeO, SiO2, MgO, Al2O3) into oxygen gas and metal alloys. The oxygen is liquefied and used as propellant for landers, while the metals (e.g. Ferro-alloys) are further processed and used in structural building materials and parts manufacturing. A system model was developed that accounted for the major processes of an MRE plant (from excavation of raw materials to storage of products) to assess the feasibility of a lunar MRE plant. The System Engineering and Integration (SE&I) ISRU Modeling and Analysis (SIMA) team utilized its previously documented system sizing model, the Mission Analysis and Integration Tool (MAIT) [1] as framework of the system model. MAIT uses MATLAB/Simulink to integrate subsystem models into a complete system model of the MRE plant. Total mass, volume, and power requirements were computed for numerous iterations of a MRE plant. System Model: Figure 1: MRE Plant Block Diagram The regolith excavation model determines the mass and power needed to excavate sufficient regolith. The preheating auger initiates the regolith heating process before regolith enters the MRE re-actor to reduce the energy required to turn the solid into a molten liquid. The MRE reactor is modeled in COMSOL Multiphysics and based on the research by Dominguez, Sibille, and Schreiner [2, 3, 4]. This preliminary reactor model provides an accurate calculation of thermal equilibrium during electrochemical operation of the reactor system to assess the optimal mass and power required to process the inlet flow of regolith. The model also computes the outlet flowrates of oxygen and molten products. For this analysis, the primary components of the metal alloy considered were iron and silicon. The oxygen is then purified using an Yttrium Stabilized Zirconia (YSZ) electrode, followed by liquefaction using a 90K cryocooler to be stored as liquid oxygen in insulated cylindrical tanks. In future iterations of the system model, the molten metal tapped from the MRE reactor will undergo additional processing or refinement. However, downstream handling of metals is currently a technology gap that is missing a high TRL subsystem model. Therefore, for this analysis, the accumulated metal alloy stream terminates after leaving the MRE reactor. Study Goals: This analysis investigates multiple input variables to the system to determine the sensitivity of a (near) complete plant at full-scale. This preliminary investigation ran parametric sweeps on the MRE reactor geometry, electrical current supply, layers of multi-layer insulation (MLI) on the reactor, size of the electrodes in the oxygen purification model, and regolith composition (based on landing site location). Three production targets of oxygen (1,000, 10,000, and 50,000 kg/yr) were investigated for this analysis. The parametric sweeps conducted in this analysis provide valuable insight into the expected impact of the various model inputs on plant size. This information can be used to identify the most critical components of the plant and guide future decisions on allocating funding for research and development, providing subsystem developers with appropriate interfaces with downstream and upstream processes, and assessing the overall feasibility of MRE when compared to other ISRU plants. References: [1] Carlson, A. et al. (2024) ICES, ICES-2024-53. [2] Dominguez, D.A., and Sibille, L. (2011) AIAA, AIAA-2011-700. [3] Schreiner, S.S. (2015) MIT, Dissertation. [4] Schreiner, S.S. et al. (2016) ASR, 57(7), pp.1585-1603.

ISRU↗

The importance of cycle-by-cycle data in performing rapid battery technology development and validation

Lithium-ion battery (LiB) technology is playing a crucial role in transforming the predominantly fossil fuel-based transportation and stationary storage sectors to achieve a low-carbon economy. Rapid innovation in the LiB materials to electrode to cell design is happening to satisfy the performance, life, and safety metrics required by those myriads of applications. Lately, advanced analytics, such as machine-learning or artificial intelligence (ML/AI) techniques, are being used more frequently to aid in expedited LiB technology development, performance validation, and life prediction. The success of these techniques often relies on a large volume of well-defined and high-quality battery test data. On the other hand, most battery developers and research and development (R&D) communities are still following a classical approach to develop batteries, which is running calendar- and/or cycle-aging tests, performing reference performance tests (RPTs), and conducting post-mortem analyses periodically without paying attention to the wealth of data often not collected during the calendar or cycle life aging tests. This sparse data collection approach is time- and resource-intensive, requiring data capture and evaluation of months to years of RPT data to diagnose accurate battery state of performance, health, and safety. Even so, the underlying aging modes and mechanisms can be missed. If collected properly, battery test data during cycling or calendaring can be efficiently combined with ML/AI techniques to create powerful tools in the rapid diagnosis of battery state of performance, health, and safety along with insights into underlying aging modes and mechanisms. In this report, we discuss the importance of effective cycle-by-cycle (CBC) data collection with example case studies. Within a reasonable timeframe, RPT data are often inadequate in capturing many of the crucial battery aging dynamics, which often predominantly show up in CBC test data. Finally, we also show examples of ML/AI techniques that use CBC data in rapid diagnosis and projection of LiB state of health (SOH) to motivate the scientific community in collecting and using CBC data to facilitate expeditious technology development and validation.

25 ENERGY STORAGE↗

Testing Fundamental Properties of Ionic Liquids for Colloid Microthruster Applications

NASA's New Millennium Program is scheduled to test a Disturbance Reduction System (DRS) on Space Technology 7 (ST7) as part of the European Space Agency's (ESA's) LISA Pathfinder Mission in late 2009. Colloid Micronewton Thrusters (CMNTs) will be used to counteract forces, mainly solar photon pressure, that could disturb gravitational reference sensors as part of the DRS. The micronewton thrusters use an ionic liquid, a room temperature molten salt, as propellant. The ionic liquid has a number of unusual properties that have a direct impact on thruster design. One of the most important issues is bubble formation before and during operation, especially during rapid pressure transitions from atmospheric to vacuum conditions. Bubbles have been observed in the feed system causing variations in propellant flow rate that can adversely affect thruster control. Bubbles in the feed system can also increase the likelihood that propellant will spray onto surfaces that can eventually lead to shorting high voltage electrodes. Two approaches, reducing the probability of bubble formation and removing bubbles with a new bubble eliminator device in the flow system, were investigated at Busek Co., Inc. and the Jet Propulsion Laboratory (JPL) to determine the effectiveness of both approaches. Results show that bubble formation is mainly caused by operation at low pressure and volatile contaminants in the propellant coming out of solution. A specification for the maximum tolerable level of contamination has been developed, and procedures for providing system cleanliness have been tested and implemented. The bubble eliminator device has also been tested successfully and has been implemented in recent thruster designs at Busek. This paper focuses on the propellant testing work at JPL, including testing of a breadboard level bubble eliminator device.

bubble formation↗

Propellant-Flow-Actuated Rocket Engine Igniter

A rocket engine igniter has been created that uses a pneumatically driven hammer that, by specialized geometry, is induced into an oscillatory state that can be used to either repeatedly impact a piezoelectric crystal with sufficient force to generate a spark capable of initiating combustion, or can be used with any other system capable of generating a spark from direct oscillatory motion. This innovation uses the energy of flowing gaseous propellant, which by means of pressure differentials and kinetic motion, causes a hammer object to oscillate. The concept works by mass flows being induced through orifices on both sides of a cylindrical tube with one or more vent paths. As the mass flow enters the chamber, the pressure differential is caused because the hammer object is supplied with flow on one side and the other side is opened with access to the vent path. The object then crosses the vent opening and begins to slow because the pressure differential across the ball reverses due to the geometry in the tube. Eventually, the object stops because of the increasing pressure differential on the object until all of the kinetic energy has been transferred to the gas via compression. This is the point where the object reverses direction because of the pressure differential. This behavior excites a piezoelectric crystal via direct impact from the hammer object. The hammer strikes a piezoelectric crystal, then reverses direction, and the resultant high voltage created from the crystal is transferred via an electrode to a spark gap in the ignition zone, thereby providing a spark to ignite the engine. Magnets, or other retention methods, might be employed to favorably position the hammer object prior to start, but are not necessary to maintain the oscillatory behavior. Various manifestations of the igniter have been developed and tested to improve device efficiency, and some improved designs are capable of operation at gas flow rates of a fraction of a gram per second (0.001 lb/s) and pressure drops on the order of 30 to 50 kilopascal (a few psi). An analytical model has been created and tested in conjunction with a precisely calibrated reference model. The analytical model accurately captures the overall behavior of this innovation. The model is a simple "volume-orifice" concept, with each chamber considered a single temperature and pressure "node" connected to adjacent nodes, or to vent paths through flow control orifices. Mass and energy balances are applied to each node, with gas flow predicted using simple compressible flow equations.

Wollen, Mark↗

Light-field control of real and virtual charge carriers

We report light-driven electronic excitation is a cornerstone for energy and information transfer. In the interaction of intense and ultrafast light fields with solids, electrons may be excited irreversibly, or transiently during illumination only. As the transient electron population cannot be observed after the light pulse is gone, it is referred to as virtual, whereas the population that remains excited is called real. Virtual charge carriers have recently been associated with high-harmonic generation and transient absorption, but photocurrent generation may stem from real as well as virtual charge carriers. However, a link between the generation of the carrier types and their importance for observables of technological relevance is missing. Here we show that real and virtual charge carriers can be excited and disentangled in the optical generation of currents in a gold–graphene–gold heterostructure using few-cycle laser pulses. Depending on the waveform used for photoexcitation, real carriers receive net momentum and propagate to the gold electrodes, whereas virtual carriers generate a polarization response read out at the gold–graphene interfaces. On the basis of these insights, we further demonstrate a proof of concept of a logic gate for future lightwave electronics. Our results offer a direct means to monitor and excite real and virtual charge carriers. Individual control over each type of carrier will markedly increase the integrated-circuit design space and bring petahertz signal processing closer to reality.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Chemical contributions to silicon anode calendar aging are dominant over mechanical contributions

Silicon (Si) anodes are a promising candidate for increasing the energy density of lithium (Li)-ion batteries for electric vehicles. However, they have recently been identified as having poor calendar life that is insufficient for commercial needs, in addition to the well-known issue of their poor cycle life resulting from large volume expansion. Here, a specially designed protocol with variable rest periods between intermittent cycling is used to evaluate the impact of the mechanical disruption of Si and solid electrolyte interphase (SEI) from cycling on calendar aging measurements. Si was found to undergo more mechanical degradation during calendar aging with intermittent cycling than graphite. However, Si anode capacity fade was still dominated by time, especially for rest periods greater than or equal to 1 month between cycling. Postmortem dQ/dV half-cell analysis indicated this was mainly due to Li inventory loss and an increase in electrode resistance. Isothermal microcalorimetry further demonstrated that Si passivation is more disrupted than graphite passivation with intermittent cycling and suggested that there may be a chemical buildup of a detrimental species in the electrolyte, leading to a large spike in heat after the Si and SEI are disrupted by cycling.

25 ENERGY STORAGE↗

Fabrication of porous transport electrodes: Development of quantitative approach for quality control

This work focuses on porous transport electrodes (PTEs), which integrate the anodic catalyst with the adjacent Ti porous transport layer (PTL). Challenges in catalyst deposition on PTLs, particularly at low loadings, motivated this study to evaluate various fabrication methods and characterization approaches. This work investigated Pt-treated PTLs coated with Ir-based catalysts using several common methods, including airbrush coating, rod coating, ultrasonic spray coating, electrodeposition, and sputter deposition, with catalyst loadings ranging from 2.9 to 0.1 mg/cm 2 , providing the opportunity for comparisons across a large set of samples produced by different methods. Two widely accessible characterization techniques: X-ray computed tomography (XCT) and scanning electron microscopy energy dispersive X-ray spectroscopy (SEM-EDS) were explored. Initial evaluation of selected samples with XCT provided qualitative insights into catalyst distribution, however comprehensive quantitative analysis was limited. SEM-EDS enabled detailed information on the catalyst distribution both qualitatively and quantitatively using two metrics. Atomic and surface area % ratios of Pt:Ir and Ti:Ir revealed trends in catalyst loading and losses into the PTL pores, as well as evaluating the homogeneity of catalyst coatings. The analysis demonstrated that ultrasonic spray coating, electrodeposition, and sputter coating produced the most homogeneous coatings, with minimal catalyst losses observed for electrodeposition and sputter coating. By adapting common techniques with novel, standardized methodologies, this work establishes a universally applicable framework for cross-study comparison of PTEs. The SEM-EDS approach provides a practical, accessible tool for PTE characterization and contributes a reference dataset supporting both research development and rapid quality control.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coke Deposition and Smoke Formation in Turbojet Engines

In the early development of jet engines, it was occasionally found that excessive amounts of coke or other carbonaceous deposits were formed in the combustion chamber. Sometimes a considerable amount of smoke was noted in the-exhaust gases. Excessive coke deposits may adversely affect jet-engine performance in several ways. The formation of excessive amounts of coke on or just downstream of a fuel nozzle (figs. 116(a) and (b)) changes the fuel-spray pattern and possibly affects combustor life and performance. Similar effects on performance can result from the deposition of coke on primary-air entry ports (fig. 116(c)). Sea-level or altitude starting may be impaired by the deposition of coke on spark-plug electrodes (fig. 116(b)), deposits either grounding the electrodes completely or causing the spark to occur at positions other than the intended gap. For some time it was thought that large deposits of coke in turbojet combustion chambers (fig. 116(a)) might break away and damage turbine blades; however, experience has indicated that for metal blades this problem is insignificant. (Cermet turbine blades may be damaged by loose coke deposits.) Finally, the deposition of coke may cause high-temperature areas, which promote liner warping and cracking (fig. 116(d)) from excessive temperature gradients and variations in thermal-expansion rates. Smoke in the exhaust gases does not generally impair engine performance but may be undesirable from a tactical or a nuisance standpoint. Appendix B of reference 1 and references 2 to 4 present data obtained from full-scale engines operated on test stands and from flight tests that indicate some effects on performance caused by coke deposits and smoke. Some information about the mechanism of coke formation is given in reference 5 and chapter IX. The data indicate that (1) high-boiling fuel residuals and partly polymerized products may be mixed with a large amount of smoke formed in the gas phase to account for the consistency, structure, and chemical composition of the soft coke in the dome and (2) the hard deposits on the liner are similar to petroleum coke and may result from the liquid-phase thermal cracking of the fuel. During the early development period of jet engines, it was noted that the excessive coke deposits and exhaust smoke were generally obtained when fuel-oil-type fuels were used. Engines using gasoline-type fuels were relatively free from the deposits and smoke. These results indicated that some type of quality control would be needed in fuel specifications. Also noted was the effect of engine operating conditions on coke deposition. It is possible that, even with a clean-burning fuel, an excessive amount of coke could be formed at some operating conditions. In this case, combustor redesign could possibly reduce the coke to a tolerable level. This chapter is a summary of the various coke-deposition and exhaust-smoke problems connected- with the turbojet combustor. Included are (1) the effect of coke deposition on combustor life or durability and performance; (2) the effect of combustor design, operating conditions, inlet variables, and fuel characteristics on coke deposition; (3) elimination of coke deposits; (4) the effect of operating conditions and fuel characteristics on formation of exhaust smoke; and (5) various bench test methods proposed for determining and controlling fuel quality.

Hibbard, R. R.↗

High Throughput Source-less Plasma Deposition of Structured Silicon Anodes for Lithium-Ion Batteries

Amprius developed a manufacturing solution for silicon nanowire anode that relies on an inexpensive, high throughput, and high gas precursor utilization plasma deposition method that uses the anode foils as electrodes for plasma generation. The capacitively couple plasma (CCP) method is used in semiconductor and photovoltaic industry and Amprius modified existing high throughput equipment to use anode foils and to deposit amorphous silicon. The equipment was installed ahead of the program at Amprius site. The rest of the tasks included foil handling and process development. The equipment passed site acceptance tests (SAT) and the process parameter mapping was completed, indicating that the target process window limits produce output materials at the rate and with yield and specifications that meet the manufacturing target criteria. Amprius has hired supporting personnel to optimize processes and run the equipment. A parallel task verified the baseline performance of the silicon anode material, to be used as reference for the new manufacturing method.

25 ENERGY STORAGE↗

Detonation to Deflagration-Mode Transitions in Pulsed Plasma Accelerators

PULSED plasma accelerators typically operate by storing energy in a capacitor bank and then discharging this energy through a gas. The current in such discharges will ionize the gas and produce a strong magnetic field, which interacts with the flowing current to accelerate the plasma through the Lorentz body force. For the present work, two plasma accelerator types employing this general scheme are of interest: the gas-fed pulsed plasma thruster (PPT) 1 and the quasi-steady magnetoplasmadynamic (MPD) accelerator. 2 The gas-fed pulsed plasma accelerator is generally understood as a completely transient device discharging in ∼1-10 μs. When the capacitor bank is discharged through the gas, a current sheet forms at the breech of the thruster and propagates forward under a j × B body force, entraining and accelerating propellant it encounters. This process is sometimes referred to in literature as 'snowplowing' the propellant or accelerating the gas in a detonation-mode because the current sheet representation approximates that of a strong detonation shockwave propagating through the gas. For these devices, acceleration of the initial current sheet ceases when either the current sheet reaches the end of the device and is ejected or when the current in the circuit reverses, striking a new 'crowbar' discharge at the breech and depriving the initial sheet of additional acceleration. In general, PPTs typically claim thrust efficiencies (ratio of jet kinetic energy to input electrical energy) registering in the teens or lower. 3 In the quasi-steady MPD accelerator, the pulse is lengthened to ∼1 ms or longer and maintained at an approximately constant level during discharge through the use of a pulse-forming network (PFN) of capacitors. After an initial transient discharge, which is typically short relative to the overall discharge period, the plasma assumes a relatively steady-state configuration, known as 'quasi-steady' MPD operation. 2 In this state, ionized gas flows through a stationary current channel in a manner that is sometimes referred to as deflagration-mode operation owing to the similarities to deflagration waves in gases. The plasma experiences electromagnetic acceleration as the plasma flows through the current channel towards the exit of the device. Quasi-steady MPD thrusters claim efficiencies up to 50% for certain propellants.4 There has been significant and sustained research over several decades on both gas-fed PPTs and quasi-steady MPD thrusters, however there have been pulsed thrusters that do not appear to exactly fit either classification, instead possessing a mixture of operational qualities characteristic of both thruster variants. The Coaxial High ENerGy (CHENG) thruster by Cheng, et al.5 operated on the short 10 μs timescales characteristic of PPTs, but claimed the high thrust densities, high efficiencies, and low electrode erosion rates that are more consistent with the MPD/deflagration mode of plasma acceleration. Gas-fed PPT research by Ziemer, et al. 3, 6 identified two separate regimes of performance in those thrusters. The regime at higher mass bits (termed Mode I in that work) possessed relatively constant thrust efficiency as a function of mass bit, while the second regime at very low mass bits (termed Mode II) exhibited an increase in efficiency with decreasing mass bit. Work by Poehlmann et al.7 and by Sitaraman and Raja8 sought to understand the performance of the CHENG thruster and the Mode I/Mode II performance in PPTs by modeling the acceleration using the Hugoniot Relation, with the detonation and deflagration modes of plasma acceleration representing two distinct sets of solutions to the relevant conservation laws. In these works, it was proposed that the values of the various controllable parameters determined whether the accelerator would operate in detonation or deflagration mode. Our hypothesized view of the acceleration process in the CHENG thruster and in PPTs experiencing a transition from Mode I to Mode II is inspired by observations of the transition from the PPT mode of operation to the quasi-steady MPD mode. Specifically, the quasi-steady MPD was discovered by driving a PPT to extended pulse lengths. Above a certain pulse length threshold the transient plasma current sheet transitions into a stable plasma acceleration mode that 'replicates in every observable detail steady flow self-field magnetoplasmadynamic acceleration.' 9 In the present work, instead of treating the accelerator as if it were only operating in a single mode during a pulse, we consider the initial stage of the discharge in all cases as a current sheet forming at the breach of the accelerator and moving towards the exit as a detonation wave. If the current sheet reaches the exit of the accelerator before the discharge is completed, the view of the acceleration mode transitions to the deflagration mode-type found in quasi-steady MPD thrusters. In previous work10 we presented a modeling framework that first captured the time-evolution of the current sheet (detonation) mode of the thruster and then transitioned into the quasi-steady MPD (deflagration) mode of plasma acceleration. In the present work, variations of the controllable parameters - specifically the pulsed circuit properties, the amount of mass injected into the thruster, and the relative timing between the initial gas injection and the initiation of the plasma current sheet - will be used to explore the thruster performance. A range of parameters are explored to demonstrate that standard gas-fed pulsed plasma accelerators, the CHENG thruster, and the quasi-steady MPD accelerator are variations of the same device, with the overall acceleration of the plasma depending upon the behavior of the plasma discharge during initial transient phase and the relative lengths of the detonation and deflagration modes of operation.

Polzin, Kurt A.↗

Estimating the energy requirement for hydrogen production in proton exchange membrane electrolysis cells using rapid operando hydrogen crossover analysis

Hydrogen (H 2 ) crossover in proton exchange membrane water electrolyzers refers to the process by which hydrogen produced at the cathode traverses the membrane and mixes with the oxygen produced at the anode. This phenomenon reduces efficiency and may pose flammability hazards. In this work we present a method for quantifying the H 2 content of the anode exhaust gas using a gas chromatograph that is capable of sampling data every 2 min. Subsequent theory is presented to calculate the crossover flux, overall H 2 efficiency, and H 2 energy requirements. Results the effects of membrane thickness using Nafion TM N117 (178 um) and Nafion TM NR212 (51 um) membranes. Furthermore, it was found that thinner membranes lead to improved VI performance but exhibit higher crossover rates. Despite their increased crossover, leading to decreased hydrogen efficiency, the calculated required energy for NR212 membrane-electrode assemblies (MEAs) was significantly lower than that of N117 MEAs.

08 HYDROGEN↗

A Multi-Physics Study on High-Specific Power Li-O2 Batteries for Electric Aircraft

Commercialization of lithium-air batteries faces many challenges, such as electrolyte decomposition, short cycle life, low energy and power density, etc. However, commercialization of Li-O2 batteries for aeronautics is much more challenging due to additional safety constraints on cyclability and performance (high specific power and specific energy). For this presentation, we will discuss inter-related aspects of physics-based modeling of a pack: cell and battery model calibration. In addition, we will evaluate and present optimal battery designs for high discharge current density, high discharge time, and low battery mass using simulation-based optimization.The Finite Element Model (FEM) used to simulate a Li-O2 cell is based on the work of Bevara [1]. The different aspects of the model are based on: porous electrode theory and concentrated electrolyte theory; quantum tunneling model for the resistance of conformal layer of discharge product (Li2O2) [1]; Butler-Volmer kinetics for electrochemical reaction; Fick's diffusion for oxygen transport; and an oxygen dissolution model is applied at the air/electrolyte interface [2]. The electrolyte properties such as ion conductivity, ion diffusion, oxygen diffusion, and mass density of the electrolyte were taken from Molecular Dynamics (MD) simulations [3]; while the other model parameters, which includes mass of cell components, were calibrated to match experiments at high discharge current densities. The cell mass includes the anode, cathode, separator, electrolyte, and other components (such as current collector). This calibrated model is used to perform parametric studies on cathode thickness, porosity, tortuosity, carbon particle size, electrolyte transport and material properties, partial pressure of oxygen, discharge time, and discharge current density to study optimal designs for high specific power and energy. References:1. Bevara, V. & Andrei, P. (2014), J. Electrochem. Soc. 161 (14), A2068-A2079.2.Mehta, M. & Andrei, P. (2015), J. Power Sources. 286, 299-308.3.Liyana-Arachchi, T.; Haskins, J.; Burke, C.; Diederichsen, K.; McCloskey, B.; & Lawson, J. (2018), J. Phys. Chem. B. 122 (36), 8548 - 8559.4.Choi, W.; Kikumoto, H.; Choudhary, R. & Ooka, R. (2018), Applied Energy, 209, 306-321.

Mehta, Mohit↗