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At least 235 records · Page 13

Experimental considerations and applications for time-resolved impedance on silicon-anode battery systems

Dynamic electrochemical impedance spectroscopy (dEIS) utilizes a superimposed multi-sinusoidal waveform and enables temporally resolved investigations on various electrochemical processes; however, the signal-to-noise ratio must be maximized while retaining linearity and stationarity within the system. In the present work, we probe the impact of the waveform’s total amplitude as well as the waveform and phase profiles. The equal amplitude multi-sinusoidal waveform with 35 mV total amplitude (<1 mV per frequency) and random phase profile exhibits the lowest impedance noise. This input signal is sufficient in avoiding the high frequency signal attenuation from the potentiostat’s low-pass filter. Additionally, we demonstrate the optimized dEIS waveform’s utility in investigating surface passivation within thin-film and composite silicon (Si) anodes. Within a two-electrode Si-lithium metal coin cell, the charge transfer resistance (RCT) associated with alloying kinetics dominates the overall impedance. RCT increases with state of charge indicating a kinetic bottleneck at higher lithiation states. To explore this further, we utilize a three-electrode Si-LiNi0.8Mn0.1Co0.1O2 pouch cell to deconvolute the Si impedance contributions. The evolution of the solid electrolyte interphase (SEI) and charge transfer resistances correlate to specific Li–Si alloy phases. We attribute this to the influence of Si particle volume expansion on SEI instabilities and a kinetic bottleneck at higher lithiation states.

Lam, Steven [ORNL]↗

Open-Air Manufacturing of Efficient Large-Area Perovskite Solar Cells to Meet Stability and Cost Targets

This SETO-funded project (DE-EE0009516) developed a fully open-air manufacturing pathway for perovskite solar cells and modules, eliminating vacuum-based processing steps while improving device stability. Open-air ultrasonic spray deposition, solution combustion synthesis, rapid thermal processing, and atmospheric plasma curing were developed and optimized for all functional device layers — perovskite absorber, hole transport layers (HTLs), electron transport layers (ETLs), transparent conducting oxides (TCOs), and rear electrodes — without reliance on vacuum. Sprayed organic ETLs preserved perovskite crystal structure and enabled power conversion efficiencies exceeding 20%, and open-air processed TCOs and rear electrodes achieved optoelectronic performance comparable to sputtered alternatives at substantially lower manufacturing cost. Device stability was assessed through accelerated aging protocols aligned with IEC and ISOS standards, combined with high-throughput optical diagnostics that identified key degradation mechanisms and antagonistic interactions among heat, humidity, and illumination stressors. A comprehensive technoeconomic analysis quantified the cost and throughput advantages of open-air manufacturing over conventional vacuum-based processes, identifying vacuum deposition as the dominant cost driver and demonstrating a clear pathway toward the $0.02/kWh target. The project produced five peer-reviewed journal publications, eleven conference presentations, two patents/applications, and five Ph.D. dissertations.

14 SOLAR ENERGY↗

A Multiphysics Study to Improve Specific Energy of Primary Batteries for Low Temperature Operation for Deep Space Missions

Several lander missions on the outer planets such as Europa, Enceladus, and Titan require electrical power to operate scientific and communication equipment. The traditional power generation methods, such as a photovoltaic array, are not feasible as their efficiency drops significantly at these vast distances. The novel radioisotope power systems are not practical today based on current lander designs and the effectiveness of these systems. To perform in situ science on distant planets, a high specific energy battery (>700 Wh/kg) needs to operate for about 480 hours under cold temperatures (-40C or 0C) [1]. While a primary battery such as Li-CFx can provide high specific energy at room temperature, its specific capacity decreases significantly at low temperatures. One of the causes for this drop is low ion and electrical conductivity, and slower reaction kinetics. Slower transport and facile kinetics lead to an increase in the battery’s resistance and higher voltage drops during the cell operation, thus reducing specific capacity. Both the transport and kinetics show a strong dependence on temperature. Thus, a small temperature rise can lead to an increase in the reaction rate and ion conductivity; since the temperature, cell resistance, and specific capacity are interdependent. A conventional battery model accounts for ohmic, thermodynamic, and, electrochemical, and chemical decomposition heating. The ohmic heating can be controlled by designing a resistive microstructure and varying the ratios of the active materials [2]. The kinetics can be improved by increasing the surface area, reducing the particle size, or adding a catalyst. These parameters are often optimized to achieve high specific energy at room temperatures. A similar optimization study is not available at low temperatures and for a primary (high specific energy) battery. For this presentation, we will explore the effect of geometrical, microstructural, and material properties on optimal specific capacity at low temperatures through multiphysics simulations. The ion transport resistance depends on the porosity and the tortuosity of an electrode and the separator.

M. Mehta↗

Performance of a small, graphite electrode, multistage depressed collector with a 500-W, continuous wave, 4.8- to 9.6-GHz traveling wave tube

A small, isotropic graphite multistage depressed collector (MDC) and a short permanent magnet refocuser were designed, fabricated, and evaluated in conjunction with a 500-W, continuous-wave (CW), 4.8 to 9.6 GHz traveling wave tube (TWT). A novel performance optimization system and technique were used to optimize the TWT-MDC performance for saturated broad-band operation. The MDC performance was evaluated in both four- and three-stage configurations. Average TWT overall and four-stage collector efficiencies of 43.8 and 82.6 percent, respectively, were obtained for saturated octave-bandwidth operation. The isotropic graphite electrode material performed well, and shows considerable promise. However, considerably more test experience is required before definitive conclusions on its suitability for space and airborne TWT's can be made.

Ramins, Peter↗

Low Temperature Double-Layer Capacitors Using Asymmetric and Spiro-Type Quaternary Ammonium Salts

Double-layer capacitors capable of operating at extremely low temperatures (e.g., as low as -80.degree. C.) are disclosed. Electrolyte solutions combining a base solvent (e.g., acetonitrile) and a cosolvent are employed to lower the melting point of the base electrolyte. Example cosolvents include methyl formate, ethyl acetate, methyl acetate, propionitrile, butyronitrile, and 1,3-dioxolane. A quaternary ammonium salt including at least one of triethylmethylammonium tetrafluoroborate (TEMATFB) and spiro-(1,1')-bipyrrolidium tetrafluoroborate (SBPBF.sub.4), is used in an optimized concentration (e.g., 0.10 M to 0.75 M), dissolved into the electrolyte solution. Conventional device form factors and structural elements (e.g., porous carbon electrodes and a polyethylene separator) may be employed.

Brandon, Erik J.↗

Design optimization of MAPS-based detectors using a data-driven fast simulation approach

A parametric simulation tool for pixel sensors is presented. A realistic pixel response is simulated purely based on measurement input, without requiring detailed knowledge of the underlying manufacturing process. As such, it provides an efficient alternative to the use of Technology Computer-Aided Design simulations, which typically depend on proprietary process information. Due to its parametric approach, the package is fast and thus particularly useful for larger detector systems and high hit rate environments. This work presents measurements, simulation and its validation for the MALTA2 sensor. It is a small collection electrode monolithic active pixel sensor produced in the Tower 180 nm complementary metal-oxide-semiconductor imaging process. Modifications to the sensor’s periphery, mainly in the hit merger, are studied in order to optimize the performance for tracking and calorimetry. This optimization is of special interest as part of the MALTA3 sensor redesign in the 65 nm Tower Partners Semiconductor Co. process.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Robust Oxygen‐Vacancy‐Engineered Co(OH) 2 /Cu Heterostructures Boost Nitrate Electroreduction to Ammonia beyond 2 A cm −2

Electrocatalytic nitrate reduction reaction (NO 3 RR) presents a sustainable paradigm for green NH 3 synthesis and NO 3 − wastewater valorization. However, overcoming sluggish NO 3 RR kinetics under industrial-current operation persists as a critical challenge. Herein, robust oxygen vacancy-enriched heterostructures (O v -Co(OH) 2 /Cu) are engineered through in situ electrochemical reconstruction. By coupling Cu-mediated NO 3 − -to-NO 2 − conversion with O v -Co(OH) 2 -accelerated NO 2 − -to-NH 3 transformation, this heterostructured system delivers an unprecedented NH 3 yield rate of 167.8 mg h −1 cm −2 and 97.7% Faradaic efficiency at >2 A cm −2 , while maintaining exceptional current tolerance over 25 h. Operando spectroscopic characterizations and theoretical calculations reveal that the introduction of O v in Co(OH) 2 synergistically accelerates water dissociation to ensure continuous hydrogen supply and optimizes *NOOH adsorption, reducing the energy barrier for the rate-limiting step (*NO 2 to *NOOH). To demonstrate practical viability, a membrane-electrode-assembly electrolyzer integrating NO 3 RR with glycerol oxidation reaction achieves highly effective co-production of NH 3 and formate alongside wastewater treatment. In conclusion, this work offers new insights into the rational design of electrocatalysts through in situ reconstruction-induced vacancy engineering for scalable and practical NO 3 RR applications.

ammonia synthesis↗

Exsolution of NiCo alloys over Ruddlesden-Popper perovskite for mild electrochemical synthesis of ammonia on protonic ceramic electrochemical cells

Ammonia synthesis from renewable energies on protonic ceramic electrochemical cells (PCECs) shows great potential. The primary challenges in ammonia synthesis on PCECs include sluggish catalytic activity, competition from the hydrogen evolution reaction, and unsatisfactory durability of the cathode, which is the active site of ammonia generation. Here, in this study, we report an elaborate design of the cathode with an intended formula of Pr 4 Ni 1.79 Co 1.2R u 0.01 O 10-δ , where NiCo alloy nanoparticles are exsolved from Ruddlesden-Popper perovskite substrates after the reduction in 5 % H 2 /Ar at 400 °C for 1 h, for electrocatalysis of the nitrogen reduction reaction to ammonia. The host material Pr 4 Ni 1.8 Co 1.2 O 10-δ with embeddable layered structure and stability was deliberately chosen to fix the Ru cation and maximize the catalytic activity of NiCo. Also, density functional theory calculations suggest that Ru doping provides an optimal balance between structural stability and redox activity, facilitating the controlled exsolution of NiCo nanoparticles and enhancing catalytic performance. As a result, the composite electrode with exsolved NiCo alloy and abundant oxygen vacancies on fuel-electrode-supported PCECs achieves a superior electrochemical activity towards ammonia synthesis: a peak ammonia formation rate of 27.84 μg h −1 cm −2 and excellent Faradaic efficiencies of 62.6 % at 350 °C.

30 DIRECT ENERGY CONVERSION↗

Highly dense atomic Fe–Ni dual metal sites for efficient CO 2 to CO electrolyzers at industrial current densities

Carbon-supported, atomically dispersed, nitrogen-coordinated metal sites (e.g., Fe and Ni) are arguably the most promising catalysts for the electrochemical reduction of CO 2 to CO due to their unique catalytic properties and the use of earth-abundant elements. However, conventional single metal sites are constrained by their structural simplicity, causing either too weak or too strong absorption/desorption of multiple critical intermediates (e.g., *COOH and *CO). Current catalysts also suffer from ultra-low loadings (<1.0 wt%) of atomic metal active sites in catalysts, leading to inadequate performance for CO 2 -to-CO conversion. Here, we develop dual Ni/Fe metal site catalysts with significantly increased atomically dispersed metal loadings (up to 4.8 wt%). A gas-phase chemical vapor deposition (CVD) approach to introducing single Ni sites was integrated with Fe 2 O 3 /ZIF-8 precursors, followed by an optimal thermal activation. The optimized CVD-Ni/Fe–N–C catalyst exhibited remarkable electrocatalytic performance for the CO 2 reduction to CO in a continuous membrane-electrode-assembly electrolyzer, achieving a maximum CO faradaic efficiency (FE CO ) of 96% at a current density of 700 mA cm −2 in a near-neutral electrolyte. Furthermore, a desirable but challenging acidic flow-cell electrolyzer was designed using this dual metal site catalyst to improve CO 2 utilization, accomplishing a FE CO of up to 95% at a CO partial current density close to 600 mA cm −2 . Density functional theory (DFT) calculations suggest a synergetic effect between Fe–Ni pairs facilitating *COOH intermediate formation and *CO desorption simultaneously during CO 2 to CO conversion. This is key to breaking the linear scaling relationship of conventional single-metal site catalysts during the CO 2 reduction reaction.

36 MATERIALS SCIENCE↗

Transition region ignition characteristics of n-heptane fuel sprays

Ignition studies were perferred on monodisperse n-heptane sprays at atmospheric pressure over a range of equivalence ratios and droplet diameters. A capacitive discharge spark ignition system was used as the ignition source, providing independent control of spark energy and duration. Preliminary measurements were made to optimize spark duration and spark gap, optimum conditions being those at which the maximum frequency or probability of ignition was observed. The effect of spark duration on ignition frequency for several spark energies was determined for equivalence ratios of 0.5 and 1.0 and initial droplet diameters of 28 and 68 microns. Spark duration had little effect on ignition frequency over the entire 15 to 170 mu s range examined. Spark durations of 70 to 80 mu s were used for all subsequent work. The spark gap was optimized at equivalence ratios of 0.6, 0.8 and 1.0 and initial droplet diameters of 30, 40, 50, 60 and 70 microns by varying the electrode spacing from 0.5 to 5.0 mm while maintaining a constant spark energy. The optimum gap was determined to be 3.0 mm for nearly all conditions.

Danis, A. M.↗

Combustion characteristics in the transition region of liquid fuel sprays

A number of important effects have been observed in the droplet size transition region in spray combustion systems. In this region, where the mechanism of flame propagation is transformed from diffusive to premixed dominated combustion, the following effects have been observed: (1) maxima in burning velocity; (2) extension of flammability limits; (3) minima in ignition energy; and (4) minima in NOx formation. A monodisperse aerosol generator has been used to form and deliver a well controlled liquid fuel spray to the combustion test section where measurements of ignition energy have been made. The ignition studies were performed on monodisperse n-heptane sprays at atmospheric pressure over a range of equivalence ratios and droplet diameters. A capacitive discharge spark ignition system was used as the ignition source, providing independent control of spark energy and duration. Preliminary measurements were made to optimize spark duration and spark gap, optimum conditions being those at which the maximum frequency or probability of ignition was observed. Using the optimum electrode spacing and spark duration, the frequency of ignition was determined as a function of spark energy for three overall equivalence ratios (0.6, 0.8, and 1.0) and for initial droplet diameters of 25, 40, 50, 60, and 70 micro m.

Cernansky, N. P.↗

Ignition characteristics of rich n-heptane fuel sprays in the transition region

Ignition studies were performed on monodisperse n-heptane sprays at atmospheric pressure over a range of equivalence ratios and droplet diameters. A capacitive discharge spark ignition system was used as the ignition source, providing independent control of spark energy and duration. Preliminary measurements were made to optimize spark duration and spark gap, optimum conditions being those at which the maximum frequency or probability of ignition was observed. Using the optimum electrode spacing and spark duration, the frequency of ignition was determined as a function of spark energy for three overall equivalence ratios (0.6, 0.8, and 1.0) and for initial droplet diameters of 25, 40, 50, 60, and 70 microns. An LDA system was used to determine the actual equivalence ratio at the spark gap, which varied from 1.5 to 4.7. The spark energy at which the frequency of ignition was 90 percent was defined as the minimum ignition energy. These data indicated that the ignitability of the sprays was enhanced as the equivalence ratio was increased, but was diminished as the droplet size was increased. The increase in minimum ignition energy with increasing droplet size and fixed equivalence ratio was nearly linear over the range of parameters studied. However, the effect became smaller with increasing equivalence ratio.

Danis, A. M.↗

On the Development of a Magnetically Vectored Variable ISP Plasma Rocket

The development of a Magnetically Vectored Variable I(sub sp) Plasma Rocket at the Advanced Space Propulsion Laboratory (ASPL) is in progress at NASA's Johnson Space Center. The facility is using a small, 3.2 m tandem mirror device to study the application of RF heated magnetically contained plasmas for space propulsion. The central cell radius is 0.1 m and fields of 0.2 T and 2 T are possible in the central and end-cell mirror sections, respectively. A magnetoplasmadynamic (MPD) injector has just been acquired and will be used along with other methods of plasma refueling. A 1 MW magnet power supply upgrade is being developed with full implementation by the Spring of 1997. Two microwave systems for discharge initiation and plasma heating at 2.45 GHz and 14.0 GHz, respectively, are in operation. Additionally, RF systems with 200 kW and 1 MW of power are being modified and conditioned for operation. The concept provides electrode-less operation and variable thrush'specific impulse at constant power (200 -30 N /5000-30,000 seconds at 10 MW with a 60% efficiency). Optimization for speed or payload are possible with the same engine, giving the rocket great flexibility. Missions to Mars in 90 days are described, and missions to Pluto are under study.

Feliciano, Enectali Figueroa↗

NASA Tech Briefs, March 2008

Topics covered include: WRATS Integrated Data Acquisition System; Breadboard Signal Processor for Arraying DSN Antennas; Digital Receiver Phase Meter; Split-Block Waveguide Polarization Twist for 220 to 325 GHz; Nano-Multiplication-Region Avalanche Photodiodes and Arrays; Tailored Asymmetry for Enhanced Coupling to WGM Resonators; Disabling CNT Electronic Devices by Use of Electron Beams; Conical Bearingless Motor/Generators; Integrated Force Method for Indeterminate Structures; Carbon-Nanotube-Based Electrodes for Biomedical Applications; Compact Directional Microwave Antenna for Localized Heating; Using Hyperspectral Imagery to Identify Turfgrass Stresses; Shaping Diffraction-Grating Grooves to Optimize Efficiency; Low-Light-Shift Cesium Fountain without Mechanical Shutters; Magnetic Compensation for Second-Order Doppler Shift in LITS; Nanostructures Exploit Hybrid-Polariton Resonances; Microfluidics, Chromatography, and Atomic-Force Microscopy; Model of Image Artifacts from Dust Particles; Pattern-Recognition System for Approaching a Known Target; Orchestrator Telemetry Processing Pipeline; Scheme for Quantum Computing Immune to Decoherence; Spin-Stabilized Microsatellites with Solar Concentrators; Phase Calibration of Antenna Arrays Aimed at Spacecraft; Ring Bus Architecture for a Solid-State Recorder; and Image Compression Algorithm Altered to Improve Stereo Ranging.

Source record↗

Design considerations for optimizing the transient CHI injector on QUEST

Transient coaxial helicity injection (transient CHI) on the QUEST (Q-shu University Experiment with Steady-State ST) spherical tokamak (ST) has recently validated the floating biased electrode configuration for solenoid-free plasma startup. In support of a significant divertor upgrade on QUEST, the details of the transient CHI injector geometry on QUEST have been examined more closely using tokamak simulation code (TSC) simulations. QUEST uses a HIT-II-like (Helicity Injected Torus) injector configuration in which the injector region is comprised of coaxial injector electrodes located in the lower part of the machine. TSC simulations indicate high injector flux operation may benefit from an increased gap between the coaxial electrodes. This is the first study to examine the differences between an open and closed electrode configuration for solenoid-free plasma startup using transient CHI. Results show that both configurations can generate similar levels of closed flux, but the closed configuration may be easier to implement in some ST designs as a much smaller portion of the injector needs to be close to the injector flux coil. Results show that increasing the electrode gap width from the present 10.8 cm to about 15–20 cm would increase the closed flux fraction by about 40%. The results presented in this paper are generally applicable to the CHI design for other STs.

coaxial helicity injection↗

Preliminary investigation of power flow and electrode phenomena in a multi-megawatt coaxial plasma thruster

This paper summarizes preliminary experimental and theoretical research that was directed towards the study of quasisteady-state power flow in a large, un-optimized, multi-megawatt coaxial plasma thruster. The report addresses large coaxial thruster operation and includes evaluation and interpretation of the experimental results with a view to the development of efficient, steady-state megawatt-class magnetoplasmadynamic (MPD) thrusters.

Schoenberg, Kurt↗

High Throughput Electrochemical Screening of Phosphate-Rich Nonflammable Electrolytes in Lithium-Ion Batteries

Frequent fires and explosions in lithium-ion batteries (LIBs) used in grid energy storage systems (ESS) highlight the necessity of revisiting nonflammable phosphate electrolytes as alternatives to the currently used flammable carbonates. However, previous studies have shown the difficulty of integrating phosphate solvents into LIB electrolytes due to compatibility issues with graphite. In this work, we developed a high-throughput (HTP) electrochemical characterization method, akin to pH test paper, to rapidly screen potential phosphate electrolytes and graphite materials. Through HTP screening, we identified 101 promising combinations out of 1,740. This number was reduced to 26 after testing in Li/Graphite half cells. The optimized phosphate-rich electrolyte (60 v% phosphate) with cosolvents demonstrated 300 stable cycles at 0.1 C in Graphite/LiFePO 4 (LFP) full cells with thick electrodes (∼3.0 mAh cm −2 ), surpassing prior research findings. This unique HTP method provides a powerful tool to expedite the development of safe LIBs for ESS applications.

25 ENERGY STORAGE↗

Study of magnetic perturbations on SEC vidicon tubes

A laboratory measurements program was conducted to determine the tolerances that must be imposed to achieve optimum performance from SEC-vidicon data sensors in the LST mission. These measurements along with other data were used to formulate recommendations regarding the necessary telemetry and remote control for the television data sensors when in orbit. The study encompassed the following tasks: (1) Conducted laboratory measurements of the perturbations which an external magnetic field produces on a magnetically focused, SEC-vidicon. Evaluated shielding approaches. (2) Experimentally evaluated the effects produced on overall performance by variations of the tube electrode potentials, and the focus, deflection and alignment fields. (3) Recommended the extent of ground control of camera parameters and camera parameter telemetry required for optimizing the performance of the television system in orbit. The experimental data are summarized in a set of graphs.

Long, D. C.↗