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At least 145 records · Page 8

A high-volume resonator for L-band DNP-NMR

DNP-NMR and EPR experiments that operate at or greater than L-band (i.e., ν 0 (e – ) = 1–2 GHz) are typically limited to maximum sample volumes of several hundred µL. These experiments rely on well-known resonator designs for DNP/EPR irradiation such as the loop-gap resonator and Alderman-Grant coil, where their maximum volumes limit further application to imaging experiments and high-throughput screening beyond L-band. Herein, we demonstrate a birdcage (BC) resonator design that can accommodate several mL of sample while operating around 1.5 GHz. The sample volume is maximized by using two identical BC resonators in a stacked configuration. Simulations are used to optimize the BC design and the performance is validated experimentally with liquid-state Overhauser-DNP-NMR experiments. This BC design exploits just the parasitic capacitance of conductive rings and features no fixed tuning capacitors. An enhancement of –77 is achieved on a 10 mM 4-Amino-TEMPO in H 2 O sample for a 5 mL sample volume. Finally, the associated sample heating is minimal due to the low-E-fields generated and the large sample mass with +3.4 K when driving 100 W for several seconds.

47 OTHER INSTRUMENTATION↗

Facile synthesis of co-doped Carbon nanofibers for supercapacitor applications

Here, in this study, the synthesis and electrochemical performance of carbon nanofibers (CNFs) co-doped with aluminum (Al) and nitrogen (N) and decorated with zinc oxide (ZnO) nanoparticles are investigated. After electrospinning polyacrylonitrile (PAN) nanofibers, the nanofiber mats are coated with Al and ZnO precursors by the dip coating method and converted into carbon nanofibers by thermal treatments at 850 °C. Co-doping and nanoparticle decoration affect the efficacy of carbon nanofibers as supercapacitors. With a maximal specific capacitance of 206.28 Fg -1 , it is believed that our produced carbon nanofibers, which can effectively store the renewable energy resources required to meet the rising energy demand, offer superior electrochemical properties compared to traditional supercapacitor materials. The effective incorporation of Al, N, and ZnO into the CNF structure, in conjunction with enhanced electrochemical performance, represents a significant advancement in the development of functional carbon nanofibers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Expanding the interlayer spacing of MXene through nanoarchitecture design

MXenes, a diverse class of two-dimensional transition metal carbides and nitrides with distinct surface chem istries, offer remarkable electrochemical and physicochemical properties. Yet, their performance can be hindered by the intrinsic restacking of layers, which restricts surface activity. This review outlines recent advances in interlayer spacing modulation strategies designed to overcome this limitation. A wide range of guest spe cies–including mono- and polyatomic ions, small molecules, low-dimensional nanomaterials, and polymers–are discussed with respect to their intercalation mechanisms, structural effects, and capacity to introduce functional enhancements. These intercalating species interact with MXene via electrostatic forces, hydrogen bonding, redox reactions, or covalent linkages, resulting in stable, expanded nanoarchitectures. The influence of expanded spacing on capacitive behavior is briefly highlighted to illustrate its practical relevance. Although Ti 3 C 2 T x is currently the most extensively investigated MXene, applying these interlayer engineering strategies to other MXene compositions will be essential for accessing a wider range of properties and functionalities.

36 MATERIALS SCIENCE↗

Electrochemical dynamics of imidazolium ionic liquids at graphene electrodes for energy storage applications

Electric double layer capacitors (EDLCs) are prominent energy storage systems that constitute the foundation of more reliable and sustainable energy infrastructures. Modern EDLCs often incorporate ionic liquids (ILs) as a key component in their electrolytes, leveraging the high electrochemical stability of ILs to enhance device performance. The performance and functionality of these capacitors also hinge on the interfacial behavior of ILs at electrode surfaces, which remain insufficiently understood. Here, we performed synchrotron infrared nanospectroscopy (SINS) in combination with density functional theory (DFT) calculations to investigate the electric double layers (EDLs) of three imidazolium-based ILs in a custom-designed graphene liquid cell. This approach revealed new insights into the dynamics of IL EDLs and the underpinning factors originating from the IL structures. Variations in anion size and structure were found to tune the ILs’ ability to form EDLs with compact and closely-correlated ion arrangements, which are critical for enhancing their capacitive performance. These findings highlight the intricate interactions between ions governed by their structures and charge behaviors, which underscores the opportunities for targeted design of IL-based electrolytes to optimize EDLC functionality.

Electric double layers↗

Demonstrating the β-Ga 2 O 3 Schottky diodes for alpha radiation detection

Schottky barrier diodes were fabricated on (001) monoclinic β-Ga 2 O 3 wafers with low doped epitaxial layers of 7.0 × 10 15 cm −3 . Circular Ni Schottky contacts with area 2 mm 2 were deposited by electron beam evaporation. Devices were characterized electrically by performing forward and reverse current-voltage sweeps with a range of −100 V–2 V, as well as capacitance-voltage sweeps to −30 V. The breakdown voltage was also determined to be −180 V for the devices. Experiments measuring the electrical response from incident X-ray radiation was performed. A response time to X-ray radiation of less than 1 s was recorded and a decay time of approximately 2 s after removing X-ray source, which primarily attribute to X-ray switching on and off time. Energy spectra of alpha particles from a 0.9 μCi 241 Am button source was collected at various voltage biases using devices with the lowest measured leakage current while reverse biased. The total count rate was observed to increase linearly with increasing device bias. In conclusion, the peak channel number was observed to increase with increasing bias with the best resolution of 9.5% at −100 V reverse bias.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Single channel PICOSEC Micromegas detector with improved time resolution

This paper presents design guidelines and the experimental verification of a single-channel PICOSEC Micromegas (MM) detector with an improved time resolution. The design encompasses the detector board, vessel, auxiliary mechanical parts, and electrical connectivity for high voltage (HV) and signals, focusing on improving the stability, reducing noise, and ensuring signal integrity to optimize timing performance. A notable feature is the simple and fast reassembly procedure, facilitating quick replacement of the detector internal components that allows for an efficient measurement strategy involving different detector components. The paper also examines the influence of parasitic capacitance and inductance on the output signal integrity. To validate the design, a prototype assembly and three interchangeable detector boards with varying readout pad diameters were manufactured. Detectors were initially tested in the laboratory. Finally, the timing performance of the detectors with different pad sizes was verified using 150 GeV muons. Notably, a record time resolution for a PICOSEC Micromegas detector technology with a CsI photocathode of 12.5 ± 0.8 ps was achieved for a detector with 10 mm diameter readout pad size.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Design and fabrication of a four-rod radio frequency quadrupole with a variable aperture

Radiofrequency quadrupole (RFQ) linear accelerators with variable aperture cell parameters offer an effective means of accelerating high-intensity ion beams exceeding 100 mA and have been implemented in various RFQ designs. However, in a four-rod RFQ, the use of dielectric perturbation methods to measure the voltage distribution behind the rod electrodes is not applicable when implementing variable aperture geometries, because changes in the rod shape influence the electric field at the location of the perturbation element. Therefore, it was necessary to design the rod profile for each cell such that the electric field distribution behind the rods remains unaffected by changes in the aperture. In this study, we present a method to adjust the voltage distribution by modifying the geometry of the rod electrodes according to each cell's aperture parameters. This design approach enables the integration of variable aperture cells into a four-rod RFQ linac, significantly enhancing the achievable beam current. To ensure uniform capacitance and maintain a constant rod-electrode voltage despite variations in the average aperture radius, we developed a systematic method for shaping the rod electrodes. This method was refined using two-dimensional (2D) and three-dimensional (3D) electromagnetic field simulations to optimize the electrode cross-sectional profiles. The fabricated rod electrodes were then installed in a four-rod RFQ, and the electric field distribution was measured using the perturbation method and tuned by adjusting the base plates. As a result, the measured variation of ±1.1 % confirms that this design methodology can produce a sufficiently uniform voltage distribution for high-current beam acceleration. These results demonstrate the practical feasibility of a variable-aperture four-rod RFQ linac.

43 PARTICLE ACCELERATORS↗

Effects of Particle Mixing and Gravitational Settling on Charge Transport in Carbon Flow-Electrode Cells

Flowable carbon slurries are actively studied and under development for charge transport in various electrochemical systems including flow capacitors, capacitive deionization cells, semi-solid flow batteries, and lithium extraction. However, much less is known about in operando slurry flow dynamics and their corresponding effect on charge transport. We performed an experimental study of mixing and settling dynamics of slurry electrodes within an electrochemical flow cell during continuous operations. The electrochemical cell consisted of two horizontal co-flowing channels, separated by a cation-exchange membrane (CEM). Here we used high-speed optical imaging of planes parallel to gravity and simultaneous electrochemical measurements. At low flow rates, dense yet dynamic particle beds formed on the bottom electrode in each channel, which unexpectedly yielded the highest currents. This approach enables the operation of the flow cell at low system-average particle concentrations while leveraging gravity-driven particle settling to locally enhance carbon concentrations precisely at the current collector sites. Conversely, high flow rates were characterized by thin particle beds and well-mixed particle flows. In the latter case, the electrodes in closest proximity (located on either side of the CEM) achieved a current higher than the other electrode pairs. The observations have implications for slurry control and electrode designs in electrochemical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Polarity of Co-solvents Regulates the Charge Storage Mechanisms in Supercapacitors with Concentrated Electrolytes

Developing better energy storage devices depends on comprehending the underlying mechanisms involved in charge storage. With the continuous conception of new electrolytes, this task becomes progressively more urgent and complex. An example is the utilization of co-solvated concentrated solutions. While these show promising electrochemical responses, their dynamic properties (especially under confinement) and their relationships with performance are not fully understood. Here, we combined modified step potential electrochemical spectroscopy and quasielastic neutron scattering to investigate systems composed of activated mesoporous carbon (AMC) and concentrated solutions of lithium bis(trifluoromethanesulfonyl)imide in acetonitrile co-solvated with either toluene or acetone. Further, we report that acetone does not impair surface-controlled mechanisms, contrary to the case with toluene, which competes with charged species to populate the AMC’s pores without contributing to charge storage. In turn, toluene promotes a greater overall capacitance owing to Faradaic processes, which may be related to changes in the solvation structures under confinement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Curvature Memory in Electrically Stimulated Lipid Membranes

Here, we demonstrate, using non-equilibrium molecular dynamics simulations, that lipid membrane capacitance varies with surface charge accumulation linked to membrane shape and curvature changes. Specifically, we show that lipid membranes exhibit a hysteretic response when exposed to oscillatory electric fields. The electromechanical coupling in these membranes leads to hysteretic buckling, in which the membrane can spontaneously buckle in one of two distinct directions along the electric field, even for the same ionic charge accumulation at the water–membrane interface. In this regard, these binary buckled membrane states suggest potential applications in neuromorphic computing. Their bistable nature, characterized by two distinct and stable configurations, could serve as a foundation for implementing memory storage systems and logic operations. Furthermore, we introduce a circuit model that captures these dynamic effects, offering insights into emergent memory effects in electrically stimulated lipid membranes. Finally, this work presents lipid bilayers as dynamic, adaptable elements and suggests a new platform for exploring energy storage, information processing, and memory encoding at the lipid membrane level.

59 BASIC BIOLOGICAL SCIENCES↗

Tea ( Camellia sinensis ) Extract-Mediated Green Synthesis of Co 3 O 4 and Co 3 O 4 @Graphene Nanocomposites for Multifunctional Applications in Pollutant Degradation, Sensing, and Energy Storage

A novel solution-mixing method was proposed to synthesize Co 3 O 4 /graphene nanocomposites (Co 3 O 4 @Gr) using a green tea leaf (Camellia sinensis) extract as the reducing agent. XRD analysis shows that the as-prepared Co 3 O 4 @Gr exhibits a cubic spinel crystal structure. From morphological analysis, the obtained Co 3 O 4 NS forms spherical clusters that are uniformly distributed on the graphene surface. FT-IR and Raman analyses confirmed the strong molecular and vibrational interactions between the Co 3 O 4 NS and Gr. The suppressed PL intensity peak of the Co 3 O 4 @Gr NCs indicated significant inhibition in the recombination of charge carriers between the hybrid orbitals within the composites. As a result, the catalytic efficiency of Co 3 O 4 @Gr NCs increased to 80% compared to pristine Co 3 O 4 , which exhibited only 45% efficiency against methylene blue (MB) dye. Moreover, the as-prepared NCs exhibited a detection limit of 0.01−224 μM, demonstrating a superior low-DPA detection with high sensitivity. The Co 3 O 4 @Gr/GCE exhibits admirable selectivity for various pesticides, fungicides, and metal ions, with outstanding reproducibility and stability. From electrochemical investigations, the highest specific capacitance values of the as-synthesized Co 3 O 4 @Gr were 349 F/g at a scan rate of 5 mV/s and 158 F/g at a current density of 1 A/g.

Capacitors↗

Unveiling the Role of In Situ Al 2 O 3 Passivation in Molecular-Ink-Processed CuIn(S,Se) 2 Photovoltaics

Here, we report on the optimization of in situ passivation of ink-based CuIn(S,Se) 2 thin-film solar cells via controlled incorporation of Al 2 O 3 in CuIn(S,Se) 2 films by the addition of Al(NO 3 ) 3 to the molecular ink precursor. For this purpose, the Al/(Al + In) (AAI) metal ratio was varied from 0.05 to 0.30. We observe that the efficiency of the cells made of Al 2 O 3 -incorporated CuIn(S,Se) 2 is consistently higher than those without Al 2 O 3 , especially due to an improvement in open-circuit voltage (V OC ) and fill factor (FF), for all tested AAI ratios. With an AAI of 0.05, a maximum efficiency of 11.2% and an average efficiency of 8.5% (measured across 18 cells) was achieved, compared to 8.5% maximum efficiency and 6.5% average efficiency for Al-free CuIn(S,Se) 2 . Furthermore, we find that cells made of Al 2 O 3 -incorporated CuIn(S,Se) 2 with an AAI of 0.2 show a narrow distribution in the photovoltaic performance, indicating higher reproducibility and higher FF. Energy-dispersive X-ray spectroscopy shows that, at AAI = 0.2, Al 2 O 3 is distributed more homogeneously at the surface of the Al 2 O 3 -incorporated CISSe. Capacitance-voltage measurements reveal a reduced defect density by incorporation of Al 2 O 3 , which could be partly responsible for the higher V OC . Furthermore, using detailed surface analysis with various X-ray and electron spectroscopy methods, we derive chemical and electronic structure information from the surface. With ultraviolet photoelectron (UPS) and inverse photoemission spectroscopies (IPES), the electronic band gap of the CuIn(S,Se) 2 thin-film surface is found to increase from 1.22 to 1.88 eV (+-0.12 eV) with Al 2 O 3 incorporation. This is accompanied by a clear reduction of the conduction band spike at the CdS/CISSe interface due to Al 2 O 3 addition, as derived by both UPS and IPES as well as temperature-dependent V OC measurements.

14 SOLAR ENERGY↗

Mechanism-Informed Breakdown: Understanding Degradation by Controlling Voltage-Hold Patterns in Proton Exchange Membrane Water Electrolyzers

Low catalyst loadings pose challenges to performance stability in proton exchange membrane (PEM) water electrolysis over extended operation. To study the impact of degradation mechanisms and voltage loss rates, different stress tests are applied to membrane electrode assemblies. Potential cycling conditions were observed to induce higher degrees of iridium (Ir) oxide crystallization, ionomer degradation, and catalyst layer (CL) thinning, which likely contributed to higher kinetic loss rates. On the other hand, while Ir migrating into the PEM (Ir band) generally impairs performance, the interconnected and more uniform Ir band formed under a constant 2 V hold may allow for Ir at the catalyst/membrane interface to remain electronically connected and kinetically accessible, as well as indicate greater Ir site access during the applied stressor. The 2 V hold also demonstrates improved kinetic durability through a lower Tafel slope, faster polarization kinetics, and reduced charge transfer resistance. In contrast, potential cycling caused the migration of disconnected Ir agglomerates into the membrane bulk and created a steady increase in charge transfer resistance, a more dramatic decrease in capacitance (46.7% loss), and significant damage to the surrounding ionomer, indicating a decline in both the quality and quantity of active sites in the anode CL. This work underscores the distinct degradation pathways associated with load holds versus cycling, highlighting the role of catalyst-ionomer interactions in kinetic performance and long-term stability. These insights can inform operational strategies for PEM electrolyzers powered by intermittent energy sources, aiming to minimize efficiency losses over extended operation.

36 MATERIALS SCIENCE↗

Ionic Associations and Hydration in the Electrical Double Layer of Water-in-Salt Electrolytes

Water-in-Salt-Electrolytes (WiSEs) are an exciting class of concentrated electrolytes finding applications in energy storage devices because of their expanded electrochemical stability window, good conductivity and cation transference number, and fire-extinguishing properties. These distinct properties are thought to originate from the presence of an anion-dominated ionic network and interpenetrating water channels for cation transport, which indicates that associations in WiSEs are crucial to understanding their properties. Currently, associations have mainly been investigated in the bulk, while little attention has been given to the electrolyte structure near electrified interfaces. Here, we develop a theory for the electrical double layer (EDL) of WiSEs, where we consistently account for the thermoreversible associations of species into Cayley tree aggregates. The theory predicts an asymmetric structure of the EDL. At negative voltages, hydrated Li + dominates, and cluster aggregation is initially slightly enhanced before disintegration at larger voltages. At positive voltages, when compared to the bulk, clusters are strictly diminished. Performing atomistic molecular dynamics (MD) simulations of the EDL of WiSE provides EDL data for validation and bulk data for parametrization of our theory. Validating the predictions of our theory against MD showed good qualitative agreement. Furthermore, we performed electrochemical impedance measurements to determine the differential capacitance of the studied LiTFSI WiSE and also found reasonable agreement with our theory. Overall, the developed approach can be used to investigate ionic aggregation and solvation effects in the EDL, which, among other properties, can be used to understand the precursors for solid-electrolyte interphase formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Topology Optimization of Curved Electrodes with Suggested Simplified Corrugated Designs

The demand for space-efficient energy storage, from grid to device scale, has soared with the rapid electrification of society. To increase energy density while maintaining high rate performance, shaping electrodes has been shown to be an effective strategy. Computational optimization can suggest designs that improve energy storage performance; however, generated designs are often complex, leading to manufacturing challenges. Additionally, most optimization is typically conducted in standard rectangular domains, whereas some applications, such as in the aerospace industry or in consumer electronics, may benefit from optimized electrodes that fit in a nonstandard form factor. Here, in this work, we use topology optimization to design capacitive full-cell electrodes in a curved domain. We propose a simplified corrugated electrode design based on the optimization results and show that the energy stored in the simplified design is only reduced by about 5–27% when compared to that in the fully optimized design, with more deviation occurring when ionic transport in the porous electrode is particularly impeded. Overall, we find that these simplified designs are promising, particularly given the more conventional manufacturing techniques required, and have a 42–369% increase in energy stored compared to monolithic electrodes.

Energy - Storage↗

Bicarbonate-Carbonate Selectivity through Nanofiltration for Direct Air Capture of Carbon Dioxide

Direct air capture (DAC) of carbon dioxide is one approach among many proposed that is capable of offsetting hard-to-avoid emissions. In previous work, we developed the alkalinity concentration swing (ACS) method, which is driven through concentrating an alkaline solution that has been loaded with atmospheric CO 2 by desalination technologies, such as reverse osmosis or capacitive deionization. Though the ACS is promising in terms of energy usage and implementation, its absorption rate and water requirements are infeasible for a large-scale DAC process. Here, we propose an improvement on the ACS, the bicarbonate-enriched alkalinity concentration swing (BE-ACS), which selects bicarbonate ions from a stream of aqueous alkaline solution that has absorbed atmospheric CO 2 . The bicarbonate-rich stream is then concentrated, which greatly increases its CO 2 partial pressure, and then CO 2 is extracted from solution. We experimentally investigate the use of pressure-driven nanofiltration (NF) membrane-based separation to select bicarbonate ions over carbonate ions. We screen commercial membranes and select one high-performance membrane for detailed studies, quantifying its bicarbonate-carbonate selectivity factor and bicarbonate-passage factor. Feed pH, the combined concentration of aqueous CO 2 , bicarbonate, and carbonate species (or dissolved inorganic carbon), alkalinity, and permeation flux are systematically varied to study NF separation properties. We find that the selectivity factor, which exceeds 30 times in certain regimes, increases with higher feed pH and higher alkalinity. Lastly, the performance metrics of the selected NF membrane are input into a theoretical BE-ACS cycle analysis, and the required energy input and cycle capacity output are evaluated. Ideal cycle energy is found to be as low as around 250 kJ/mol, with opportunities identified for further decreases through process engineering and forward osmosis energy recovery.

animal feed↗

Flexible and Extensive Platinum Ion Gel Condensers for Programmable Catalysis

Catalytic condensers composed of ion gels separating a metal electrode from a platinum-on-carbon active layer were fabricated and characterized to achieve more powerful, high surface area dynamic heterogeneous catalyst surfaces. Ion gels comprised of poly(vinylidene difluoride)/1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide were spin coated as a 3.8 μm film on a Au surface, after which carbon sputtering of a 1.8 nm carbon film and electron-beam evaporation of 2 nm Pt clusters created an active surface exposed to reactant gases. Electronic characterization indicated that most charge condensed within the Pt nanoclusters upon application of a potential bias, with the condenser device achieving a capacitance of ∼20 μF/cm 2 at applied frequencies of up to 120 Hz. The maximum charge of ∼10 14 |e – | cm –2 was condensed under stable device conditions at 200 °C on catalytic films with ∼10 15 sites cm –2 . Grazing incidence infrared spectroscopy measured carbon monoxide adsorption isobars, indicating a change in the CO* binding energy of ∼19 kJ mol –1 over an applied potential bias of only 1.25 V. Condensers were also fabricated on flexible, large area Kapton substrates allowing stacked or tubular form factors that facilitate high volumetric active site densities, ultimately enabling a fast and powerful catalytic condenser that can be fabricated for programmable catalysis applications.

Catalysis↗

Field-Coupled Water Splitting with Metal-Free Donor–Acceptor Covalent Organic-Framework Junctions

Advancing metal-free electrocatalysts for hydrogen and oxygen evolution reactions (HER/OER) across acidic and alkaline media requires coordinated control of intermediate binding thermodynamics, interfacial charge delivery, and near-electrode transport dynamics. Here, we design amide-linked benzene–triazine covalent organic frameworks (BTA/TzTA-Hz COFs) and integrate them with carbon nanotubes (CNTs) to form COF–CNT junctions that establish a built-in interfacial electric field. Density functional theory (DFT) and electrostatic potential maps indicate complementary active motifs, with benzene-proximal fragments associated with HER and triazine-proximal motifs associated with OER. CNT integration shifts the contact-potential difference by ≈0.20 V, while operando electrochemical impedance spectroscopy suggests partially separable high-frequency junction-charging and lower-frequency Faradaic/transport responses. A 300 mT static magnetic field lowers the HER and OER overpotentials by tens of millivolts. Under anodic bias, the effective interfacial charging capacitance increases, and Mott–Schottky analysis shows an apparent ∼0.15 V flat-band shift with an essentially unchanged slope. Together, these observations are consistent with field-perturbed interfacial charging and altered bias partitioning. Field-dependent impedance and bubble imaging are consistent with magnetohydrodynamic convection that promotes bubble detachment and near-electrode mass transport for both half-reactions, and they reveal an OER-specific high-frequency perturbation under anodic bias. Under field, the heterostructure reaches an OER onset overpotential of ∼261 mV and requires an overpotential of 366 mV at 10 mA cm –2 in alkaline electrolyte. These results illustrate how reticular-framework chemistry, junction engineering, and both built-in and applied fields can program reactivity through interfacial electrostatics and near-electrode transport in organic-framework electrocatalysts.

Garcia-Enriquez, Lissette [Univ. of Texas at El Pa↗