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Results for “differential capacitance”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Charge fluctuations from molecular simulations in the constant-potential ensemble

We revisit the statistical mechanics of charge fluctuations in capacitors. In constant-potential classical molecular simulations, the atomic charges of electrode atoms are treated as additional degrees of freedom which evolve in time so as to satisfy the constraint of fixed electrostatic potential for each configuration of the electrolyte. The present work clarifies the role of the overall electroneutrality constraint, as well as the link between the averages computed within the Born–Oppenheimer approximation and that of the full constant-potential ensemble. This allows us in particular to derive a complete fluctuation–dissipation relation for the differential capacitance, that includes a contribution from the charge fluctuations (around the charges satisfying the constant-potential and electroneutrality constraints) also present in the absence of an electrolyte. We provide a simple expression for this contribution from the elements of the inverse of the matrix defining the quadratic form of the fluctuating charges in the energy. We then illustrate numerically the validity of our results, and recover the expected continuum result for an empty capacitor with structureless electrodes at large inter-electrode distances. By considering a variety of liquids between graphite electrodes, we confirm that this contribution to the total differential capacitance is small compared to that induced by the thermal fluctuations of the electrolyte.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS2001

Silicon micromachined accelerometer/seismometer and method of making the same

A silicon-based microaccelerometer for seismic application is provided using a low-resonant frequency (10 Hz), large proof mass (1 gram), and high Q suspension to achieve high sensitivity of less than 1 ng with a bandwidth a 0.05 to 50 Hz. The proof mass is cut away from a planar substrate in the form of a disk using abrasive cutting, which disk closely fits but does not touch a surrounding angular frame. The spring of the microaccelerometer between the angular frame and the proof mass is provided from two continuous, 3 microns thick membranes. The fixed capacitive electrodes are provided on separate, subsequently bonded substrates, and movable capacitive plates are provided on the membranes. By fabricating capacitive plates on the separate substrates, the gap between the fixed and movable capacitive plates in the differential capacitive sensor is closely controlled. The use of continuous membranes for the spring produces a shock resistant, robust sensor.

Martin, Richard D.↗
DOE OSTI2015

Direct observation of electrical properties of grain boundaries in sputter-deposited CdTe using scan-probe microwave reflectivity based capacitance measurements

Here, polycrystalline CdTe in 12% efficient solar cells has been studied using scanning microwave impedance microscopy (sMIM). The CdS/CdTe junctions were grown on transparent-conducting-oxide-coated soda lime glass using rf sputter deposition. sMIM based capacitance measurements were performed on the exposed surface of CdCl 2 treated CdTe adjacent to thermal-evaporation-deposited Cu/Au back contacts. The sMIM instrument was operated at ~3 GHz, and capacitance measurements were performed as a function of ac and dc voltage biases applied to the tip, with and without sample illumination. Although dc capacitance measurements are affected by sample topography, the differential capacitance measurement was shown to be topography independent. It was found that the grain boundaries exhibit a depleted carrier concentration as compared to the grain bulk. This depletion effect is enhanced under photo-generated carrier separation or under sufficiently large probe tip biases opposite to the majority carrier charge.

14 SOLAR ENERGY↗
NASA NTRS2016

Interfacial Structure and Capacitance of Li-doped Ionic Liquid Electrolytes from Molecular Simulations

Ionic liquids have been proposed as candidate electrolytes for high-energy density, rechargeable batteries, supercapacitors, and hybrid energy storage devices. Though Li-salt is often present in these systems, its influence on interfacial properties is largely uncharacterized. We, thereby, present an extensive computational analysis, supported by experimental comparisons, of the properties of a representative set of these electrolytesat an ideal carbon interface as a function of Li-salt doping and voltage. We have performed polarizable molecular (MD) dynamics simulations, using the APPLEP force field, to evaluate electric double layer (EDL) capacitance and distribution of Li+ in the EDL. Differential capacitance exhibits the characteristic camel profile and is insensitive to Li-doping. Li+ localizes in the second molecular layer of the EDL, which is a result of confinement from free energy barriers associated with ion layering. Joint MDelectronic structure computations show the electrochemical window of the electrolytes to be a weak function of Li-doping. Estimates of supercapacitor specific energy are made using the computed window and capacitance. The magnitude and trends in specific energy are in good agreement with experiment.

batteries↗
DOE OSTI2022

Capacitance of Carbon Nanotube/Graphene Composite Electrodes with [BMIM + ][BF$_4^–$]/Acetonitrile: Fixed Voltage Molecular Dynamics Simulations

The capacitance of nanoporous carbon electrode materials is dictated by the physical interactions with electrolyte ions and molecules at the accessible interior electrode surface. While significant progress has been made in designing and synthesizing carbon materials with well-defined and relatively homogeneous nanoporosity, the majority of materials remain heterogeneous, and the resulting properties reflect an average over this distribution. In this regard, computer simulations can be a valuable tool to predict or validate structure/property relationships by systematically investigating well-defined, model electrode morphologies. In this work, we utilize fixed-voltage molecular dynamics simulations to predict structure/capacitance relationships for five different model morphologies of carbon nanotube/graphene (CNT/G) composite electrodes with 1-butyl-3-methylimidazolium tetrafluoroborate/acetonitrile electrolyte. The CNT/G electrode models are inspired by experimental “layer-by-layer” syntheses and strike a balance between realism and computational tractability. Comparison between different model electrode architectures elucidates important structure/property relationships. We find that CNT/graphene contact points serve as “hot spots” with significantly enhanced charge separation relative to the rest of the electrode. Furthermore, we demonstrate a specific nanoconfinement motif that provides substantial 3–4$\times$ enhancement of local capacitance, resulting in a ~40% increase of the total electrode differential capacitance. Because the accessible surface area of the model CNT/G electrodes is precisely determined, a comparison of per-area capacitance across systems is unambiguous. Our results thus complement a prior computational demonstration of capacitance enhancement in nanoconfinement while elucidating additional interaction motifs at CNT/G electrochemical interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Optical power dependence of capacitance in uni-traveling-carrier photodetectors

Optical power dependence of capacitance in uni-traveling-carrier photodetectors is analyzed by founding a differential capacitance model. The trend of capacitance variation against optical power by simulation gets a good agreement with the measured results. The relationship between light-intensity-dependent capacitance and DC saturation characteristics of the device is also investigated at different collection layer thicknesses. The optical power at the maximum point of capacitance is near that at the DC saturation point. With the thickness of collection layer increasing, the maximum capacitance decreases and optical power at capacitance maximum point also becomes small.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1990

High Temperature Capacitive Strain Gage

Capacitive strain gages designed for measurements in wind tunnels to 2000 F were built and evaluated. Two design approaches were followed. One approach was based on fixed capacitor plates with a movable ground plane inserted between the plates to effect differential capacitive output with strain. The second approach was based on movable capacitor plates suspended between sapphire bearings, housed in a rugged body, and arranged to operate as a differential capacitor. A sapphire bearing gage (1/4 in. diameter x 1 in. in size) was built with a range of 50,000 and a resolution of 200 microstrain. Apparent strain on Rene' 41 was less than + or - 1000 microstrain from room temperature to 2000 F. Three gage models were built from the Ground Plane Differential concept. The first was 1/4 in. square by 1/32 in. high and useable to 700 F. The second was 1/2 in. square by 1/16 in. high and useable to 1440 F. The third, also 1/2 in. square by 1/16 in. high was expected to operate in the 1600 to 2000 F range, but was not tested because time and funding ended.

Wnuk, Stephen P., Jr.↗
DOE OSTI2014

Modifying the characteristics of carbon nanotubes grown on metallic substrates for ultracapacitor applications

This paper reports the design, fabrication, and testing of carbon nanotube (CNT)-based ultracapacitor electrodes and provides quantitative results, showing that total electrode surface area—and, correspondingly, the total cell capacitance—is highly sensitive to the amount of catalyst material deposited prior to CNT growth. We deposit between 0.6 and 1.0 nm of iron catalyst on metallic (tungsten) substrates and synthesized vertically aligned CNT forests directly by thermal chemical vapor deposition. A capacitance maximum is observed with electrodes prepared with 0.8 nm of catalyst. Geometrical arguments based on average CNT diameter and areal density are used to corroborate this result. The CNTs' differential capacitance is found to be independent of their areal density, mean diameter, length, and the amount of catalyst used to grow them.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

Dynamics of electronic transitions and frequency dependence of negative capacitance in semiconductor diodes under high forward bias

We observed qualitatively dissimilar frequency dependence of negative capacitance under high charge injection in two sets of functionally different junction diodes: III-V based light emitting and Si-based non-light emitting diodes. Using an advanced approach based on bias activated differential capacitance, we developed a generalized understanding of negative capacitance phenomenon which can be extended to any diode based device structure. We explained the observations as the mutual competition of fast and slow electronic transition rates which are different in different devices. This study can be useful in understanding the interfacial effects in semiconductor heterostructures and may lead to superior device functionality.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Electroanalytical Investigation of the Electrode–Electrolyte Interface of Quaternary Ammonium Ionic Liquids: Impact of Alkyl Chain Length and Ether Functionality

The influence of ionic associations and potential-dependent interactions on the electrode–electrolyte interfacial structure of ionic liquids (ILs) is studied by electrochemical impedance spectroscopy (EIS) and surface-enhanced Raman spectroscopy (SERS) for a variety of asymmetric quaternary ammonium ILs. Specifically, the impact of cation alkyl chain length (C = 4, 8 and 16) and ether functionality on the interfacial structuring of ILs at the glassy carbon electrode surface is examined. Ammonium cations with alkyl chain length of 8 and 16 carbons are found to stabilize the formation of the bis(trifluorosulfonyl)imide, [TFSI], anion dense Stern layer at positive electrode potentials leading to larger capacitances. The longer alkyl chain of the cation is believed to screen the ion–ion repulsion among the anions by intruding into the interfacial anion layer. SERS suggests the presence of carbon-containing rings at the interface at both positive and negative electrode potentials, which can be explained by the buckling of the long alkyl chains. Inclusion of an ether functionality allowed for more symmetry in the camel-shaped potential-dependent differential capacitance curves, suggesting similar excess ion density at both positive and negative potentials. This work contributes to understanding and predicting the interfacial electrode capacitance in ILs by understanding the balance of ionic interactions and the associated repulsions at electrode–electrolyte interfaces that are pertinent to electrochemical energy storage, electrocatalysis, and electrochemical sensors.

25 ENERGY STORAGE↗
DOE OSTI2017

Impurity Effects on Charging Mechanism and Energy Storage of Nanoporous Supercapacitors

Room-temperature ionic liquids (RTILs) have been widely used as electrolytes to enhance the capacitive performance of electrochemical capacitors also known as supercapacitors. Whereas impurities are ubiquitous in RTILs (e.g., water, alkali salts, and organic solvents), little is known about their influences on the electrochemical behavior of electrochemical devices. In this work, we investigate different impurities in RTILs within the micropores of carbon electrodes via the classical density functional theory (CDFT). We find that under certain conditions impurities can significantly change the charging behavior of electric double layers and the shape of differential capacitance curves even at very low concentrations. More interestingly, an impurity with a strong affinity to the nanopore can increase the energy density beyond a critical charging potential. As a result, our theoretical predictions provide further understanding of how impurity in RTILs affects the performance of supercapacitors.

25 ENERGY STORAGE↗
DOE OSTI2022

Anion Effects on the Interfacial Structure and Bulk Physical Properties in Choline-Based Hydrogen-Bonded Electrolytes

Electrolytes consisting of choline (Ch) salts with acetate (Ac) and oxalate (Ox) anions were studied in mixtures with ethylene glycol (EG), in comparison to chloride (Cl)- and bis(trifluorosulfonyl)imide (TFSI)-containing systems to understand the impact of anion size and charge density on the bulk electrolyte and interfacial properties. These represent hydrogen-bonded concentrated electrolytes where the Ch salts are the H-bond acceptors (HBAs) and EG is the H-bond donor (HBD) in 1:2 and 1:4 HBA:HBD ratios. Increased H-bonding in Ch 2 Ox with EG compacts the liquid compared to ChAc, consistent with the increased dissociation energies of the HBA:HBD clusters with Ox –2 calculated by density functional theory (DFT), thus leading to denser and more viscous liquids. Electrochemical impedance spectroscopy (EIS) and surface-enhanced Raman spectroscopy (SERS) were used to investigate interfacial charge density and the electrode surface species. Differential capacitance curves demonstrate weak dependence on potential except for ChAc:EG, where Ac – is found to adsorb on the Au surface, in particular at +0.055 V vs Ag quasi-reference while no specific adsorption was observed on glassy carbon (GC). In situ SERS measurement confirms the formation of a surface layer in the ChAc:EG systems resulting from a Au–acetate interaction. Despite the structural similarities, Ox –2 did not show specific binding or any dependence of capacitance on potential as a result of strongly solvating EG molecules via H-bonds. Furthermore, this study shows that the charge density of the HBAs impacts both bulk properties and the electrical double-layer formation in concentrated H-bonded electrolytes that is relevant to electrochemical kinetics and morphology in electrodeposition processes and energy storage applications.

25 ENERGY STORAGE↗
DOE OSTI2025

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↗
DOE OSTI2024

Hydrogen-induced tunable remanent polarization in a perovskite nickelate

Materials with field-tunable polarization are of broad interest to condensed matter sciences and solid-state device technologies. Here, using hydrogen (H) donor doping, we modify the room temperature metallic phase of a perovskite nickelate NdNiO 3 into an insulating phase with both metastable dipolar polarization and space-charge polarization. We then demonstrate transient negative differential capacitance in thin film capacitors. The space-charge polarization caused by long-range movement and trapping of protons dominates when the electric field exceeds the threshold value. First-principles calculations suggest the polarization originates from the polar structure created by H doping. We find that polarization decays within ~1 second which is an interesting temporal regime for neuromorphic computing hardware design, and we implement the transient characteristics in a neural network to demonstrate unsupervised learning. These discoveries open new avenues for designing ferroelectric materials and electrets using light-ion doping.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Permanent polarization and charge distribution in organic light-emitting diodes (OLEDs): Insights from near-infrared charge-modulation spectroscopy of an operating OLED

Vapor-deposited Alq{sub 3} layers typically possess a strong permanent electrical polarization, whereas NPB layers do not. (Alq{sub 3} is tris(8-quinolinolato)aluminum(III); NPB is 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl.) The cause is a net orientation of the Alq{sub 3} molecules with their large dipole moments. Here we report on consequences for an organic light-emitting diode (OLED) with an NPB hole-transport layer and Alq{sub 3} electron-transport layer. The discontinuous polarization at the NPB|Alq{sub 3} interface has the same effect as a sheet of immobile negative charge there. It is more than compensated by a large concentration of injected holes (NPB{sup +}) when the OLED is running. We discuss the implications and consequences for the quantum efficiency and the drive voltage of this OLED and others. We also speculate on possible consequences of permanent polarization in organic photovoltaic devices. The concentration of NPB{sup +} was measured by charge-modulation spectroscopy (CMS) in the near infrared, where the NPB{sup +} has a strong absorption band, supplemented by differential-capacitance and current-voltage measurements. Unlike CMS in the visible, this method avoids complications from modulation of the electroluminescence and electroabsorption.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

The structure and properties of a simple model mixture of amphiphilic molecules and ions at a solid surface

We investigate microscopic structure, adsorption, and electric properties of a mixture that consists of amphiphilic molecules and charged hard spheres in contact with uncharged or charged solid surfaces. The amphiphilic molecules are modeled as spheres composed of attractive and repulsive parts. The electrolyte component of the mixture is considered in the framework of the restricted primitive model (RPM). The system is studied using a density functional theory that combines fundamental measure theory for hard sphere mixtures, weighted density approach for inhomogeneous charged hard spheres, and a mean-field approximation to describe anisotropic interactions. Our principal focus is in exploring the effects brought by the presence of ions on the distribution of amphiphilic particles at the wall, as well as the effects of amphiphilic molecules on the electric double layer formed at solid surface. In particular, we have found that under certain thermodynamic conditions a long-range translational and orientational order can develop. The presence of amphiphiles produces changes of the shape of the differential capacitance from symmetric or non-symmetric bell-like to camel-like. Moreover, for some systems the value of the potential of the zero charge is non-zero, in contrast to the RPM at a charged surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Constant-potential molecular dynamics simulations of molten salt double layers for FLiBe and FLiNaK

We report the results of constant-potential molecular dynamics simulations of the double layer interface between molten 2LiF–BeF 2 (FLiBe) and 23LiF–6NaF–21KF (FLiNaK) fluoride mixtures and idealized solid electrodes. Employing methods similar to those used in studies of chloride double layers, we compute the structure and differential capacitance of molten fluoride electric double layers as a function of applied voltage. The role of molten salt structure is probed through comparisons between FLiBe and FLiNaK, which serve as models for strong and weak associate-forming salts, respectively. In FLiBe, screening involves changes in Be–F–Be angles and alignment of the oligomers parallel to the electrode, while in FLiNaK, the electric field is screened mainly by rearrangement of individual ions, predominantly the polarizable potassium cation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Ferro-ionic states and domains morphology in Hf x Zr 1–x O 2 nanoparticles

Unique polar properties of nanoscale hafnia-zirconia oxides (Hf x Zr 1–x O 2 ) are of great interest for condensed matter physics, nanophysics, and advanced applications. These properties are connected (at least partially) to the ionic–electronic and electrochemical phenomena at the surface, interfaces, and/or internal grain boundaries. Here, we calculated the phase diagrams, dielectric permittivity, spontaneous polar, and antipolar ordering, as well as the domain structure morphology in Hf x Zr 1–x O 2 nanoparticles covered by ionic–electronic charge originating from surface electrochemical adsorption. We revealed that the ferro-ionic coupling supports the polar long-range order in nanoscale Hf x Zr 1–x O 2 , induces, and/or enlarges the stability region of the labyrinthine domains toward smaller sizes and smaller environmental dielectric constant at low concentrations of the surface ions. The ferro-ionic coupling causes the transition to the single-domain ferro-ionic state at high concentrations of the surface ions. We predict that the labyrinthine domain states, being multiple-degenerated, may significantly affect the emergence of the negative differential capacitance state in the nanograined/nanocrystalline Hf x Zr 1–x O 2 films.

36 MATERIALS SCIENCE↗