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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 217 records · Page 12

First-Principles Modeling of Sodium Ion and Water Intercalation into Titanium Disulfide Interlayers for Water Desalination

Recent experiments revealed the possibility of using titanium disulfide (TiS 2 ) as the cathode material in capacitive deionization (CDI) devices for water desalination. Although it performed stably up to 70 cycles with a salt removal capacity of 14 mg/g (corresponding to a sodium ion removal capacity of 35.8 mg/g) at high molar concentration (600 mM NaCl), the maximum capacity of TiS 2 as a CDI electrode was much lower (~70 mAh/g) than as a supercapacitor (239 mAh/g). Understanding why the ion capacities of these two configurations of the same material differ will entail elucidating detailed charge/discharge mechanisms at the atomic scale. Here, we present density functional theory simulations of sodium intercalation into TiS 2 interlayers in order to gain such understanding. We systematically investigated TiS 2 stacking patterns and ion intercalation sites, energetics of the intercalated compounds, and phase transformation during sodium intercalation. The calculated structural evolution and capacitance–voltage curve agree quite well with previous measurements. We conclude that the different maximum capacities of TiS 2 measured in aqueous and dry environments originate from weaker interlayer interactions with respect to shear strain after ~33% intercalation of Na + –H 2 O pairs, which is detrimental to the mechanical stability of TiS 2 . In conclusion, this study sheds light on the underlying mechanisms of ion intercalation into layered materials and contributes to understanding requirements for future design and optimization of CDI electrode materials for water desalination.

36 MATERIALS SCIENCE↗

Memory switches based on metal oxide thin films

MnO.sub.2-x thin films (12) exhibit irreversible memory switching (28) with an OFF/ON resistance ratio of at least about 10.sup.3 and the tailorability of ON state (20) resistance. Such films are potentially extremely useful as a connection element in a variety of microelectronic circuits and arrays (24). Such films provide a pre-tailored, finite, non-volatile resistive element at a desired place in an electric circuit, which can be electrically turned OFF (22) or disconnected as desired, by application of an electrical pulse. Microswitch structures (10) constitute the thin film element, contacted by a pair of separate electrodes (16a, 16b) and have a finite, pre-selected ON resistance which is ideally suited, for example, as a programmable binary synaptic connection for electronic implementation of neural network architectures. The MnO.sub.2-x microswitch is non-volatile, patternable, insensitive to ultraviolet light, and adherent to a variety of insulating substrates (14), such as glass and silicon dioxide-coated silicon substrates.

Ramesham, Rajeshuni↗

Turbulent-like flows in quasi two-dimensional dense suspensions of motile colloids

Dense bacterial suspensions exhibit turbulent-like flows at low Reynolds numbers, driven by the activity of the microswimmers. In this study, we develop a model system to examine these dynamics using motile colloids that mimic bacterial locomotion. The colloids are powered by the Quincke instability, which causes them to spontaneously roll in a random-walk pattern when exposed to a square-wave electric field. We experimentally investigate the flow dynamics in dense suspensions of these Quincke random walkers under quasi two-dimensional conditions, where the particle size is comparable to the gap between the electrodes. The results suggest a scaling regime in the energy spectrum ∼k −4 at high wavenumbers, observed consistently across activity levels and particle concentrations. We observe that velocity time correlations decay within a single period of the square-wave field, yet an anti-correlation appears between successive field applications, indicative of a dynamic structural memory of the ensemble.

Luo, Rui [Northwestern Univ., Evanston, IL (United↗

Electrochemical patterning of amorphous carbon on diamond

The ability to pattern ion-implantation damaged or other nondiamond carbon on a diamond substrate is useful for fabricating a variety of devices. We accomplished such patterning by an unmasked implantation into a diamond substrate followed by photolithography and a selective electrochemical etch. The use of a high resistivity medium coupled with applied biases over 50 V permitted etching without requiring contact between the substrate and an electrode. Many electrolytes gave etches that exhibit high selectivity for nondiamond carbon over both diamond and dielectrics such as photoresist. Optical, electrical, and Raman spectroscopic measurements elucidate the effects of the etch on the implanted diamond surface.

Marchywka, Mike↗

Component variations and their effects on bipolar nickel-hydrogen cell performance

A 50 cell bipolar nickel-hydrogen battery was assembled to demonstrate the feasibility of constructing a high voltage stack of cells. Various component combinations were tested in this battery. The battery had approximately 1 ampere-hour of capacity and was constructed from components with an active area of 2" X 2". The components were parametrically varied to give a comparison of nickel electrodes, hydrogen electrodes, separators, fill procedures and electrolyte reservoir plate thicknesses. Groups of five cells were constructed using the same components; ten combinations were tested in all. The battery was thoroughly characterized at various change and discharge rates as well as with various pulse patterns and rates. Over a period of 1400 40% DOD LEO cycles some of the groups began to exhibit performance differences. In general, only separator variations had a significant effect on cell performance. It also appears that shunt currents may have been operating within the stack, resulting in electrolyte transfer from one cell to another, thus contributing to cell performance variations.

Manzo, Michelle A.↗

Component variations and their effects on bipolar nickel-hydrogen cell performance

A 50 cell bipolar nickel-hydrogen battery was assembled to demonstrate the feasibility of constructing a high voltage stack of cells. Various component combinations were tested in this battery. The battery had approximately 1 ampere-hour of capacity and was constructed from components with an active area of 2 x 2 inches. The components were parametrically varied to give a comparison of nickel electrodes, hydrogen electrodes, separators, fill procedures and electrolyte reservoir plate thicknesses. Groups of five cells were constructed using the same components; ten combinations were tested in all. The battery was thoroughly characterized at various change and discharge rates as well as with various pulse patterns and rates. Over a period of 1400 40-percent DOD LEO cycles some of the groups began to exhibit performance differences. In general, only separator variations had a significant effect on cell performance. It also appears that shunt currents may have been operating within the stack, resulting in electrolyte transfer from one cell to another, thus contributing to cell performance variations.

Manzo, Michelle A.↗

Modeling Electrodeposition in 3D Porous Architectures for Solid-State Li-Metal Batteries

Li-metal storage in three-dimensional (3D) electrodes is considered a potential dendrite-mitigation strategy. The large surface area and high porosity of these electrodes result in reduced local Li-plating current densities. The porous topology provides a scaffold for Li-deposition and stripping, maintaining both mechanical integrity and Li accessibility. The goal of this study is to understand how characteristics, such as geometry and material properties, affect the current distribution and deposition pattern. To this end, we developed a computational method to track material growth driven by electrodeposition within a complex geometry. This method ensures that the finite-element discretization remains conforming to the moving boundary while preserving an adequate mesh quality, and thus maintains solution accuracy. Using this new computational tool, we analyze the conditions under which porous anode architectures effectively expand the surface area of the charge-transfer interface, and self-regulate current density and dendrite growth.

3D electrode architectures↗

Genesis and Propagation of Fractal Structures During Photoelectrochemical Etching of n-Silicon

The genesis, propagation, and dimensions of fractal-etch patterns that form anodically on front- or back-illuminated n-Si(100) photoelectrodes in contact with 11.9 M NH 4 F (aqueous) have been investigated during either a linear potential sweep or a constant potential hold ( E = +6.0 V versus Ag/AgCl). Optical images collected in situ during electrochemical experiments reflected the location and underlying mechanism of initiation and propagation of the structures on the surface. X-ray photoelectron spectroscopic (XPS) data collected for samples emersed from the electrolyte at varied times provided detailed information about the chemistry of the surface during fractal etching. The fractal structure was strongly influenced by the orientation of the crystalline Si sample. Furthermore, the etch patterns were initially generated at points along the circumference of bubbles that formed upon immersion of n-Si(100) samples in the electrolyte, most likely due to the electrochemical and electronic isolation of areas beneath bubbles. XPS data showed the presence of a tensile-stressed silicon surface throughout the etching process as well as the presence of SiO x F y on the surface. The two-dimensional fractal dimension, D f,2D , of the patterns increased with etching time to a maximum observed value of D f,2D = 1.82. Promotion of fractal etching near etch masks that electrochemically and electronically isolated areas of the photoelectrode surface enabled the selective placement of highly branched structures at desired locations on an electrode surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Poling thin-film x-cut lithium niobate for quasi-phase matching with sub-micrometer periodicity

Quasi-phase-matched grating structures in lithium niobate waveguides with sub-micrometer periodicities will benefit the development of short-wavelength nonlinear optical devices. Here, we report on the reproducible formation of periodically poled domains in x-cut single-crystalline thin-film lithium niobate with periodicities as short as 600 nm. Shaped single-voltage poling pulses were applied to electrode structures that were fabricated by a combination of electron-beam and direct-writing laser lithography. Evidence of successful poling with good quality was obtained through second-harmonic microscopy and piezoresponse force microscopy imaging. For the sub-micrometer period structures, we observed patterns with a double periodicity formed by domain interactions and features with sizes <200 nm.

Zhao, Jie (ORCID:0000000306230125)↗

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.↗

GaN vertical-channel junction field-effect transistors with regrown p-GaN by metal organic chemical vapor deposition (MOCVD)

Fabricating a vertical-channel junction field-effect transistor includes forming an unintentionally doped GaN layer on a bulk GaN layer by metalorganic chemical vapor deposition, forming a Cr/SiO 2 hard mask on the unintentionally doped GaN layer, patterning a fin by electron beam lithography, defining the Cr and SiO 2 hard masks by reactive ion etching, improving a regrowth surface with inductively coupled plasma etching, removing hard mask residuals, regrowing a p-GaN layer, selectively etching the p-GaN layer, forming gate electrodes by electron beam evaporation, and forming source and drain electrodes by electron beam evaporation. The resulting vertical-channel junction field-effect transistor includes a doped GaN layer, an unintentionally doped GaN layer on the doped GaN layer, and a p-GaN regrowth layer on the unintentionally doped GaN layer. Portions of the p-GaN regrowth layer are separated by a vertical channel of the unintentionally doped GaN layer.

Zhao, Yuji↗

Modeling of Current-Voltage Characteristics in Large Metal-Semiconducting Carbon Nanotube Systems

A model is proposed for two observed current-voltage (I-V) patterns in recent experiment with a scanning tunneling microscope tip and a carbon nanotube [Collins et al., Science 278, 100 (1997)]. We claim that there are two contact modes for a tip (metal)-nanotube (semiconductor) junction depending whether the alignment of the metal and the semiconductor band structures is (1) variable (vacuum-gap) or (2) fixed (touching) with V. With the tip grounded, the tunneling case in (1) would produce large dI/dV with V > 0, small dI/dV with V < 0, and I = 0 near V = 0 for an either n- or p-nanotube. However, the Schottky mechanism in (2) would result in forward current with V < 0 for an n-nanotube, while with V > 0 for an p-nanotube. The two observed I-V patterns are thus entirely explained by a tip-nanotube contact of the two types, where the nanotube must be n-type. We apply this model to the source-drain I-V characteristics in a long nanotube-channel field-effect-transistor with metallic electrodes at low temperature [Zhou et al., Appl. Phys. Lett. 76, 1597 (2000)], and show that two independent metal-semiconductor junctions in series are responsible for the observed behavior.

Yamada, Toshishige↗

Parametrically disciplined operation of a vibratory gyroscope

Parametrically disciplined operation of a symmetric nearly degenerate mode vibratory gyroscope is disclosed. A parametrically-disciplined inertial wave gyroscope having a natural oscillation frequency in the neighborhood of a sub-harmonic of an external stable clock reference is produced by driving an electrostatic bias electrode at approximately twice this sub-harmonic frequency to achieve disciplined frequency and phase operation of the resonator. A nearly symmetric parametrically-disciplined inertial wave gyroscope that can oscillate in any transverse direction and has more than one bias electrostatic electrode that can be independently driven at twice its oscillation frequency at an amplitude and phase that disciplines its damping to zero in any vibration direction. In addition, operation of a parametrically-disciplined inertial wave gyroscope is taught in which the precession rate of the driven vibration pattern is digitally disciplined to a prescribed non-zero reference value.

Shcheglov, Kirill V.↗

YBa2Cu3O(7-x)/Au/Nb device structures

Fabrication and testing of planar and edge geometry YBaCuO/Au/Nb superconductor/normal-metal/superconductor (SNS) device structures is described. Weak-link devices of this type serve as sensitive probes of the electrical quality of the YBaCuO/Au interface. The devices are fabricated using laser-ablated, in situ, c-axis-oriented YBaCuO thin films, with both annealed and unannealed YBaCuO/Au interfaces. The planar SNS structures are formed by sequential, in situ deposition of YBaCuO, Au, and Nb, followed by etching, planarization, and wiring electrode definition to produce junctions ranging from 5 to 20 micron on a side. Resulting RnA products are 1-10 x 10 to the -8th ohm-sq cm with critical current densities up to 5 kA/sq cm. For the edge geometry devices, the YBaCuO film edges are patterned using Ar ion milling, followed by a low energy ion cleaning step and in situ deposition of Au and Nb. Devices with areas in the 10 to the -7th to 10 to the -8th sq cm range have been fabricated with RnA products lower than 10 to the -8th ohm-sq cm and critical current densities up to 3kA/sq cm. Both types of devices show ac Josephson steps under microwave irradiation. The best results have been obtained with annealed YBaCuO/Au interfaces.

Hunt, B. D.↗

Brain-Computer Interfaces for 1-D and 2-D Cursor Control: Designs Using Volitional Control of the EEG Spectrum or Steady-State Visual Evoked Potentials

We have developed and tested two EEG-based brain-computer interfaces (BCI) for users to control a cursor on a computer display. Our system uses an adaptive algorithm, based on kernel partial least squares classification (KPLS), to associate patterns in multichannel EEG frequency spectra with cursor controls. Our first BCI, Target Practice, is a system for one-dimensional device control, in which participants use biofeedback to learn voluntary control of their EEG spectra. Target Practice uses a KF LS classifier to map power spectra of 30-electrode EEG signals to rightward or leftward position of a moving cursor on a computer display. Three subjects learned to control motion of a cursor on a video display in multiple blocks of 60 trials over periods of up to six weeks. The best subject s average skill in correct selection of the cursor direction grew from 58% to 88% after 13 training sessions. Target Practice also implements online control of two artifact sources: a) removal of ocular artifact by linear subtraction of wavelet-smoothed vertical and horizontal EOG signals, b) control of muscle artifact by inhibition of BCI training during periods of relatively high power in the 40-64 Hz band. The second BCI, Think Pointer, is a system for two-dimensional cursor control. Steady-state visual evoked potentials (SSVEP) are triggered by four flickering checkerboard stimuli located in narrow strips at each edge of the display. The user attends to one of the four beacons to initiate motion in the desired direction. The SSVEP signals are recorded from eight electrodes located over the occipital region. A KPLS classifier is individually calibrated to map multichannel frequency bands of the SSVEP signals to right-left or up-down motion of a cursor on a computer display. The display stops moving when the user attends to a central fixation point. As for Target Practice, Think Pointer also implements wavelet-based online removal of ocular artifact; however, in Think Pointer muscle artifact is controlled via adaptive normalization of the SSVEP. Training of the classifier requires about three minutes. We have tested our system in real-time operation in three human subjects. Across subjects and sessions, control accuracy ranged from 80% to 100% correct with lags of 1-5 seconds for movement initiation and turning.

Trejo, Leonard J.↗

Transport Modeling for Metallic Electrode: Semiconducting Nanotube Systems

Recently, current-voltage (I-V) characteristics have been reported by Collins et al. for a system with a scanning tunneling microscope (STM) tip and a carbon nanotube. The STM tip was driven forward into a film of many entangled nanotubes on a substrate, and then was retracted, so that one of nanotubes bridged the STM and the film. I-V characteristics had two different patterns for different heights. One showed large dI/ dV with V greater than 0, small dI/dV with V less than 0, and I = 0 near V = 0 (type-I), while the other showed rectification, i.e., I does not equal 0 only with V less than 0 (type-II), with the tip grounded. We propose a physical mechanism to explain the observed I-V patterns. We consider that the observed characteristics strongly reflected the nature of the tip (metal) - nanotube (semiconductor) contact. The other end of the nanotube was entangled well in the film, and simply provided a good Ohmic contact. We will argue that there are two different contact modes: vacuum gap and touching modes, depending on the presence or absence of a tiny vacuum gap d approx. 0.1 - 0.2 nm at the junction. These modes may be related to physisorption and chemisorption, respectively. Once admitting their existence, it is naturally shown that I-V characteristics are type-I in the vacuum gap mode, and type-II in the touching mode. We argue that the nanotube had to be an n-type semiconductor judging from the I-V characteristics, contrary to often observed p-type in the transistor applications, where p-type is probably due to the oxidation in air or the trapped charges in the silicon dioxide. Additional information is contained in the original extended abstract.

Yamada, Toshishige↗

Voltage and temperature effects on low cobalt lithium-ion battery cathode degradation

Degradation of low cobalt lithium-ion cathodes was tested using a full factorial combination of upper cut-off voltage (4.0 V and 4.3 V vs. Li/Li + ) and operating temperature (25 °C and 60 °C). Half-cell batteries were analyzed with electrochemical and microstructural characterization methods. Electrochemical performance was assessed with galvanostatic cycling, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) supported by distribution of relaxation times (DRT) analysis. Electrode microstructure was characterized with scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray absorption near edge structure (XANES) imaging. Higher cut-off voltage cycling shows presence of NiO x formation, a low diffusivity rock-salt phase, in both CV and XRD data. XRD patterns confirmed that the rock-salt phase was beginning to form at the low cut-off voltage at high temperature, but in much lower intensity than at the high cut-off voltage. Higher temperature accelerates degradation processes at both voltages. Degradation factors at high temperature include NiO x formation, cathode material dissolution, and electrolyte decomposition. SEM analysis suggests that supporting phases may isolate and disconnect active material particles reducing capacity retention and battery life cycle. DRT analysis and XANES imaging show that both high temperature samples revealed a NiO x phase based on an increased diffusive impedance and a visible shift in the XANES spectra. The low cut-off voltage, high temperature sample showed a split peak and shift to lower energies indicating early formation of the NiO x phase. The diffusive impedance, which hinders intercalation and deintercalation, is driven by the formation of the NiO x phase. While primarily driven by cut-off voltage, elevated temperature also contributes to this degradation mechanism.

electrochemical impedance spectroscopy↗