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At least 37 records · Page 2

Norbornene-Based Polymer Electrolytes for Lithium Cells

Norbornene-based polymers have shown promise as solid electrolytes for lithium-based rechargeable electrochemical cells. These polymers are characterized as single-ion conductors. Single-ion-conducting polymers that can be used in lithium cells have long been sought. Single-ion conductors are preferred to multiple-ion conductors as solid electrolytes because concentration gradients associated with multiple-ion conduction lead to concentration polarization. By minimizing concentration polarization, one can enhance charge and discharge rates. Norbornene sulfonic acid esters have been synthesized by a ring-opening metathesis polymerization technique, using ruthenium-based catalysts. The resulting polymer structures (see figure) include sulfonate ionomers attached to the backbones of the polymer molecules. These molecules are single-ion conductors in that they conduct mobile Li+ ions only; the SO3 anions in these polymers, being tethered to the backbones, do not contribute to ionic conduction. This molecular system is especially attractive in that it is highly amenable to modification through functionalization of the backbone or copolymerization with various monomers. Polymers of this type have been blended with poly(ethylene oxide) to lend mechanical integrity to free-standing films, and the films have been fabricated into solid polymer electrolytes. These electrolytes have been demonstrated to exhibit conductivity of 2 10(exp -5)S/cm (which is high, relative to the conductivities of other solid electrolytes) at ambient temperature, plus acceptably high stability. This type of norbornene-based polymeric solid electrolyte is in the early stages of development. Inasmuch as the method of synthesis of these polymers is inherently flexible and techniques for the fabrication of the polymers into solid electrolytes are amenable to optimization, there is reason to anticipate further improvements.

Cheung, Iris↗

Conductance of Ion Channels - Theory vs. Experiment

Transmembrane ion channels mediate a number of essential physiological processes in a cell ranging from regulating osmotic pressure to transmission of neural signals. Kinetics and selectivity of ion transport is of critical importance to a cell and, not surprisingly, it is a subject of numerous experimental and theoretical studies. In this presentation we will analyze in detail computer simulations of two simple channels from fungi - antiamoebin and trichotoxin. Each of these channels is made of an alpha-helical bundle of small, nongenomically synthesized peptides containing a number of rare amino acids and exhibits strong antimicrobial activity. We will focus on calculating ionic conductance defined as the ratio of ionic current through the channel to applied voltage. From molecular dynamics simulations, conductance can be calculated in at least two ways, each involving different approximations. Specifically, the current, given as the number of charges transferred through the channel per unit of time, can be obtained from the number of events in which ions cross the channel during the simulation. This method works well for large currents (high conductance values and/or applied voltages). If the number of crossing events is small, reliable estimates of current are difficult to achieve. Alternatively, conductance can be estimated assuming that ion transport can be well approximated as diffusion in the external potential given by the free energy profile. Then, the current can be calculated by solving the one-dimensional diffusion equation in this external potential and applied voltage (the generalized Nernst-Planck equation). To do so three ingredients are needed: the free energy profile, the position-dependent diffusion coefficient and the diffusive flux of ions into the channel. All these quantities can be obtained from molecular dynamics simulations. An important advantage of this method is that it can be used equally well to estimating large and small currents. In addition, once the free energy profile becomes available the full current-voltage dependence can be readily obtained. For both channels we carried out calculations using both approaches. We also tested the main assumptions underlying the diffusive model, such as uncorrelated nature of individual crossing events and Fickian diffusion. The accuracy and consistency of different methods will be discussed. Finally we will discuss how comparisons between calculated and measured ionic conductance and selectivity of transport can be used for determining structural models of the channels.

Pohorille, Andrew↗

Superacid-Based Lithium Salts For Polymer Electrolytes

Solid polymer electrolytes exhibiting high lithium-ion conductivities made by incorporating salts of superacids into thin films of polyethylene oxide (PEO). These and other solid-polymer electrolytes candidates for use in rechargeable lithium-based electrochemical cells. Increases in room-temperature lithium-ion conductivities of solid electrolytes desirable because they increase achievable power and energy densities.

Nagasubramanian, Ganesan↗

Rod-Coil Block Polyimide Copolymers

This invention is a series of rod-coil block polyimide copolymers that are easy to fabricate into mechanically resilient films with acceptable ionic or protonic conductivity at a variety of temperatures. The copolymers consist of short-rigid polyimide rod segments alternating with polyether coil segments. The rods and coil segments can be linear, branched or mixtures of linear and branched segments. The highly incompatible rods and coil segments phase separate, providing nanoscale channels for ion conduction. The polyimide segments provide dimensional and mechanical stability and can be functionalized in a number of ways to provide specialized functions for a given application. These rod-coil black polyimide copolymers are particularly useful in the preparation of ion conductive membranes for use in the manufacture of fuel cells and lithium based polymer batteries.

Mary Ann B Meador↗

Chemical Passivation of Li(exp +)-Conducting Solid Electrolytes

Plates of a solid electrolyte that exhibits high conductivity for positive lithium ions can now be passivated to prevent them from reacting with metallic lithium. Such passivation could enable the construction and operation of high-performance, long-life lithium-based rechargeable electrochemical cells containing metallic lithium anodes. The advantage of this approach, in comparison with a possible alternative approach utilizing lithium-ion graphitic anodes, is that metallic lithium anodes could afford significantly greater energy-storage densities. A major impediment to the development of such cells has been the fact that the available solid electrolytes having the requisite high Li(exp +)-ion conductivity are too highly chemically reactive with metallic lithium to be useful, while those solid electrolytes that do not react excessively with metallic lithium have conductivities too low to be useful. The present passivation method exploits the best features of both extremes of the solid-electrolyte spectrum. The basic idea is to coat a higher-conductivity, higher-reactivity solid electrolyte with a lower-conductivity, lower-reactivity solid electrolyte. One can then safely deposit metallic lithium in contact with the lower-reactivity solid electrolyte without incurring the undesired chemical reactions. The thickness of the lower-reactivity electrolyte must be great enough to afford the desired passivation but not so great as to contribute excessively to the electrical resistance of the cell. The feasibility of this method was demonstrated in experiments on plates of a commercial high-performance solid Li(exp +)- conducting electrolyte. Lithium phosphorous oxynitride (LiPON) was the solid electrolyte used for passivation. LiPON-coated solid-electrolyte plates were found to support electrochemical plating and stripping of Li metal. The electrical resistance contributed by the LiPON layers were found to be small relative to overall cell impedances.

West, William↗

Electrical properties of the middle atmosphere

Probe techniques have been utilized extensively to measure middle atmospheric electrical properties such as the polar components of conductivity, ion mobility and density. The most variable of these parameters is conductivity, which is dependent on both charge mobility and concentration. Overall conductivity variations, attributable to different geophysical conditions, can exceed several orders of magnitude at some altitudes. Also, measurements of conductivity over the 20 to 90 km region indicate a general exponential increase with altitude, exceeding seven orders of magnitude during certain conditions. Gerdien condensers, on occasion, have measured very low-mobility positive ions in addition to the more commonly observed molecular species. These smaller mobility values appear to indicate the presence of very large ions at some altitudes, possibly charged particulates, having mass sizes greater than those identifiable by presently flown mass spectrometers. The presence of these large ions is of importance to middle atmospheric electrodynamics as a potential causal mechanism for measured large electric fields.

Mitchell, John D.↗

Nighttime auroral energy deposition in the middle atmosphere

Ionospheric rocket sounding data for eight nighttime auroral events are used to characterize relativistic electron showers and their effects on atmospheric ozone. The rockets were launched from the Poker Flat Research Range in Alaska and from Andoya, Norway over the period 1976-82. Energetic fluxes were always detected but were of insufficient magnitude to produce significant changes in stratospheric ozone. However, middle atmospheric energy sources were found to be dominated by relativistic electrons and X-ray bremmstrahlung, the latter from 40-55 km and the former from 55-60 km altitudes. The ionizing radiation is concluded to be a significant factor in mesospheric ion conductivity, mobility, electric field structure and analytical models for the ion-neutral chemistry.

Goldberg, R. A.↗

An experimental investigation of mesospheric ionization

Mesospheric ionization and its variability are examined. Data were obtained primarily by the parachute-borne blunt probe technique conducted in coordinated rocket experiments at White Sands Missile Range, New Mexico and Wallops Island, Virginia. Electrical conductivity measurements and deduced charge density values from ten rocket launches are presented and discussed. Positive ion conductivity and electron density were found to be relatively invariant with height between 45 and 60 km. Variations in positive conductivity of a factor of two and enhancements in negative conductivity by as much as a factor of four were measured by the blunt probe. A simple lumped parameter ion chemistry model is shown to satisfactorily explain the charge density values for the undisturbed lower D-region. Implications of the data in terms of this model are considered. The principal loss mechanism for positive ions in the 45 to 60 km. region is concluded to be dissociative recombination. Electron densities deduced from the conductivity data are explained by detachment involving a minor neutral constituent which is mixed between 65 and 45 km. and then cuts off sharply below 45 km. A correlation study involving blunt probe measurements shows relatively good agreement between variations in positive conductivity and temperature.

Mitchell, J. D.↗

Middle-atmosphere positive ion measurements during solar eclipses

Solar effects on middle-atmosphere electrical parameters, as demonstrated by eclipse-associated responses of conductivity, ion mobility, and charge density, are considered for the total solar eclipses at Red Lake, Ontario, Canada on February 26, 1979 and at San Marco range, Kenya, on February 16, 1980. Negative-conductivity measurements for the Canadian eclipse and probe-current measurements for the Kenyan eclipse demonstrate a rapid loss of free electrons below 80 km at totality. During the Kenyan eclipse, positive-ion responses were different for each of two distinct ion mobility groups. Between 45 and 60 km, eclipse-related positive-ion responses are associated with the low-mobility ions. It is shown that these ions are lost at totality and that an excess buildup occurs following totality. Above 70 km, positive-ion loss at totality is associated with the more mobile ions and only low-mobility positive ions are measured in this region. The buildup in total ion density following totality is thought to result from a reduction in ion loss associated with weak-electron recovery in the region.

Mitchell, J. D.↗

Generation of High Pressure Oxygen via Electrochemical Pumping in a Multi-stage Electrolysis Stack

An oxygen pump can produce high-purity high-pressure oxygen. Oxygen ions (O.sup.2-) are electrochemically pumped through a multi-stage electrolysis stack of cells. Each cell includes an oxygen-ion conducting solid-state electrolyte between cathode and anode sides. Oxygen dissociates into the ions at the cathode side. The ions migrate across the electrolyte and recombine at the anode side. An insulator is between adjacent cells to electrically isolate each individual cell. Each cell receives a similar volt potential. Recombined oxygen from a previous stage can diffuse through the insulator to reach the cathode side of the next stage. Each successive stage similarly incrementally pressurizes the oxygen to produce a final elevated pressure.

Setlock, John A↗

Generation of High Pressure Oxygen via Electrochemical Pumping in a Multi-Stage Electrolysis Stack

An oxygen pump can produce high-purity high-pressure oxygen. Oxygen ions (O(2-)) are electrochemically pumped through a multi-stage electrolysis stack of cells. Each cell includes an oxygen-ion conducting solid-state electrolyte between cathode and anode sides. Oxygen dissociates into the ions at the cathode side. The ions migrate across the electrolyte and recombine at the anode side. An insulator is between adjacent cells to electrically isolate each individual cell. Each cell receives a similar volt potential. Recombined oxygen from a previous stage can diffuse through the insulator to reach the cathode side of the next stage. Each successive stage similarly incrementally pressurizes the oxygen to produce a final elevated pressure.

Setlock, John A↗

Mixed Conducting Electrodes for Better AMTEC Cells

Electrode materials that exhibit mixed conductivity (that is, both electronic and ionic conductivity) have been investigated in a continuing effort to improve the performance of the alkali metal thermal-to-electric converter (AMTEC). These electrode materials are intended primarily for use on the cathode side of the sodium-ion-conducting solid electrolyte of a sodium-based AMTEC cell. They may also prove useful in sodium-sulfur batteries, which are under study for use in electric vehicles. An understanding of the roles played by the two types of conduction in the cathode of a sodium-based AMTEC cell is prerequisite to understanding the advantages afforded by these materials. In a sodium-based AMTEC cell, the anode face of an anode/solid-electrolyte/cathode sandwich is exposed to Na vapor at a suitable pressure. Upon making contact with the solid electrolyte on the anode side, Na atoms oxidize to form Na+ ions and electrons. Na+ ions then travel through the electrolyte to the cathode. Na+ ions leave the electrolyte at the cathode/electrolyte interface and are reduced by electrons that have been conducted through an external electrical load from the anode to the cathode. Once the Na+ ions have been reduced to Na atoms, they travel through the cathode to vaporize into a volume where the Na vapor pressure is much lower than it is on the anode side. Thus, the cathode design is subject to competing requirements to be thin enough to allow transport of sodium to the low-pressure side, yet thick enough to afford adequate electronic conductivity. The concept underlying the development of the present mixed conducting electrode materials is the following: The constraint on the thickness of the cathode can be eased by incorporating Na+ -ionconducting material to facilitate transport of sodium through the cathode in ionic form. At the same time, by virtue of the electronically conducting material mixed with the ionically conducting material, reduction of Na+ ions to Na atoms can take place throughout the thickness of the cathode. The net effect is to reduce the diffusion and flow resistance to sodium through the electrode while reducing the electronic resistance by providing shorter conduction paths for electrons. Reduced resistance to both sodium transport and electronic conductivity results in an increase in electric power output.

Ryan, Margaret↗

Low latitude middle atmosphere ionization studies

Low latitude middle atmosphere ionization was studied with data obtained from three blunt conductivity probes and one Gerdien condenser. An investigation was conducted into the effects of various ionization sources in the 40 to 65 Km altitude range. An observed enhancement of positive ion conductivity taking place during the night can be explained by an atmsopheric effect, with cosmic rays being the only source of ionization only if the ion-ion recombination coefficient (alpha sub i) is small(10 to the -7 power cu cm/s) and varies greatly with altitude. More generally accepted values of alpha sub i ( approximately equal to 3x10 to the -7 power cu cm/s) require an additional source of ionization peaking at about 65 Km, and corresponding approximately to the integrated effect of an X-ray flux measured on a rocket flown in conjunction with the ionization measurements. The reasonable assumption of an alpha sub i which does not vary with altitude in the 50-70 Km range implies an even greater value alpha sub i and a more intense and harder X-ray spectrum.

Bassi, J. P.↗

Two-temperature models of old supernova remnants with ion and electron thermal conduction

To investigate the potential effects thermal conduction may have on the evolution of old supernova remnants, we present the results of 1D (spherically symmetric) numerical simulations of a remnant in a homogeneous interstellar medium for four different cases: (1) without thermal conduction; (2) with both electron and ion thermal conduction assuming equal temperatures; (3) with electron thermal conduction only, following electron and ion temperatures separately; and (4) with both electron and ion thermal conduction following separate temperatures. We followed the entire evolution until the completion of the remnant bubble collapse. Our most significant result is that in remnant evolution studies concerned principally with either the shell or bubble evolution at late times, reasonable results are obtained with single-temperature models. When the electron and ion temperatures are followed separately, however, ion thermal conduction cannot safely be ignored.

Cui, Wei↗

Ion Engine With Solid-Electrolyte Ion Generator

Working fluid utilized efficiently. Working fluid positive ions conducted through solid electrolyte to outside, then accelerated in external electric field. While in solid-electrolyte material, ions do not recombine with electrons: transported to surface with high ionization efficiency. Provides new way to generate beam of ions for implantation in semiconductors or other applications.

Richter, R.↗

Middle atmosphere measurements of small-scale electron density irregularities and ion properties during the MAC/Epsilon campaign

Rocket payloads designed to measure small scale electron density irregularities and ion properties in the middle atmosphere were flown with each of the three main salvos of the MAC/Epsilon campaign conducted at the Andoya Rocket Range, Norway, during October to November 1987. Fixed bias, hemispheric nose tip probes measured small scale electron density irregularities, indicative of neutral air turbulence, during the rocket's ascent; and subsequently, parachute-borne Gerdien condensers measured the region's polar electrical conductivity, ion mobility and density. One rocket was launched during daylight (October 15, 1052:20 UT), and the other two launches occurred at night (October 21, 2134 UT: November 12, 0021:40 UT) under moderately disturbed conditions which enhanced the detection and measurement of turbulence structures. A preliminary analysis of the real time data displays indicates the presence of small scale electron density irregularities in the altitude range of 60 to 90 km. Ongoing data reduction will determine turbulence parameters and also the region's electrical properties below 90 km.

Blood, S. P.↗

Electrodynamics payloads for small rockets

Totally integrated design facilitates electrical cleanliness and light weight, which are necessary in subsonic parachute-borne payloads for electrodynamics investigations. 'Blunt' probes measure ion conductivity, as do Gerdien condensers. Recent finite-element computer analyses combining flow and electrodynamics have resolved problems in determining ion densities and mobilities from Gerdien data. Three-axis electric fields are measured with deployable boom-mounted electrodes from dc through VLF. Splitting the cylindrical payload with an insulator and measuring the current between halves has provided a vertical Maxwell current detector mechanically rigid enough to measure, at ELF, energy related to coupling. A nose tip 'Smith' probe turbulence measurement is usually performed on ascent. Other instrumentation, such as photo-ionization sources and X-ray detectors, can also be included. These electrodynamic measurement payloads are about one meter in length and have a mass of about 9 kg. They can be launched with an Orion-class or smaller vehicle.

Croskey, C. L.↗

Middle atmosphere electrical structure, dynamics and coupling

The ram current to ion traps and the insensitivity of ion conductivity to compressibility provide the basis of robust techniques for middle atmosphere measurements. Gerdien condensers are more difficult to implement but provide more information. Mesospheric electrical conductivity shows many orders of magnitude variability, with depressions below gas phase model values indicating dominance by aerosol particles. The mobility of these ions has been directly measured and indicates particles of thousands of AMU. Large mesospheric fields have come into question, and diagnostic measurements show that many such measurements may be artifacts. However, some measurements of V/m fields with symmetrical and redundant sensors appear to be real. These fields complicate the 'mapping' picture of electrical coupling and may also modulate the transport of aerosol particles. They are probably related to neutral atmospheric dynamics and/or the aerosol particles. Lightning couples much more energy to the middle atmosphere and above than previously suspected, primarily in the ELF-UHF range. There are many important unanswered questions in this relatively unexplored frontier area which may be answered with low cost balloon and sounding rocket experiments.

Hale, L. C.↗