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Reid, Margaret A.

Publications and source records attributed to Reid, Margaret A..

Characterization of cobalt-dipped nickel electrodes with fibrex substrates

Nickel electrodes using fibrous substrates have poorer initial utilization of the active material than those using conventional nickel sinter substrates. Previous investigators had shown that utilization can be dramatically improved by dipping these electrodes in a cobalt solution immediately after the electrochemical impregnation, before formation and cycling is carried out. The present study looked at the gas evolution behavior of dipped and undipped electrodes, impedance curves, and the charge-discharge curves to try to understand the reasons for the improvement in utilization. Impedance measurements under open circuit conditions indicate that some of the improvement is due to a reduction in the ohmic resistance of the surface layer of the particles, in agreement with earlier work. The charge-discharge curves suggest that there may also be an additional increase in the ohmic resistance of the surface layer of the undipped electrode during charging.

Youngman, Carolyn A.↗

Impedance measurements on a spiral-wound nickel/metal hydride cell cycled in a simulated Leo orbit

A spiral-wound size C cell was cycled at 25 C in a low earth orbit (LEO) regime at 50 percent depth of discharge (DOD) with approximately five percent over-charge. The nominal capacity was 3.5 AH. The cell was cycled for 2000 cycles. Capacity checks and impedance measurements over the complete range of state of charge were made upon receipt and after 500, 1000, and 2000 cycles. The capacity of the cell was essentially unchanged until after the impedance measurements at 2000 cycles. Only small changes in the impedance parameters were observed, but there was somewhat more scatter in the data after 2000 cycles. When the cell was returned to LEO cycling after 2000 cycles, only 38 percent of the capacity could be obtained. It is believed that the cell failed because of an equipment failure at the end of the final impedance measurements which allowed an over-discharge.

Reid, Margaret A.↗

Changes in impedance of Ni/Cd cells with voltage and cycle life

Impedances of aerospace design Super Ni/Cd cells are being measured as functions of voltage and number of cycles. The cells have been cycled over 4400 cycles to date. Analysis of the impedance data has been made using a number of equivalent circuits. The model giving the best fit over the whole range of voltage has a parallel circuit of a kinetic resistance and a constant phase element in series with the ohmic resistance. The values for the circuit elements have been treated as empirical parameters, and no attempt has been made as yet to correlate them with physical and chemical changes in the electrode. No significant changes have been seen as yet with the exception of a decrease in kinetic resistance at low states of charge in the first 500 cycles.

Reid, Margaret A.↗

Impedances of Li/SO2 cells retrieved from the Long Duration Exposure Facility (LDEF satellite) and comparison with cells stored terrestrially

Impedances were measured on several Li/SO2 cells retrieved from the Long Duration Exposure Facility (LDEF) satellite. These cells were used to power instruments and recorders and had all been partially or fully discharged. Impedances were also measured on several cells that were stored in cold storage since manufacture. Unfortunately, none of the cells stored terrestrially had undergone any discharge, whereas all of the cells on the satellite were at least partially discharged early in the mission and then remained on orbit for about 5 years further. It has been observed by others that storage of an Li/SO2 cell after partial discharge, increases the resistance and thickness of the passive film on the Li electrode, as indicated by an increase in the time for recovery of voltage when a load is applied (voltage lag), or in some cases by an inability of a cell to sustain a normal current after such storage. Since the cells stored terrestrially were not discharged in the same manner as the LDEF cells, a direct comparison cannot be made. Thus, the effects of the space environment cannot be separated from the effects of storage after partial discharge. It is believed that the increases in impedance in the LDEF cells are largely due to the storage upon partial discharge rather than the effects of the space environment.

Reid, Margaret A.↗

The Nickel(111)/Alkaline Electrolyte Interface

The electrochemical properties of Ni (111) prepared and characterized in ultra high vacuum, UHV, by surface analytical techniques have been examined in alkaline media by cyclic voltammetry using an UHV-electrochemical cell transfer system designed and built in this laboratory. Prior to the transfer, the Ni(111) surfaces were exposed to saturation coverages of CO in UHV in an attempt to protect the surface from possible contamination with other gases during the transfer. Temperature Programmed Desorption, TPD, of CO-dosed Ni (111) surfaces displaying sharp c(4x2), LEED patterns, subsequently exposed to water-saturated Ar at atmospheric pressure in an auxiliary UHV compatible chamber and finally transferred back to the main UHV chamber, yielded CO2 and water as the only detectable products. This indicates that the CO-dosed surfaces react with water and/or bicarbonate and hydroxide as the most likely products. Based on the integration of the TPD peaks, the combined amounts of H2O and CO2 were found to be on the order of a single monolayer. The reacted c(4x2)CO/Ni(111) layer seems to protect the surface from undergoing spontaneous oxidation in strongly alkaline solutions. This was evidenced by the fact that the open circuit potential observed immediately after contact with deaerated 0.1 M KOH was about 0.38 V vs. DHE, drifting slightly towards more negative values prior to initiating the voltametric scans. The average ratio of the integrated charge obtained in the first positive linear scan in the range of 0.35 to 1.5 V vs. DHE (initiated at the open circuit potential) and the first (and subsequent) linear negative scans in the same solution yielded for various independent runs a value of 3.5 +/- 0.3. Coulometric analysis of the cyclic voltammetry curves indicate that the electrochemically formed oxyhydroxide layer involves a charge equivalent to 3.2 +/- 0.4 layers of Ni metal.

Wang, Kuilong↗

Impedances of Nickel Electrodes Cycled in Various KOH Concentrations

Impedances were measured of electrodes from boiler-plate cells cycled i n KOH concentrations from 21% to 36%. These cells under accelerated conditions at 80% DOD to failure, defined discharge voltage. Cell life ranged from about 1,000 t o 40 impedances were measured at five voltages corresponding to charge. The results were analyzed using a standard circuit model including a Warburg impedance term. The kinetic resistances and Warburg slopes were greater for those electrodes which had failed earliest. Other circuit models have also been examined. The results are considered indicative but not conclusive, since the cells had been stored after failure for varying lengths of time which is known to affect the impedance. In order to minimize the effects of storage, the electrodes were cycled 10 times before the impedance measurements were taken.

Reid, Margaret A.↗

Impedance studies of nickel/cadmium and nickel/hydrogen cells using the cell case as a reference electrode

Impedance measurements have been made on several Ni/Cd and Ni/H2 flight-weight cells using the case as a reference electrode. For these measurements, the voltage of the case with respect to the anode or cathode is unimportant provided that it remains stable during the measurement of the impedance. In the cells measured so far, the voltage of the cell cases with respect to the individual electrodes differ from cell to cell, even at the same overall cell voltage, but they remain stable with time. The measurements can thus be used to separate the cell impedance into the contributions of each electrode, allowing improved diagnosis of cell problems.

Reid, Margaret A.↗

Impedances of Ni electrodes and Ni/H2 cells from different manufacturers

The consistency of impedance measurements within each group of flightweigth Ni/H2 cells being tested for Space Station Freedom confirms that impedance measurements are reproducible provided that the same conditions of cycling and storage are maintained. However, electrodes and cells from different manufacturers vary widely, even with the same cycling and storage conditions. Measurements on cells from two manufacturers that have been cycled for 500-800 cycles show that there are not only major changes upon cycling, but there are substantial differences in the behavior of cells from different manufacturers with cycling.

Reid, Margaret A.↗

Impedance studies of Ni/Cd and Ni/H2 cells using the cell case as a reference electrode

Impedance measurements have been made on several Ni/Cd and Ni/H2 flightweight cells using the case as a reference electrode. For these measurements the voltage of the case with respect to the anode or cathode is unimportant provided that it remains stable during the measurement of the impedance. In the cells measured so far, the voltages of the cell cases with respect to the individual electrodes differ from cell to cell even at the same overall cell voltage, but they remains stable with time. The measurements can thus be used to separate the cell impedance into the contributions of each electrode, allowing improved diagnosis of cell problems.

Reid, Margaret A.↗

Impedances of electrochemically impregnated nickel electrodes as functions of potential, KOH concentration, and impregnation method

Impedances of fifteen electrodes form each of the four U.S. manufactures were measured at 0.200 V vs. the Hg/HgO reference electrode. This corresponds to a voltage of 1.145 for a Ni/H2 cell. Measurements were also made of a representative sample of these at 0.44 V. At the higher voltage, the impedances were small and very similar, but at the lower voltage there were major differences between manufacturers. Electrodes from the same manufacturers showed only small differences. The impedances of electrodes from two manufacturers were considerably different in 26 percent KOH from those in 31 percent KOH. These preliminary results seen to correlate with the limited data from earlier life testing of cells from these manufacturers. The impedances of cells being tested for Space Station Freedom are being followed, and more impendance measurements of electrodes are being performed as functions of manufacturer, voltage, electrolyte concentration, and cycle history in hopes of finding better correlations of impedance with life.

Reid, Margaret A.↗

Impedance studies of Ni/Cd and Ni/H cells using the cell case as reference electrode

Many impedance studies were carried out on Ni electrodes and Ni/Cd and Ni/H batteries. In order for impedance to become a diagnostic tool, accurate and reproducible measurements must be made, and some way of separating the contributions of the individual electrodes must be found. Using the PAR and the Solartron impedance equipment, studies have found that consistent measurements can be made if the cells or electrodes are equilibrated at the voltage of interest. In the charged state, equilibration times required are short, on the order of a few hours or less, but the equilibration time required becomes progessively longer as the voltage is lowered. The cell case can be used as a reference electrode during impedance measurements. The voltage of the case with respect to the electrodes is unimportant provided that it does not change appreciably during the course of the measurement. Measurements were made with several uncycled Ni/Cd cells, one from a lot which was known to have faulty Cd electrodes and another from a lot which showed excellent cycle life and presumably had good Cd electrodes. The impedances of the Ni electrodes vs. the case were similar, while the impedance of the poor Cd electrodes vs. the case. A 50 AH Ni/H cell was also investigated. After subtraction of the ohmic resistances, the sums of the impedances of the individual electrodes were very close to the impedance of the total cell. This indicates that the method is valid for examining the characteristics of the individual electrodes in situ.

Reid, Margaret A.↗

Changes in impedance of Ni electrodes upon standing and cycling

Impedances of Ni electrodes vary with many factors including voltage, cycling, and manufacturer. However, results from Ni/H2 cells being tested for Space Station Freedom show that consistent results are obtained within a group of cells from the same manufacturer if the cells are cycled and stored in the same manner. Impedance changes with storage and cycling are being investigated. Impedances are low in the fully charged state but rise abruptly by several orders of magnitude at a voltage corresponding to a very low state-of-charge. After standing for several months, this increase occurred at a higher voltage, consistent with an increase in structural order during storage which hinders diffusion of protons and reduces high rate capacity. Early measurements on the effects of cycling on Ni/H2 cells being tested for Space Station Freedom show differences between cells from different manufacturers.

Reid, Margaret A.↗

I-BIEM, an iterative boundary integral equation method for computer solutions of current distribution problems with complex boundaries: A new algorithm. I - Theoretical

A new algorithm for an iterative computation of solutions of Laplace's or Poisson's equations in two dimensions, using Green's second identity, is presented. This algorithm converges strongly and geometrically and can be applied to curved, irregular, or moving boundaries with nonlinear and/or discontinuous boundary conditions. It has been implemented in Pascal on a number of micro- and minicomputers and applied to several geometries. Cases with known analytic solutions have been tested. Convergence to within 0.1 percent to 0.01 percent of the theoretical values are obtained in a few minutes on a microcomputer.

Cahan, B. D.↗