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NASA NTRS2005

Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cells Stacks

This viewgraph presentation gives a detailed review of the Direct Methanol Based Fuel Cell (DMFC) stack and investigates the Ruthenium that was found at the exit of the stack. The topics include: 1) Motivation; 2) Pathways for Cell Degradation; 3) Cell Duration Testing; 4) Duration Testing, MEA Analysis; and 5) Stack Degradation Analysis.

Direct Methanol Fuel Cells, (DMFC)↗

NASA NTRS1993

Electrochemical impedance spectroscopy of lithium-titanium disulfide rechargeable cells

The two-terminal alternating current impedance of Li/TiS2 rechargeable cells was studied as a function of frequency, state-of-charge, and extended cycling. Analysis based on a plausible equivalent circuit model for the Li/TiS2 cell leads to evaluation of kinetic parameters for the various physicochemical processes occurring at the electrode/electrolyte interfaces. To investigate the causes of cell degradation during extended cycling, the parameters evaluated for cells cycled 5 times were compared with the parameters of cells cycled over 600 times. The findings are that the combined ohmic resistance of the electrolyte and electrodes suffers a tenfold increase after extended cycling, while the charge-transfer resistance and diffusional impedance at the TiS2/electrolyte interface are not significantIy affected. The results reflect the morphological change and increase in area of the anode due to cycling. The study also shows that overdischarge of a cathode-limited cell causes a decrease in the diffusion coefficient of the lithium ion in the cathode.

Narayanan, S. R.↗

NASA NTRS1972

Non-gassing nickel-cadmium battery electrodes and cells

Supposedly long-lived nickel-cadmium batteries often fail due to severe gassing on charge. In order to increase the lives of such cells attempts are being made to construct nongassing positive and negative electrodes. The gassing characteristics of both electrodes in negative limited cells were determined as a function of charge rate, charge temperature, and loading. Cycle life tests, up to 70 cycles, of some of the cells show they operate in a nongassing manner with very low degradation rates.

Luksha, E.↗

NASA NTRS1985

Verification of computer-aided designs of traveling-wave tubes utilizing novel dynamic refocusers and graphite electrodes for the multistage depressed collector

A computational procedure for the design of TWT-refocuser-MDC systems was used to design a short dynamic refocusing system and highly efficient four-stage depressed collector for a 200-W, 8- to 18-GHz, TWT. The computations were carried out with advanced, multidimensional computer programs which model the electron beam as a series of disks of charge and follow their trajectories from the RF input of the TWT, through the slow-wave structure and refocusing section, to their points of impact in the depressed collector. Secondary emission losses in the MDC were treated semi-quantitatively by injecting a representative beam of secondary electrons into the MDC analysis at the point of impact of each primary beam. A comparison of computed and measured TWT and MDC performance showed very good agreement. The electrodes of the MDC were fabricated from a particular form of isotropic graphite that was selected for its low secondary electron yield, ease of machinability, and vacuum properties. This MDC was tested (at CW) for more than 1000 hr with negligible degradation in TWT and MDC performances.

Ramins, P.↗

NASA NTRS1986

Verification of an improved computational design procedure for TWT-dynamic refocuser-MDC systems with secondary electron emission losses

A computational procedure for the design of TWT-refocuser-MDC systems was used to design a short 'dynamic' refocusing system and highly efficient four-stage depressed collector for a 200-W 8-18-GHz TWT. The computations were carried out with advanced multidimensional computer programs which model the electron beam as a series of disks of charge and follow their trajectories from the RF input of the TWT, through the slow-wave structure and refocusing section, to their points of impact in the depressed collector. Secondary emission losses in the MDC were treated semiquantitatively by injecting a representative beam of secondary electrons into the MDC analysis at the point of impact of each primary beam. A comparison of computed and measured TWT and MDC performance showed very good agreement. The electrodes of the MDC were fabricated from a particular form of isotropic graphite that was selected for its low secondary electron yield, thermal expansion characteristics, ease of machinability and vacuum properties. This MDC was tested at CW for more than 1000 h with negligible degradation in TWT and MDC performances.

Ramins, P.↗

NASA NTRS2019

Transparent Conducting Oxides as Cathodes in Li-O2 Batteries: A First Principles Computational Investigation

Li-O2 batteries have traditionally used carbon based electrodes (graphite, buckypaper) as the cathode of choice due toits good electrical conductivity, stability against non-aqueous electrolytes like dimethoxyethane (DME) and ease ofhandling. But, the carbon cathode also leads to formation of carbonate by-products that increase overpotentials duringcharging leading to degradation of the cathode and reduction of cyclability. Recent investigations have focused on using metal-oxides like SnO2, TiO2 as viable cathodes-alternatives in Li-O2 systems. In this paper, we investigate transparent conducting oxides (TCOs) as cathodes with focus on the interface between the TCO surfaces and the discharge product, Li2O2, in the Li-O2 battery using first principles computations.

transparent conducting oxides↗

NASA NTRS1992

Special tests and destructive physical analyses as used by the Aerospace Corporation with nickel-hydrogen cells

The destructive physical analysis (DPA) of electrochemical devices is an important part of the overall test. Specific tests were developed to investigate the degradation mode or the failure mechanism that surfaces during the course of a cell being assembled, acceptance tested, and life-cycle tested. The tests that have been developed are peculiar to the cell chemistry under investigation. Tests are often developed by an individual or group of researchers as a result of their particular interest in an unresolved failure mechanism or degradation mode. A series of production, operational, and storage issues that were addressed by the Electrochemistry Group at The Aerospace Corporation are addressed. As a result of these investigations, as well as associated research studies carried out to develop a clearer understanding of the nickel oxyhydroxide electrode, a series of unique and useful specialized tests were developed. Some of these special tests were assembled to describe the methods that were found to be particularly useful in resolving a wide spectrum of manufacturing, operational, and storage issues related to nickel-hydrogen cells. The general methodology of these tests is given here with references listed to provide the reader with a more detailed understanding of the tests. The tests are classified according to the sequencing, starting with the impregnation of the nickel plaque material and culminating with the storage of completed cells. The details of the wet chemical procedures that were found to be useful because of their accuracy and reproducibility are given. The equations used to make the appropriate calculations are listed.

Zimmerman, A. H.↗

NASA NTRS1974

Long life, rechargeable nickel-zinc battery

A production version of the inorganic separator was evaluated for improving the life of the nickel-zinc system. Nickel-zinc cells (7-10 Ah capacities) of different electrode separator configurations were constructed and tested. The nickel-zinc cells using the inorganic separator encasing the zinc electrode, the nickel electrode, or both electrodes had shorter lives than cells using Visking and cellophane separation. Cells with the inorganic separation all fell below 70% of their theoretical capacity within 30 cycles, but the cells constructed with organic separation required 80 cycles. Failure of the cells using the ceramic separator was irreversible capacity degradation due to zinc loss through cracks developed in the inorganic separator. Zinc loss through the separator was minimized with the use of combinations of the inorganic separator with Visking and cellophane. Cells using the combined separation operated 130 duty cycles before degrading to 70% of their theoretical capacity.

Luksha, E.↗

NASA NTRS1981

Chemical and morphological characteristics of lithium electrode surfaces

Lithium electrode surfaces were analyzed for chemical and morphological characteristics, using electron spectroscopy chemical analysis (ESCA) and scanning electron microscopy (SEM). Samples included lithium metal and lithium electrodes which were cycled in a 1.5 M lithium arsenic hexafluoride/two-methyl tetrahydrofuran electrolyte. Results show that the surface of the as-received lithium metal was already covered by a film composed of LiO2 and an Li2O/CO2 adduct with a thickness of approximately 100-200 A. No evidence of Ni3 was found. Upon exposure of the lithium electrode to a 1.5 M LiAsF6/2-Me-THF electrochemical environment, a second film was observed to form on the surface, consisting primarily of As, Si, and F, possibly in the form of lithium arsenic oxyfluorides or lithium fluorosilicates. It is suggested that the film formation may be attributed to salt degradation.

Yen, S. P. S.↗

NASA NTRS2018

Transition Metal Oxides as Cathodes in Li-O2 battery: A First Principles Investigation

Li-O2 batteries have traditionally used carbon based electrodes (graphite, buckypaper) as the cathode of choice due to its good electrical conductivity, stability against non-aqueous electrolytes like Dimethyl ether (DME) and ease of handling. But, the carbon cathode also leads to formation of carbonate by-products that increase overpotentials during charging leading to degradation of cathode and reduction of cyclability. In this work, we investigate some of the well-known oxides as cathodes with focus on the interface between the oxide surfaces and the discharge product: Li2O2, in the Li-O2 battery using first principles computations. Our results show that attention must be paid on choosing the appropriate surface of the oxides. We extend the analysis to suggest other possible oxide chemistries that should be investigated as cathodes in Li-O2 batteries.

Li-O2 battery↗

NASA NTRS2012

Some Aspects of the Failure Mechanisms in BaTiO3-Based Multilayer Ceramic Capacitors

The objective of this presentation is to gain insight into possible failure mechanisms in BaTiO3-based ceramic capacitors that may be associated with the reliability degradation that accompanies a reduction in dielectric thickness, as reported by Intel Corporation in 2010. The volumetric efficiency (microF/cm3) of a multilayer ceramic capacitor (MLCC) has been shown to not increase limitlessly due to the grain size effect on the dielectric constant of ferroelectric ceramic BaTiO3 material. The reliability of an MLCC has been discussed with respect to its structure. The MLCCs with higher numbers of dielectric layers will pose more challenges for the reliability of dielectric material, which is the case for most base-metal-electrode (BME) capacitors. A number of MLCCs manufactured using both precious-metal-electrode (PME) and BME technology, with 25 V rating and various chip sizes and capacitances, were tested at accelerated stress levels. Most of these MLCCs had a failure behavior with two mixed failure modes: the well-known rapid dielectric wearout, and so-called 'early failures." The two failure modes can be distinguished when the testing data were presented and normalized at use-level using a 2-parameter Weibull plot. The early failures had a slope parameter of Beta >1, indicating that the early failures are not infant mortalities. Early failures are triggered due to external electrical overstress and become dominant as dielectric layer thickness decreases, accompanied by a dramatic reduction in reliability. This indicates that early failures are the main cause of the reliability degradation in MLCCs as dielectric layer thickness decreases. All of the early failures are characterized by an avalanche-like breakdown leakage current. The failures have been attributed to the extrinsic minor construction defects introduced during fabrication of the capacitors. A reliability model including dielectric thickness and extrinsic defect feature size is proposed in this presentation. The model can be used to explain the Intel-reported reliability degradation in MLCCs with respect to the reduction of dielectric thickness. It can also be used to estimate the reliability of a MLCC based on its construction and microstructure parameters such as dielectric thickness, average grain size, and number of dielectric layers. Measures for preventing early failures are also discussed in this document.

Liu, David Donhang↗

NASA NTRS1993

NASA Lewis advanced IPV nickel-hydrogen technology

Individual pressure vessel (IPV) nickel-hydrogen technology was advanced at NASA Lewis and under Lewis contracts. Some of the advancements are as follows: to use 26 percent potassium hydroxide electrolyte to improve cycle life and performance, to modify the state of the art cell design to eliminate identified failure modes and further improve cycle life, and to develop a lightweight nickel electrode to reduce battery mass, hence reduce launch and/or increase satellite payload. A breakthrough in the LEO cycle life of individual pressure vessel nickel-hydrogen battery cells was reported. The cycle life of boiler plate cells containing 26 percent KOH electrolyte was about 40,000 accelerated LEO cycles at 80 percent DOD compared to 3,500 cycles for cells containing 31 percent KOH. Results of the boiler plate cell tests have been validated at NWSC, Crane, Indiana. Forty-eight ampere-hour flight cells containing 26 and 31 percent KOH have undergone real time LEO cycle life testing at an 80 percent DOD, 10 C. The three cells containing 26 percent KOH failed on the average at cycle 19,500. The three cells containing 31 percent KOH failed on the average at cycle 6,400. Validation testing of NASA Lewis 125 Ah advanced design IPV nickel-hydrogen flight cells is also being conducted at NWSC, Crane, Indiana under a NASA Lewis contract. This consists of characterization, storage, and cycle life testing. There was no capacity degradation after 52 days of storage with the cells in the discharged state, on open circuit, 0 C, and a hydrogen pressure of 14.5 psia. The catalyzed wall wick cells have been cycled for over 22,694 cycles with no cell failures in the continuing test. All three of the non-catalyzed wall wick cells failed (cycles 9,588; 13,900; and 20,575). Cycle life test results of the Fibrex nickel electrode has demonstrated the feasibility of an improved nickel electrode giving a higher specific energy nickel-hydrogen cell. A nickel-hydrogen boiler plate cell using an 80 mil thick, 90 percent porous Fibrex nickel electrode has been cycled for 10,000 cycles at 40 percent DOD.

Smithrick, John J.↗

NASA NTRS1986

Performance and properties of arsenic passivated lithium-titanium disulfide cells

In order to inhibit chemical degradation associated with the lithium-electrolyte interaction in ambient temperature lithium cells, an attempt was made to synthetically passivate the anode via ion implantation of arsenic. Solvent reduction is reduced although salt reaction with lithium is still present. The performance of the Li-TiS2 cell differs from those with standard electrodes, but further work is necessary to clarify the efficacy of this mode of passivation.

Yen, S. P. S.↗

NASA NTRS2003

MOS Circuitry Would Detect Low-Energy Charged Particles

Metal oxide semiconductor (MOS) circuits for measuring spatially varying intensities of beams of low-energy charged particles have been developed. These circuits are intended especially for use in measuring fluxes of ions with spatial resolution along the focal planes of mass spectrometers. Unlike prior mass spectrometer focal-plane detectors, these MOS circuits would not be based on ion-induced generation of electrons, and photons; instead, they would be based on direct detection of the electric charges of the ions. Hence, there would be no need for microchannel plates (for ion-to-electron conversion), phosphors (for electron-to-photon conversion), and photodetectors (for final detection) -- components that degrade spatial resolution and contribute to complexity and size. The developmental circuits are based on linear arrays of charge-coupled devices (CCDs) with associated readout circuitry (see figure). They resemble linear CCD photodetector arrays, except that instead of a photodetector, each pixel contains a capacitive charge sensor. The capacitor in each sensor comprises two electrodes (typically made of aluminum) separated by a layer of insulating material. The exposed electrode captures ions and accumulates their electric charges during signal-integration periods.

Sinha, Mahadeva↗

NASA NTRS2017

A Thermal Runaway Failure Model for Low-Voltage BME Ceramic Capacitors with Defects

Reliability of base metal electrode (BME) multilayer ceramic capacitors (MLCCs) that until recently were used mostly in commercial applications, have been improved substantially by using new materials and processes. Currently, the inception of intrinsic wear-out failures in high quality capacitors became much greater than the mission duration in most high-reliability applications. However, in capacitors with defects degradation processes might accelerate substantially and cause infant mortality failures. In this work, a physical model that relates the presence of defects to reduction of breakdown voltages and decreasing times to failure has been suggested. The effect of the defect size has been analyzed using a thermal runaway model of failures. Adequacy of highly accelerated life testing (HALT) to predict reliability at normal operating conditions and limitations of voltage acceleration are considered. The applicability of the model to BME capacitors with cracks is discussed and validated experimentally.

reliability↗

NASA NTRS1973

Non-gassing nickel-cadmium battery electrodes and cells: Testing of 25 Ah cells

The testing of 30 practical size, experimental 25 ampere hour cells constructed as part of an earlier negative limited cell development program is discussed. The test results showed that the negative limited cell is a possible means of developing a long-lived secondary cell. The cells were tested for 500 cycles using an accelerated regime approximating a 90-minute orbit period. Three groups of ten cells were tested at 0,25, and 40 C. The cycle data showed that the negative limited cells had higher degradation rates at the higher operating temperatures. At the conclusion of 500 cycles, the three groups had average capacities of 16.83, 12.74, and 5.71 ampere hours for testing at 0, 25, 40 C, respectively. The conditioning capacities of these cells was in the 25 ampere hours range. The internal cell pressures of the three groups was also temperature dependent and was, in general, in the 2 psig range during the course of the test program. No periodic variation of the internal pressure with the state-of-charge was observed except with some cells tested at 40 C.

Luksha, E.↗

NASA NTRS1986

Effect of impregnation method on cycle life of the nickel electrode

The nickel electrode has been identified as the life limiting component for individual pressure vessel (IPV) nickel-hydrogen cells when cycled under a low earth orbit (LEO) cycle regime at deep depths of discharge. As a part of an overall program to develop a long life nickel electrode for nickel-hydrogen cells, the effect of two different methods of electrochemical impregnation on the cycle life of the nickel electrode was investigated. One method was the Pickett (aqueous/ethanolic) process. The other was the modified Bell (aqueous) process. The plaques for both impregnation methods were made by sintering dry carbonyl nickel powder in a reducing atmosphere. The plaques contain a nickel screen substrate. Electrodes made from both processes were cycle tested in Air Force design IPV nickel-hydrogen cells. The only factor different for this test was the method of plaque impregnation; all other factors were the same. The cells were cycled to failure under a 90 min LEO cycle regime at a deep depth of discharge (80 percent DOD). Failure for this test was defined to occur when the cell voltage degraded to 1.0 V prior to the completion of the 35 min discharge.

Smithrick, J. J.↗

NASA NTRS1986

Effect of impregnation method on cycle life of the nickel electrode

Smithrick, J. J.↗