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At least 19 records

Use of Hydrogel Electrolyte in Zn-MnO2 Rechargeable Batteries: Characterization of Safety, Performance, and Cu2+ Ion Diffusion

Achieving commercially acceptable Zn-MnO2 rechargeable batteries depends on the reversibility of active zinc and manganese materials, and avoiding side reactions during the second electron reaction of MnO2. Typically, liquid electrolytes such as potassium hydroxide (KOH) are used for Zn-MnO2 rechargeable batteries. However, it is known that using liquid electrolytes causes the formation of electrochemically inactive materials, such as precipitation Mn3O4 or ZnMn2O4 resulting from the uncontrollable reaction of Mn3+ dissolved species with zincate ions. In this paper, hydrogel electrolytes are tested for MnO2 electrodes undergoing two-electron cycling. Improved cell safety is achieved because the hydrogel electrolyte is non-spillable, according to standards from the US Department of Transportation (DOT). The cycling of “half cells” with advanced-formulation MnO2 cathodes paired with commercial NiOOH electrodes is tested with hydrogel and a normal electrolyte, to detect changes to the zincate crossover and reaction from anode to cathode. These half cells achieved ≥700 cycles with 99% coulombic efficiency and 63% energy efficiency at C/3 rates based on the second electron capacity of MnO2. Other cycling tests with “full cells” of Zn anodes with the same MnO2 cathodes achieved ~300 cycles until reaching 50% capacity fade, a comparable performance to cells using liquid electrolyte. Electrodes dissected after cycling showed that the liquid electrolyte allowed Cu ions to migrate more than the hydrogel electrolyte. However, measurements of the Cu diffusion coefficient showed no difference between liquid and gel electrolytes; thus, it was hypothesized that the gel electrolytes reduced the occurrence of Cu short circuits by either (a) reducing electrode physical contact to the separator or (b) reducing electro-convective electrolyte transport that may be as important as diffusive transport.

25 ENERGY STORAGE↗

Popcorning Failures in Polymer and MnO2 Tantalum Capacitors

Popcorning is a well-known effect in plastic encapsulated microcircuits (PEM) and it occurs in chip tantalum capacitors. The sensitivity of components to the presence of moisture during soldering is characterized by the moisture sensitivity level (MSL); however, contrary to PEMs, there is no standard procedure for establishing MSL for tantalum capacitors.The effect of absorbed moisture on soldering related degradation and failures in tantalum capacitors have not been studied properly yet, and there is no sufficient information regarding the difference in the sensitivity to soldering between polymer and MnO2 capacitors. In this work, 16 types of polymer and 9 types of MnO2 tantalum capacitors with different moisture content have been tested before and after reflow soldering. The level of moisture release during soldering has been estimated and thermo-mechanical analysis used to assess deformation of capacitorsduring soldering simulations. Results show that moisture uptake in similar parts is approximately two times greater in polymer than in MnO2 capacitors. Cracking of the case and degradation of parameters can occur in both types of parts, but MnO2 capacitors are much more likely to fail catastrophically with a short circuit and possible ignition during the first power-on cycle. This type of failure in MnO2 capacitors is lot-related, can occur even at derated voltages and relatively low levels of moisture sorption that corresponds to room conditions. Baking before soldering is an effective measure to prevent failures even in lots susceptible to popcorning damage.

Capacitor↗

Effect of Soldering on Polymer and MnO2 Tantalum Capacitors

Soldering might have a strong effect on performance and reliability of most surface mount technology components, including tantalum capacitors. High quality tantalum capacitors are likely the only type of components where soldering simulation is the first step during screening. Nevertheless, post-soldering failures of tantalum capacitors happen and require additional analysis. Popcorning is a well-known effect in plastic encapsulated microcircuits (PEM) and it occurs also in chip tantalum capacitors. The sensitivity of parts to the presence of moisture during soldering is characterized by the moisture sensitivity level (MSL); however, contrary to PEMs, there is no standard procedure for establishing MSL for tantalum capacitors. The effect of absorbed moisture on soldering related degradation and failures in tantalum capacitors have not been studied properly yet, and there is no sufficient information regarding the difference in the sensitivity to soldering between polymer and MnO2 tantalum capacitors. In this work, 16 types of polymer and 9 types of MnO2 cathodes tantalum capacitors with different moisture content have been tested before and after reflow soldering. The level of moisture release after soldering has been estimated and thermo-mechanical analysis used to assess deformation of capacitors during soldering simulations. Results show that moisture uptake in similar parts is approximately two times greater in polymer than in MnO2 capacitors. Cracking of the case and degradation of parameters can occur in both types of parts, but MnO2 capacitors are much more likely to fail catastrophically with a short circuit and possible ignition during the first power-on cycle. This type of failure in MnO2 capacitors is lot-related, can occur even at derated voltages and relatively low levels of moisture sorption corresponding to room conditions. Baking before soldering is an effective measure to prevent failures even in lots susceptible to popcorning damage. Recommendations for baking and testing to establish MSL are suggested.

Alexander Teverovsky↗

A new concept for high-cycle-life LEO: Rechargeable MnO2-hydrogen

The nickel-hydrogen secondary battery system is now the one of choice for use in GEO satellites. It offers superior energy density to that of nickel-cadmium, with a lifetime that is at least comparable in terms of both cycle life and overall operating life. While the number of deep cycles required for GEO use is small, LEO satellites with long lifetimes (5 to 10 years) will require secondary battery systems allowing 30,000 to 60,000 useful cycles which are characterized by an approximately 2C charge rate and C average discharge rate. Recent work has shown that birnessite MnO2 doped with bismuth oxide can be cycled at very high rates (6C) over a very large number of cycles (thousands) at depths-of-discharge in the 85 to 90 percent range, based on two electrons, which discharge at the same potential in a flat plateau. The potential is about 0.7 V vs. hydrogen, with a cut-off at 0.6 V. At first sight, this low voltage would seem to be a disadvantage, since the theoretical energy density will be low. However, it permits the use of lightweight materials that are immune from corrosion at the positive. The high utilization and low equivalent weight of the active material, together with the use of teflon-bonded graphite for current collection, result in very light positives, especially when these are compared with those in a derated nickel-hydrogen system. In addition, the weight of the pressure vessel falls somewhat, since the dead volume is lower. Calculations show that a total system will have 2.5 times the Ah capacity of a derated nickel-hydrogen LEO battery, so that the energy density, based on 1.2 V for nickel-hydrogen and 0.7 V for MnO2-hydrogen, will be 45 percent higher for comparable cycling performance.

Appleby, A. John↗

High-rate Li-MnO2 cells for aerospace use

A series of comparative studies were undertaken on representative cells as objectively as possible in order to appreciate the respective advantages of the different systems. After reviewing the first test results our attention was soon focussed on the following four lithium systems: (1) Li-SOCl2; (2) Li-SO2; (3) Li-(CF(sub x))(sub n); and (4) Li-MnO2. This resulted in the decision in 1982 to adopt the Li-MnO2 system for high-rate applications.

Becker-Kaiser, R.↗

Direct Conversion of MnO2 into Atomic Mn Sites for Oxygen Reduction

Development of platinum group metal (PGM)-free catalysts has been investigated to replace the platinum group metal catalyst in future inexpensive polymer electrolyte membrane (PEM) fuel cells. Usually, synthetic methods for these PGM-free catalysts involve introducing transition-metal salts or molecules. Herein, we demonstrate a facile synthetic method to prepare PGM-free Mn-N-C catalysts by directly converting manganese oxides into highly active MnN4 sites. Typically, MnO2 is used as a Mn source. Ammonium chloride and benzimidazole are introduced during high-temperature treatment to enhance catalytic activity and stability further. Ammonia generated from the decomposition of ammonium chloride can improve the intrinsic ORR activity of MnNx moieties through chemical or electronic effects by introducing additional nitrogen groups. The Mn-N-C catalyst exhibits promising ORR activity, achieving a half-wave potential of 0.83 V in 0.5 M H2SO4, outperforming most PGM-free ORR catalysts. The robust carbon structure resulting from organic-molecule treatment is also verified by electrochemical and physical characterization, thereby improving the catalyst's durability.

Yang, Xiaoxuan↗

A new concept for high-cycle-life LEO: Rechargeable MnO2-hydrogen

The nickel-hydrogen secondary battery system, developed in the early 1970s, has become the system of choice for geostationary earth orbit (GEO) applications. However, for low earth orbit (LEO) satellites with long expected lifetimes the nickel positive limits performance. This requires derating of the cell to achieve very long cycle life. A new system, rechargeable MnO2-Hydrogen, which does not require derating, is described here. For LEO applications, it promises to have longer cycle life, high rate capability, a higher effective energy density, and much lower self-discharge behavior than those of the nickel-hydrogen system.

Appleby, A. J.↗

Nanostructured MnO2-Based Cathodes for Li-Ion/Polymer Cells

Nanostructured MnO2-based cathodes for Li-ion/polymer electrochemical cells have been investigated in a continuing effort to develop safe, high-energy-density, reliable, low-toxicity, rechargeable batteries for a variety of applications in NASA programs and in mass-produced commercial electronic equipment. Whereas the energy densities of state-of-the-art lithium-ion/polymer batteries range from 150 to 175 W h/kg, the goal of this effort is to increase the typical energy density to about 250 W h/kg. It is also expected that an incidental benefit of this effort will be increases in power densities because the distances over which Li ions must diffuse through nanostructured cathode materials are smaller than those through solid bulk cathode materials.

Skandan, Ganesh↗

Reliability Issues with Polymer and MnO2 Tantalum Capacitors for Space Applications

This work gives a comparative analysis of degradation processes, failure modes and mechanisms in MnO2 and polymer technology capacitors. Analyzed conditions include effects of vacuum and radiation, soldering (pop-corning), long-term storage and operation at high temperatures, stability at low and high temperatures, and anomalous transients. Screening and qualification procedures to assure space-grade quality of CPTCs are suggested.

tantalum capacitors↗

Reliability Issues with Polymer and MnO2 Tantalum Capacitors for Space Applications

This presentation gives a comparative analysis of degradation processes, failure modes and mechanisms in MnO2 and polymer technology capacitors. Analyzed conditions include effects of vacuum and radiation, soldering (pop-corning), long-term storage, operation at high temperatures, stability at low and high temperatures, and anomalous transients. Screening and qualification procedures to assure space-grade quality of CPTCs are suggested.

capacitor↗

Infant Mortality and Wear-Out Failures in Polymer and MnO2 Tantalum Capacitors

Reliability testing of modern tantalum capacitors shows the presence of both types, infant mortality (IM) and wearout (WO) failures. To assure reliable operation, the probability of IM failures should be reduced to below the specified level, and the time of WO inception should be greater than the required useful life of the parts at operation conditions. In this work, several types of MnO2 and polymer cathode tantalum capacitors have been tested at highly accelerated conditions to assess voltage acceleration factors, determine adequate burn-in conditions, and assess the useful life. A modified time dependent dielectric breakdown (TDDB) model has been suggested to explain both types of failure, and a physical mechanism of degradation that is based on migration and reactions of oxygen vacancies explains increase of the defect related, IM failures with the level of stress.

tantalum capacitors↗

Memory Switches Based On MnO2-x Thin Films

Thin films of Mn02-x at intersections between metallic row and column conductors serve as switching elements for nonvolatile electronic memories. "On"-state resistance adjustable, and on-to-off transition irreversible. Elements electrically programmable and especially suitable for use in associative electronic memories based on neural-network concepts.

Ramesham, Rajeshuni↗

Degradation and ESR Failures in MnO2 Chip Tantalum Capacitors

Equivalent series resistance (ESR) of chip tantalum capacitors determines the rate of energy delivery and power dissipation thus affecting temperature and reliability of the parts. Employment of advanced capacitors with reduced ESR decreases power losses and improves efficiency in power systems. Stability of ESR is essential for correct operations of power units and might cause malfunctioning and failures when ESR becomes too high or too low. Several cases with ESR values in CWR29 capacitors exceeding the specified limit that were observed recently raised concerns regarding environmental factors affecting ESR and the adequacy of the existing screening and qualification testing. In this work, results of stress testing of various types of military and commercial capacitors obtained over years by GSFC test lab and NEPP projects that involved ESR measurements are described. Environmental stress tests include testing in humidity and vacuum chambers, temperature cycling, long-term storage at high temperatures, and various soldering simulation tests. Note that in many cases parts failed due to excessive leakage currents or reduced breakdown voltages. However, only ESR-related degradation and failures are discussed. Mechanisms of moisture effect are discussed and recommendations to improve screening and qualification system are suggested.

Equivalent Series Resistance (ESR)↗