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At least 19 records

High resolution electrolyte for thinning InP by anodic dissolution and its applications to EC-V profiling, defect revealing and surface passivation

An extensive experimental study was conducted using various electrolytes in an effort to find an appropriate electrolyte for anodic dissolution of InP. From the analysis of electrochemical characteristics in the dark and under different illumination levels, x ray photoelectron spectroscopy and SEM/Nomarski inspection of the surfaces, it was determined that the anodic dissolution of InP front surface layers by FAP electrolyte is a very good choice for rendering smooth surfaces, free of oxides and contaminants and with good electrical characteristics. The FAP electrolyte, based on HF, CH3COOH, and H2O2 appears to be inherently superior to previously reported electrolytes for performing accurate EC-V profiling of InP at current densities of up to 0.3 mA/sq cm. It can also be used for accurate electrochemical revealing of either precipitates or dislocation density with application to EPD mapping as a function of depth, and for defect revealing of multilayer InP structures at any depth and/or at the interfaces.

Faur, Maria↗

Electrochemical Deburring

Electrochemical deburring removes burrs from assembled injector tubes. Since process uses liquid anodic dissolution in liquid electrolyte to proide deburring action, smoothes surfaces and edges in otherwise inaccessible areas. Tool consists of sleeve that contains metallic ring cathode. Sleeve is placed over tube, and electrolytic solution is forced to flow between tube and sleeve. The workpiece serves an anode.

Burley, R. K.↗

A study of gas solubilities and transport properties in fuel cell electrolytes

An analysis of the rate of heat generation on the dissolution of sparingly soluble gas in electrolytes was made, and it leads to the conclusion that the temperature changes to be expected are much too small to be measured with precision owing to the slowness of the gas dissolution. It appears that more accurate gas solubility measurements are the only real hope of improved precision in heats of solution and other thermodynamic properties.

Walker, R. D. J.↗

Electrochemical characterization of p(+)n and n(+)p diffused InP structures

The relatively well documented and widely used electrolytes for characterization and processing of Si and GaAs-related materials and structures by electrochemical methods are of little or no use with InP because the electrolytes presently used either dissolve the surface preferentially at the defect areas or form residual oxides and introduce a large density of surface states. Using an electrolyte which was newly developed for anodic dissolution of InP, and was named the 'FAP' electrolyte, accurate characterization of InP related structures including nature and density of surface states, defect density, and net majority carrier concentration, all as functions of depth was performed. A step-by-step optimization of n(+)p and p(+)n InP structures made by thermal diffusion was done using the electrochemical techniques, and resulted in high performance homojunction InP structures.

Wilt, David M.↗

Moisture-Induced Spallation and Interfacial Hydrogen Embrittlement of Alumina Scales

Thermal expansion mismatch stresses and interfacial sulfur activity are the major factors producing primary Al2O3 scale spallation on high temperature alloys. However, moisture-induced delayed spallation appears as a secondary, but often dramatic, illustration of an additional mechanistic detail. A historical review of delayed failure of alumina scales and TBC s on superalloys is presented herein. Similarities with metallic phenomena suggest that hydrogen embrittlement from ambient humidity, resulting from the reaction Al+3H2O=Al(OH)3+3H(+)+3e(-), is the operative mechanism. This proposal was tested by standard cathodic hydrogen charging in 1N H2SO4, applied to Rene N5 pre-oxidized at 1150 C for 1000 1-hr cycles, and monitored by weight change, induced current, and microstructure. Here cathodic polarization at -2.0 V abruptly stripped mature Al2O3 scales at the oxide-metal interface. Anodic polarization at +2.0 V, however, produced alloy dissolution. Finally, with no applied voltage, the electrolyte alone produced neither scale spallation nor alloy dissolution. These experiments thus highlight the detrimental effects of hydrogen charging on alumina scale adhesion. It is proposed that interfacial hydrogen embrittlement is produced by moist air and is the root cause of both moisture-induced, delayed scale spallation and desktop TBC failures.

Smialek, James L.↗

Moisture-Induced Delayed Spallation and Interfacial Hydrogen Embrittlement of Alumina Scales

While interfacial sulfur is the primary chemical factor affecting Al2O3 scale adhesion, moisture-induced delayed spallation appears as a secondary, but impressive, mechanistic detail. Similarities with bulk metallic phenomena suggest that hydrogen embrittlement from ambient humidity, resulting from the reaction Al(sub alloy)+3(H2O)(sub air) = Al(OH)(-) (sub 3) +3H(+) may be the operative mechanism. This proposal was tested on pre-oxidized Rene N5 by standard cathodic hydrogen charging in 1N H2SO4, as monitored by weight change, induced current, and microstructure. Cathodic polarization at -2.0 V abruptly stripped mature Al2O3 scales at the oxide-metal interface. Anodic polarization at +2.0 V, however, produced alloy dissolution. Finally, with no applied voltage, the acid electrolyte produced neither scale spallation nor alloy dissolution. Thus, hydrogen charging was detrimental to alumina scale adhesion. Moisture-induced interfacial hydrogen embrittlement is concluded to be the cause of delayed scale spallation and desktop thermal barrier coating failures.

Smialek, James L.↗

Computationally Guided Development of Components for High Energy Density Solid-State Lithium-Sulfur Batteries

All electric vertical take-off and landing vehicles (eVTOL) for urban air mobility (UAM) concepts face numerous challenging technical barriers before their introduction into the consumer marketplace. The most challenging of these technical barriers to overcome is developing an energy storage system capable of meeting the rigorous aerospace safety and performance criteria1. The performance metrics for eVTOL craft, such as specific energy, specific power, and safety, exceed those of electric automobiles by a factor of two to four. Current state-of-the-art (SOA) lithium-ion batteries are incapable of meeting the key performance criteria of energy and safety for eVTOL. Therefore, next generation advanced chemistries and designs must be developed to meet required performance metrics for electric aviation2. Beyond lithium-ion chemistries, such as lithium-sulfur, show promise in their high energy, while limitations exist in their power and cyclability due to low electrical conductivity and high intermediate solubility in organic liquid electrolytes. Several strategies to overcome the low electrical conductivity involve the use of selenium as a dopant in the active sulfur material, along with the incorporation of 2-dimensional electron-conducting holey-graphene to improve the composite cathodes electronic conductivity. Furthermore, combining this chemistry with a solid-electrolyte avoids the components’ dissolution issues3. However, the development of composite solid-state cathodes is non-trivial as several components must be intimately mixed so that the active component has sufficient access to both electrons and lithium ions to undergo full electrochemical conversion. Mathematical modeling of battery components can assist experimental design through a robust and rigorous combination of computational modeling techniques covering multiple length scales. The objective is to leverage modern computational materials methods combined with battery multiphysics tools to develop radically advanced compatible cathode and electrolyte materials, build and test solid state lithium-sulfur cells and packs. A NASA-based cross-organizational team of high-powered experts combined integrated computational predictive modeling, fundamental chemistry analysis, advanced material science, and battery cell development to tackle this very challenging, multidisciplinary problem. This presentation will show a multiscale computational modeling approach that has produced a novel particle dynamics method called Solid Electrolyte Sphere Approximation Model (SESAM). SESAM modeling targets the 1-10 µm scale structures and provides electromechanical and grain interactions for predictive design guidelines for the manufacturing of solid-state components. Parameters such as particle size and volume fraction of the constituent materials were modeled and experimentally fabricated to optimize electrochemical performance through improved microstructure design. Experimental feedback was provided through ionic and electronic conductivity assessment and structural analysis of developed materials and cell components.

battery↗

Degradation of Aluminum and Tantalum Wet Electrolytic Capacitors during High Temperature Storage

Aluminum electrolytic capacitors (AEC) are available to higher ranges of capacitance and voltage compared to tantalum electrolytic capacitors (TEC). However, evaporation of the electrolyte during operation or storage of conventional AEC that is accelerated with temperature does not allow use of these parts in space electronics. Instead, for systems requiring large value capacitors and high operating voltages, designers must use banks of TECs that increases substantially the size and weight of electronic modules. Development of hermetically sealed AECs might be beneficial for space systems provided the necessary reliability is assured. Increase in leakage current during storage of AEC is well known and is often explained by dissolution of aluminum oxide in electrolyte. However, other possible mechanisms of this effect have not been discussed. Although hermetically sealed TEC have been used in space systems for years, there is a lack of information about the effects of storage on their characteristics that is of great interest as a comparison for aluminum capacitors. This work explores degradation of AC characteristics (capacitance, dissipation factor, and equivalent series resistance) and DC characteristics (leakage and absorption currents) in different types of aluminum and tantalum hermetically sealed capacitors during long-term storage at high temperatures (100 °C, 125 °C, and 150 °C). It is shown that leakage currents are degrading in both types of capacitors, but this degradation is reversible after bias application. Mechanisms of degradation are discussed, and explanations based on the processes common for both types of capacitors are suggested. Problems associated with assessments of hermeticity and evaporation of the electrolyte in hermetically sealed capacitors are analyzed.

Alexander Teverovsky↗

Stabilization of n-type semiconductors to photoanodic dissolution by competitive electron transfer processes

The behavior of n-type CdX (X = S, Se, Te) and GaP, GaAs, and InP in alkaline electrolytes containing X(--) and X sub n(--) ions is reviewed. Of the 18 combinations of electrode and electrolyte, 12 alliances are completely stable to photoanodic dissolution of the n-type photoanode. In each case the oxidation of the chalcogenide species at the photoanode is reversed at the cathode to complete an electrochemical cycle involving no net chemical change. The best system in terms of light-to-electric energy conversion seems to be the CdTe-based cell employing the Te(--)/Te2(--) electrolyte, with roughly 10% efficiency at an output voltage of 0.35 V for monochromatic 633 nm input optical energy at about 25 mW/sq cm.

Wrighton, M. S.↗

Design Considerations for Practical Li-S Batteries for Electric Aviation

The development of high-energy, high-safety, and high-power batteries beyond electric automotive standards is critical for future electric aviation applications. Non-volatile solid-state electrolytes (SSE) offer many promising advantages over traditional flammable liquid electrolytes. Solid-state electrolytes may be an enabling technology for certain battery chemistries by preventing detrimental interactions with liquid electrolytes, for example prevention of the dissolution of intermediates in lithium-sulfur common in traditional liquid organic solvents. However, significant manufacturing challenges must be overcome before the adoption of such technology. This research was conducted to identify processing techniques for producing solid-state battery components with practical dimensions and weights for enabling high specific energy cells. Traditional research has identified a range of very high theoretical ionic conductivities but are impractical due to their instability or inability to be manufactured. Electrolytes explored in this study were produced as sulfide-polymer composites with densified thicknesses below 40 micron using a tape-casting technique and thermoplastic elastomer binder. The combination of high chemical compatibility and flexibility produced robust films that had moderate impact on the ionic conductivity but was capable of dramatically reducing the parasitic mass. Despite minimal conductivity losses, films were produced 10-15 times thinner than comparable bulk powder electrolytes thus leading to overall lower film resistance. Conductivity is maintained above 0.2mS/cm for composite electrolytes. Through the analysis of materials based on their physical properties, such as density, practical cells can be designed. Based on this, low density sulfide-solid-state electrolytes are a promising candidate for achieving the energy and safety metrics for electric aviation, however, further optimization of cathode microstructure and composite processing will be required to achieve the high power metrics and will be the focus of further studies. Additionally, fabrication challenges arise when utilizing metallic lithium foil, due to its soft nature, as overflow and mechanical short circuit can occur on assembly which remains a challenge to overcome before metallic lithium anodes can be fully realized.

batteries↗

Conversion of visible light to electrical energy - Stable cadmium selenide photoelectrodes in aqueous electrolytes

Stabilization of n-type CdSe to photoanodic dissolution is reported. The stabilization is accomplished by the competitive oxidation of S(--) or S(n)(--) at the CdSe photoanode in an electrochemical cell. Such stabilized cells are shown to sustain the conversion of low energy (not less than 1.7 eV) visible light to electricity with good efficiency and no deterioration of the CdSe photoelectrode or of the electrolyte. The electrolyte undergoes no net chemical change because the oxidation occurring at the photoelectrode is reversed at the cathode. Conversion of monochromatic light at 633 nm to electricity is shown to be up to approximately 9% efficient with output potentials of approximately 0.4 V. Conversion of solar energy to electricity is estimated to be approximately 2% efficient.

Wrighton, M. S.↗

Solid-state battery designed for electric aviation

The demand for higher energy density batteries increases as the demand for portable electronic devices and electric automotive increases, as well as a variety of other applications requiring substantially higher power and energy than attainable with current lithium-ion capabilities which includes the areas of high performance vehicles, military applications, and electric aviation. However, the improvement of energy density is insufficient alone for enabling electric aviation when considering the high flammability and risk of thermal runaway inherent in current state-of-the-art liquid electrolytes. The development of high energy, high power, and safe batteries are required to enable hybrid and fully electric aircraft. Next generation chemistries such as lithium-sulfur provide high theoretical specific energy density suitable for electric aviation without as strict of volumetric requirements observed in the automotive industry. However, due to the phase transition during discharge where sulfur generates a series of soluble intermediate polysulfides, which are lost to the liquid electrolyte, cause detrimental side effects, and severely limit cycle life battery performance is severely reduced. Additionally, the low electrical conductivity of sulfur requires a large amount of inactive carbon dramatically increasing parasitic mass. The dissolution issue make sulfur a desirable candidate to pair with a solid-state electrolyte in order to avoid polysulfide dissolution and shuttling. In addition, inorganic solid-electrolytes have low flammability providing the improved safety required. Combining this chemistry with a solid-state electrolyte provides a path for achieving the energy and safety required for electric aviation. The development of scalable thin solid-state electrolytes paired with lithium-sulfur chemistry will be discussed and how their development will aid in enabling a unique application.

Donald A. Dornbusch↗

Preliminary Testing of Electrolytic Silver Ion Generation for Spacecraft Potable Water Systems

Anodic dissolution of silver electrodes, or “silver electrolysis,” is being investigated as a means of imparting biocidal silver into potable water on exploration spacecraft. This method of water disinfection is used commercially in hospitals and marine vessels, but the spacecraft application poses unique challenges such as low water conductivity, increased importance of electrode longevity, and an interface with other systems that may be sensitive to any particles released in the electrolysis process. Testing has shown that due to the low conductivity of the water, the electroactive area of the cell can be scaled linearly to achieve a target electrolysis current despite the general non-linearity of electrochemical systems. More importantly, however, the low conductivity dictates that a large electroactive area and minimal electrode gap be employed in the design. Furthermore, thermodynamic considerations suggest that a low applied voltage is necessary to avoid undesired electrode reactions that could negatively impact long-term performance. Preliminary testing of long-term electrode health suggests that anodic oxide formation may not present as significant a challenge as anticipated; however, further testing in a system closed to the atmosphere is required to rule out the influence of atmospheric CO2 on the pH of the process water. Comparison of filtered and unfiltered silver concentration measurements indicates that release of particles larger than 0.2 μm was negligible in this preliminary test. A test article has been developed to facilitate further testing of silver electrolysis, which continues to be a candidate technology for spacecraft potable water disinfection.

silver↗

A Multi-Physics Study on High-Specific Power Li-O2 Batteries for Electric Aircraft

Commercialization of lithium-air batteries faces many challenges, such as electrolyte decomposition, short cycle life, low energy and power density, etc. However, commercialization of Li-O2 batteries for aeronautics is much more challenging due to additional safety constraints on cyclability and performance (high specific power and specific energy). For this presentation, we will discuss inter-related aspects of physics-based modeling of a pack: cell and battery model calibration. In addition, we will evaluate and present optimal battery designs for high discharge current density, high discharge time, and low battery mass using simulation-based optimization.The Finite Element Model (FEM) used to simulate a Li-O2 cell is based on the work of Bevara [1]. The different aspects of the model are based on: porous electrode theory and concentrated electrolyte theory; quantum tunneling model for the resistance of conformal layer of discharge product (Li2O2) [1]; Butler-Volmer kinetics for electrochemical reaction; Fick's diffusion for oxygen transport; and an oxygen dissolution model is applied at the air/electrolyte interface [2]. The electrolyte properties such as ion conductivity, ion diffusion, oxygen diffusion, and mass density of the electrolyte were taken from Molecular Dynamics (MD) simulations [3]; while the other model parameters, which includes mass of cell components, were calibrated to match experiments at high discharge current densities. The cell mass includes the anode, cathode, separator, electrolyte, and other components (such as current collector). This calibrated model is used to perform parametric studies on cathode thickness, porosity, tortuosity, carbon particle size, electrolyte transport and material properties, partial pressure of oxygen, discharge time, and discharge current density to study optimal designs for high specific power and energy. References:1. Bevara, V. & Andrei, P. (2014), J. Electrochem. Soc. 161 (14), A2068-A2079.2.Mehta, M. & Andrei, P. (2015), J. Power Sources. 286, 299-308.3.Liyana-Arachchi, T.; Haskins, J.; Burke, C.; Diederichsen, K.; McCloskey, B.; & Lawson, J. (2018), J. Phys. Chem. B. 122 (36), 8548 - 8559.4.Choi, W.; Kikumoto, H.; Choudhary, R. & Ooka, R. (2018), Applied Energy, 209, 306-321.

Mehta, Mohit↗

Development of gold alloy catalyst cathode for alkaline electrolyte fuel cells

A program for the development of improved catalyst and Teflon-bonded electrode structures using this improved catalyst is described, for use in fuel cell cathodes. It was found that Au-Pt was superior to the traditional platinum black as a catalyst. The impetus to the program was provided by the discovery that a life-limiting mechanism on the old catalyst was the gradual dissolution of platinum from the cathode and subsequent redeposition in the electrolyte-containing matrix.

Freed, M. S.↗

Self-discharge in bimetallic cells containing alkali metal

Theoretical analysis of thermally regenerative bimetallic cells with alkali metal anodes shows a relation between the current drawn and the rate of discharge under open-circuit conditions. The self-discharge rate of the cell is due to the dissolution and ionization of alkali metal atoms in the fused-salt electrolyte

Foster, M. S.↗