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NASA NTRS2019

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↗
NASA NTRS1989

Electrochemical studies on niobium triselenide cathode material for lithium rechargeable cells

The electrochemical behavior of NbSe3 in the battery electrolyte 1.5M LiAsF6/2Me-THF is reported. A detailed study has been carried out using various ac and dc electrochemical techniques to establish the mechanism of intercalation of three equivalents of Li with NbSe3 as well as the rate governing processes in the reduction of NbSe3. An equivalent circuit has been formulated to represent the NbSe3-solution interface. The kinetic parameters for the reduction of NbSe3 were evaluated from the ac and dc measurements. The structural change in NbSe3 on lithiation during initial discharge which results in higher cell voltages and different electrochemical response as compared to virgin NbSe3 was identified to be a loss of crystallographic order.

Ratnakumar, B. V.↗
NASA NTRS2010

Fuel-Cell-Powered Vehicle with Hybrid Power Management

Figure 1 depicts a hybrid electric utility vehicle that is powered by hydrogenburning proton-exchange-membrane (PEM) fuel cells operating in conjunction with a metal hydride hydrogen-storage unit. Unlike conventional hybrid electric vehicles, this vehicle utilizes ultracapacitors, rather than batteries, for storing electric energy. This vehicle is a product of continuing efforts to develop the technological discipline known as hybrid power management (HPM), which is oriented toward integration of diverse electric energy-generating, energy-storing, and energy- consuming devices in optimal configurations. Instances of HPM were reported in five prior NASA Tech Briefs articles, though not explicitly labeled as HPM in the first three articles: "Ultracapacitors Store Energy in a Hybrid Electric Vehicle" (LEW-16876), Vol. 24, No. 4 (April 2000), page 63; "Photovoltaic Power Station With Ultracapacitors for Storage" (LEW- 17177), Vol. 27, No. 8 (August 2003), page 38; "Flasher Powered by Photovoltaic Cells and Ultracapacitors" (LEW-17246), Vol. 27, No. 10 (October 2003), page 37; "Hybrid Power Management" (LEW-17520), Vol. 29, No. 12 (December 2005), page 35; and "Ultracapacitor-Powered Cordless Drill" (LEW-18116-1), Vol. 31, No. 8 (August 2007), page 34. To recapitulate from the cited prior articles: The use of ultracapacitors as energy- storage devices lies at the heart of HPM. An ultracapacitor is an electrochemical energy-storage device, but unlike in a conventional rechargeable electrochemical cell or battery, chemical reactions do not take place during operation. Instead, energy is stored electrostatically at an electrode/electrolyte interface. The capacitance per unit volume of an ultracapacitor is much greater than that of a conventional capacitor because its electrodes have much greater surface area per unit volume and the separation between the electrodes is much smaller.

Eichenberg, Dennis J.↗
NASA NTRS2005

Hybrid Power Management

An engineering discipline denoted as hybrid power management (HPM) has emerged from continuing efforts to increase energy efficiency and reliability of hybrid power systems. HPM is oriented toward integration of diverse electric energy-generating, energy-storing, and energy-consuming devices in optimal configurations for both terrestrial and outer-space applications. The basic concepts of HPM are potentially applicable at power levels ranging from nanowatts to megawatts. Potential applications include terrestrial power-generation, terrestrial transportation, biotechnology, and outer-space power systems. Instances of this discipline at prior stages of development were reported (though not explicitly labeled as HPM) in three prior NASA Tech Briefs articles: "Ultracapacitors Store Energy in a Hybrid Electric Vehicle"(LEW-16876), Vol. 24, No. 4 (April 2000), page 63; "Photovoltaic Power Station With Ultracapacitors for Storage" (LEW-17177), Vol. 27, No. 8 (August 2003), page 38; and "Flasher Powered by Photovoltaic Cells and Ultracapacitors" (LEW-17246), Vol. 24, No. 10 (October 2003), page 37. As the titles of the cited articles indicate, the use of ultracapacitors as energy-storage devices lies at the heart of HPM. An ultracapacitor is an electrochemical energy-storage device, but unlike in a conventional rechargeable electrochemical cell or battery, chemical reactions do not take place during operation. Instead, energy is stored electrostatically at an electrode/electrolyte interface. The capacitance per unit volume of an ultracapacitor is much greater than that of a conventional capacitor because its electrodes have much greater surface area per unit volume and the separation between the electrodes is much smaller. Power-control circuits for ultracapacitors can be simpler than those for batteries, for two reasons: (1) Because of the absence of chemical reactions, charge and discharge currents can be greater than those in batteries, limited only by the electrical resistances of conductors; and (2) whereas the charge level of a battery depends on voltage, temperature, age, and load condition, the charge level of an ultracapacitor, like that of a conventional capacitor, depends only on voltage.

Eichenberg, Dennis↗
NASA NTRS1978

Technology advancement of the electrochemical CO2 concentrating process

The overall objectives of the present program are to: (1) improve the performance of the electrochemical CO2 removal technique by increasing CO2 removal efficiencies at pCO2 levels below 400 Pa, increasing cell power output and broadening the tolerance of electrochemical cells for operation over wide ranges of cabin relative humidity; (2) design, fabricate, and assemble development hardware to continue the evolution of the electrochemical concentrating technique from the existing level to an advanced level able to efficiently meet the CO2 removal needs of a spacecraft air revitalization system (ARS); (3) develop and incorporate into the EDC the components and concepts that allow for the efficient integration of the electrochemical technique with other subsystems to form a spacecraft ARS; (4) combine ARS functions to enable the elimination of subsystem components and interfaces; and (5) demonstrate the integration concepts through actual operation of a functionally integrated ARS.

Schubert, F. H.↗
NASA NTRS2007

A Synopsis of Interfacial Phenomena in Lithium-Based Polymer Electrolyte Electrochemical Cells

The interfacial regions between electrode materials, electrolytes and other cell components play key roles in the overall performance of lithium-based batteries. For cell chemistries employing lithium metal, lithium alloy or carbonaceous materials (i.e., lithium-ion cells) as anode materials, a "solid electrolyte interphase" (SEI) layer forms at the anode/electrolyte interface, and the properties of this "passivating" layer significantly affect the practical cell/battery quality and performance. A thin, ionically-conducting SEI on the electrode surface can beneficially reduce or eliminate undesirable side reactions between the electrode and the electrolyte, which can result in a degradation in cell performance. The properties and phenomena attributable to the interfacial regions existing at both anode and cathode surfaces can be characterized to a large extent by electrochemical impedance spectroscopy (EIS) and related techniques. The intention of the review herewith is to support the future development of lithium-based polymer electrolytes by providing a synopsis of interfacial phenomena that is associated with cell chemistries employing either lithium metal or carbonaceous "composite" electrode structures which are interfaced with polymer electrolytes (i.e., "solvent-free" as well as "plasticized" polymer-binary salt complexes and single ion-conducting polyelectrolytes). Potential approaches to overcoming poor cell performance attributable to interfacial effects are discussed.

Baldwin, Richard S.↗
NASA NTRS1978

Automated electrochemical selection of coliforms

Computer-controlled sensor system monitors and quantifies coliform organisms in waste water samples through molecular hydrogen detection techniques. System includes cleanup procedures, external sterilization of each sensor interface with working fluid as well as incubation cell interiors. Sensor system may also be operated manually.

Taylor, R. E.↗
NASA NTRS1976

Integration of the electrochemical depolorized CO2 concentrator with the Bosch CO2 reduction subsystem

Regenerative processes for the revitalization of spacecraft atmospheres require an Oxygen Reclamation System (ORS) for the collection of carbon dioxide and water vapor and the recovery of oxygen from these metabolic products. Three life support subsystems uniquely qualified to form such an ORS are an Electrochemical CO2 Depolarized Concentrator (EDC), a CO2 Reduction Subsystem (BRS) and a Water Electrolysis Subsystem (WES). A program to develop and test the interface hardware and control concepts necessary for integrated operation of a four man capacity EDC with a four man capacity BRS was successfully completed. The control concept implemented proved successful in operating the EDC with the BRS for both constant CO2 loading as well as variable CO2 loading, based on a repetitive mission profile of the Space Station Prototype (SSP).

Schubert, F. H.↗
NASA NTRS2014

Lithium-Ion Electrolytes Containing Flame Retardant Additives for Increased Safety Characteristics

The invention discloses various embodiments of Li-ion electrolytes containing flame retardant additives that have delivered good performance over a wide temperature range, good cycle life characteristics, and improved safety characteristics, namely, reduced flammability. In one embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a fluorinated co-solvent, a flame retardant additive, and a lithium salt. In another embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a flame retardant additive, a solid electrolyte interface (SEI) film forming agent, and a lithium salt.

Smart, Marshall C.↗
NASA NTRS1986

Crystalline-silicon photovoltaics summary module design and reliability

The evolution of the design and reliability of solar modules was described. Design requirements involved 14 different considerations, including residential building and material electrical codes, wind-loading, hail impact, operating temperature levels, module flammability, and interfaces for both the array structure and the operation of the system. Reliability research involved in diverse investigations including glass-fracture strength, soiling levels, electrochemical corrosion, and bypass-diode qualification tests. Based on these internationally recognized studies, performance assessments, and failure analyses, the Flat-plate Solar Array Project in its 11-year duration served to nuture the development of 45 different solar module designs from 15 PV manufacturers.

Ross, R. G., Jr.↗
NASA NTRS1994

Probing the chemistry of nickel/metal hydride battery cells using electrochemical impedance spectroscopy

Electrochemical Impedance Spectroscopy (EIS) is a valuable tool for investigating the chemical and physical processes occurring at electrode surfaces. It offers information about electron transfer at interfaces, kinetics of reactions, and diffusion characteristics of the bulk phase between the electrodes. For battery cells, this technique offers another advantage in that it can be done without taking the battery apart. This non-destructive analysis technique can thus be used to gain a better understanding of the processes occurring within a battery cell. This also raises the possibility of improvements in battery design and identification or prediction of battery characteristics useful in industry and aerospace applications. EIS as a technique is powerful and capable of yielding significant information about the cell, but it also requires that the many parameters under investigation can be resolved. This implies an understanding of the processes occurring in a battery cell. Many battery types were surveyed in this work, but the main emphasis was on nickel/metal hydride batteries.

Isaac, Bryan J.↗
NASA NTRS1976

Electrochemical deposition of silver crystals aboard Skylab 4

Silver crystals were grown aboard Skylab 4 by an electro-chemical reaction and subsequently returned to earth for comparison with crystals grown at 1- and 5-g. Both the Skylab and earth-grown crystals show a variety of structures. Certain tendencies in structure dependency on gravity level, however, can be discerned. In addition, downward growing dendrite streamers; upward growing chunky crystal streamers; growth along an air/liquid interface; and ribbon, film, and fiber crystal habits were observed in experiments conducted on the ground with solutions of varying concentrations. It was also observed that the crystal structures of space and ground electro-deposited silver crystals were very similar to the structures of germanium selenide and germanium telluride crystals grown in space and on the ground by a vapor transport technique. Consideration of the data leads to the conclusions that: (1) the rate of electrochemical displacement of silver ions from a 5 percent aqueous solution by copper is predominantly diffussion controlled in space and kinetically controlled in 1- and higher-g because of augmentation of mass transport by convection; (2) downward and upward crystal streamers are the result of gravity-driven convection, the flow patterns of which can be delineated. Lateral growths along an air/liquid interface are the result of surface-tension-driven convection, the pattern of which also can be delineated; (3) electrolysis in space or low-g environments can produce either dendritic crystals with more perfect microcrystalline structures or massive, single crystals with fewer defects than those grown on ground or at higher g-levels. Ribbons or films of space-grown silicon crystals would find a ready market for electronic substrate and photocell applications. Space-grown dendritic, metal crystals present the possibility of unique catalysts. Large perfect crystals of various materials are desired for a number of electronic and optical applications; and (4) vapor transport growth of germanium selenide and germanium telluride is affected by convection mechanisms similar to the mechanisms hypothesized for the electrochemical deposition of silver crystals. Evidence and considerations leading to the preceding summaries and conclusions are presented. The implications of the findings and conclusions for technological applications are discussed, and recommendations for further experiments are presented.

Grodzka, P. G.↗
NASA NTRS1997

Electrochemical Characterization of Semiconductor Materials and Structures

For a period covering October 1, 1995 through August 12, 1996, the research group at CSU has conducted theoretical and experimental research on "Electrochemical Characterization of Semiconductor Materials and Structures. " The objective of this investigation was to demonstrate the applicability of electrochemical techniques for characterization of complex device structures based on InP and GaAs, Ge, InGaAs, InSb, InAs and InSb, including: (1) accurate EC-V net majority carrier concentration depth profiling, and (2) surface and bulk structural and electrical type defect densities. Our motivation for this R&D effort was as follows: "Advanced space solar cells and ThermoPhotoVoltaic (TPV) cells are fabricated using a large variety of III-V materials based on InP and GaAs for solar cells and low bandgap materials such as Ge, InGaAs, InAs and InSb for TPV applications. At the present time for complex device structures using these materials, however, there is no simple way to assess the quality of these structures prior to device fabrication. Therefore, process optimization is a very time consuming and a costly endeavor". Completion of this R&D effort would have had unquestionable benefits for space solar cell and TPV cells, since electrochemical characterization of the above cell structures, if properly designed can provide many useful structural and electrical material information virtually at any depth inside various layers and at the interfaces. This, could have been applied for step-by-step process optimization, which could have been used for fabrication of new generation high efficiency, low cost space PV and TPV cells.

Source record↗
NASA NTRS1983

Environmental Control and Life Support for an evolutionary Space Station

The requirements for the Space Station are being defined. The Environmental Control/Life Support System (ECLSS) is one of its 13 systems. The ECLSS is further divided into five functional categories. Major ones are the Air Revitalization and Water Reclamation Systems. The paper presents ECLSS performance requirements, average design loads and fluids interfaces. The major cost savings of regenerable ECLSS techniques versus the open loop approach are quantified. Issues impacting ECLSS design are cited. Priority regenerable ECLSS developments are reviewed including the Electrochemical CO2 Concentrator, Static Feed Electrolyzer and Automated Control/Monitor Instrumentation. Baseline and alternative approaches are cited. The ECLSS planning issues are reviewed including functional boundaries, planning schedule, technology maturity definition and technology gaps. The paper concludes with a review of water electrolysis as a Space Station utility impacting ECLSS design.

Quattrone, P. D.↗
NASA NTRS1991

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↗
NASA NTRS1988

The UW digital ozonesonde: Characteristics and flow rate calibration

During the austral springs of 1986 and 1987, a series of balloon soundings were conducted to characterize the temporal and vertical development of Antarctic ozone depletion using the electrochemical concentration cell method (ECC). An important part of this study was to perform correlative studies between ozone and aerosol particles. In order to facilitate these simultaneous measurements, a digital ozonesonde system was developed to interface with aerosol counters. The ozone measurements will be described herein. The ozonesonde modification was accomplished by converting the current output of the sonde to a frequency and adding this digital signal to the serial data stream of a Vaisala Corporation RS-80 radiosonde under microprocessor control. A number of advantages over the standard ozonesonde system currently in use are noted.

Harder, J. W.↗
NASA NTRS1989

Electrochemical cell for obtaining oxygen from carbon dioxide atmospheres

For manned missions to Mars to become a reality, an efficient and reliable means of obtaining oxygen from the carbon dioxide-rich atmosphere will be required. Otherwise, the high cost of transporting the oxygen needed to sustain the astronauts will severely restrict the expedition to the martian surface. Recently, the use of electrochemical devices has been explored as a means of obtaining oxygen from the carbon dioxide-rich atmosphere. In these devices, oxygen ions diffuse through solid oxide membranes, thus, separating oxygen from the other gases presented. This phenomenon has only recently been explored as a means of obtaining large quantities of oxygen from toxic atmospheres, although first observed by Walter nernst in 1899. Nernst observed that stabilized zirconia will conduct oxygen ions when an electrical potential is applied across metallic electrodes applied to the ceramic membrane. Diatomic oxygen molecules are dissociated at the positive electrode/electrolyte interface. The oxygen ions enter the ceramic body due to the ion density gradient which is produced by the electrical potential across the electrolytic membrane. Once the ions have diffused through the membrane, they reform diatomic oxygen molecules at the anode. The separation of oxygen from carbon dioxide is achieved by the combination of thermal and electrochemical processes. The thermal decomposition of carbon dioxide (at 1000 C) results in the production of carbon monoxide and oxygen by the reaction.

Hooker, M. W.↗
NASA NTRS2002

Carbon Materials Embedded with Metal Nanoparticles as Anode in Lithium-Ion Batteries

Carbon materials containing metal nanoparticles that can form an alloy with lithium were tested for their capacity and cycle life to store and release lithium electrochemically. Metal nanoparticles may provide the additional lithium storage capacity as well as additional channels to conduct lithium in carbon. The cycle life of this carbon-metal composite can be long because the solid-electrolyte interface (SEI) on the carbon surface may protect both lithium and the metal particles in the carbon interior. In addition, the voids in the carbon interior may accommodate the nanoparticle's volume change, and such volume change may not cause much internal stress due to small sizes of the nanoparticles. This concept of improving carbon's performance to store and release lithium was demonstrated using experimental cells of C(Pd)/0.5M Lil-50/50 (vol.%) EC and DMC/Li, where C(Pd) was graphitized carbon fibers containing palladium nanoparticles, EC was ethylene carbonate, and DMC was dimethyl carbonate. However, such improvement was not observed if the Pd nanoparticles are replaced by aluminum, possibly because the aluminum nanoparticles were oxidized in air during storage, resulting in an inert oxide of aluminum. Further studies are needed to use this concept for practical applications.

Hung, Ching-cheh↗