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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
NASA NTRS2007

Oxygen Generation from Carbon Dioxide for Advanced Life Support

The partial electrochemical reduction of CO2 using ceramic oxygen generators (COGs) is well known and has been studied. Conventional COGs use yttria-stabilized zirconia (YSZ) electrolytes and operate at temperatures greater than 700 C (1, 2). Operating at a lower temperature has the advantage of reducing the mass of the ancillary components such as insulation. Moreover, complete reduction of metabolically produced CO2 (into carbon and oxygen) has the potential of reducing oxygen storage weight if the oxygen can be recovered. Recently, the University of Florida developed ceramic oxygen generators employing a bilayer electrolyte of gadolinia-doped ceria and erbia-stabilized bismuth oxide (ESB) for NASA s future exploration of Mars (3). The results showed that oxygen could be reliably produced from CO2 at temperatures as low as 400 C. These results indicate that this technology could be adapted to CO2 removal from a spacesuit and other applications in which CO2 removal is an issue. This strategy for CO2 removal in advanced life support systems employs a catalytic layer combined with a COG so that the CO2 is reduced completely to solid carbon and oxygen. First, to reduce the COG operating temperature, a thin, bilayer electrolyte was employed. Second, to promote full CO2 reduction while avoiding the problem of carbon deposition on the COG cathode, a catalytic carbon deposition layer was designed and the cathode utilized materials shown to be coke resistant. Third, a composite anode was used consisting of bismuth ruthenate (BRO) and ESB that has been shown to have high performance (4). The inset of figure 1 shows the conceptual design of the tubular COG and the rest of the figure shows schematically the test apparatus. Figure 2 shows the microstructure of a COG tube prior to testing. During testing, current is applied across the cell and initially CuO is reduced to copper metal by electrochemical pumping. Then the oxygen source becomes the CO/CO2. This presentation details the results of testing the COG.

Bishop, s. R.↗
NASA NTRS2011

Co-Flow Hollow Cathode Technology

Hall thrusters utilize identical hollow cathode technology as ion thrusters, yet must operate at much higher mass flow rates in order to efficiently couple to the bulk plasma discharge. Higher flow rates are necessary in order to provide enough neutral collisions to transport electrons across magnetic fields so that they can reach the discharge. This higher flow rate, however, has potential life-limiting implications for the operation of the cathode. A solution to the problem involves splitting the mass flow into the hollow cathode into two streams, the internal and external flows. The internal flow is fixed and set such that the neutral pressure in the cathode allows for a high utilization of the emitter surface area. The external flow is variable depending on the flow rate through the anode of the Hall thruster, but also has a minimum in order to suppress high-energy ion generation. In the co-flow hollow cathode, the cathode assembly is mounted on thruster centerline, inside the inner magnetic core of the thruster. An annular gas plenum is placed at the base of the cathode and propellant is fed throughout to produce an azimuthally symmetric flow of gas that evenly expands around the cathode keeper. This configuration maximizes propellant utilization and is not subject to erosion processes. External gas feeds have been considered in the past for ion thruster applications, but usually in the context of eliminating high energy ion production. This approach is adapted specifically for the Hall thruster and exploits the geometry of a Hall thruster to feed and focus the external flow without introducing significant new complexity to the thruster design.

Hofer, Richard R.↗
NASA NTRS1989

New secondary batteries utilizing electronically conductive polymer cathodes

The objectives of this project are to characterize the transport properties in electronically conductive polymers and to assess the utility of these films as cathodes in lithium/polymer secondary batteries. During this research period, progress has been made in a literature survey of the historical background, methods of preparation, the physical and chemical properties, and potential technological applications of polythiophene. Progress has also been made in the characterization of polypyrrole flat films and fibrillar films. Cyclic voltammetry and potential step chronocoulometry were used to gain information on peak currents and potentials switching reaction rates, charge capacity, and charge retention. Battery charge/discharge studies were also performed.

Martin, Charles R.↗
NASA NTRS1983

The molten carbonate carbon dioxide concentrator - Cathode performance at high CO2 utilization

An experimental study of the cathode performance of the molten carbonate carbon dioxide concentrator (MCCDC) at typical gas concentrations is reported, and the behavior is described in terms of standard electrochemical kinetic analysis. Theoretical aspects of the MCCDC are discussed, including the current-generating processes, the overpotential, and the reaction kinetics. A final working equation is derived, and the electrochemical cell is described. The parameters determined by the experiments include cathode overpotentials and removal and current efficiency as a function of current density, as well as carbon dioxide removal rate as a function of flow rate. The results are compared with data for other cells; the agreement with data for the molten carbonate fuel cell suggests that the major difference between the two cells is in the wetting characteristics. The MCCDC achieves high removal efficiencies at high current efficiencies. The lowest current efficiency recorded was 80 percent, and at most current densities, current efficiencies were above 100 percent.

Weaver, J. L.↗
NASA NTRS1987

New secondary batteries utilizing electronically conductive polymer cathodes

The objectives are to optimize the transport rates in electronically conductive polypyrrole films by controlling the morphology of the film and to assess the utility of these films as cathodes in a lithium/polypyrrole secondary battery. During this research period, a better understanding was gained of the fundamental electrochemical switching processes within the polypyrrole film. Three publications were submitted based on the work completed.

Martin, Charles R.↗
NASA NTRS1989

New secondary batteries utilizing electronically conductive polymer cathodes

The objectives of this project are to optimize the transport rates in electronically conductive polypyrrole films by controlling the morphology of the film and to assess the utility of these films as cathodes in a lithium/polypyrrole secondary battery. During this research period, progress has been made in improving the charge transport rate of the supermolecular-engineered polypyrrole electrode by eliminating the polypyrrole baselayer that hampered earlier work. Also, the fibril density of the polypyrrole electrode was increased, providing more electroactive sites per unit area.

Martin, Charles R.↗
NASA NTRS1995

Improved Fabrication Of Cathodes For Solid-State Li Cells

Utilization of cathode material increased. Improved composite-cathode/polymer-electrolyte units for solid-state lithium secondary electrochemical cells fabricated in modified version of original method of fabrication. Further development of units may lead to increases in energy and power densities and in cycle lives of rechargeable lithium cells.

Nagasubramanian, Ganesan↗
DOE OSTI2023

Bifunctional porous non-noble metal phosphide catalyst for overall water splitting and methods of making and using same

A method of electrocatalytic water splitting by providing an anode and a cathode; and utilizing the anode and the cathode for alkaline water electrolysis. Each of the anode and the cathode comprises a uniform distribution of a bifunctional electrocatalyst comprising metallic phosphides on a conductive substrate. The metallic phosphides comprise arion phosphide (FeP) and dinickel phosphide (Ni 2 P). The bifunctional electrocatalyst promotes hydrogen evolution reaction (HER) at the cathode, and oxygen evolution reaction (OER) at the anode.

Ren, Zhifeng↗
DOE OSTI2024

Seawater alkalization via an energy-efficient electrochemical process for CO 2 capture

Electrochemical pH-swing strategies offer a promising avenue for cost-effective and energy-efficient carbon dioxide (CO 2 ) capture, surpassing the traditional thermally activated processes and humidity-sensitive techniques. The concept of elevating seawater’s alkalinity for scalable CO 2 capture without introducing additional chemical as reactant is particularly intriguing due to its minimal environmental impact. However, current commercial plants like chlor-alkali process or water electrolysis demand high thermodynamic voltages of 2.2 V and 1.23 V, respectively, for the production of sodium hydroxide (NaOH) from seawater. These high voltages are attributed to the asymmetric electrochemical reactions, where two completely different reactions take place at the anode and cathode. Here, we developed a symmetric electrochemical system for seawater alkalization based on a highly reversible and identical reaction taking place at the anode and cathode. We utilize hydrogen evolution reaction at the cathode, where the generated hydrogen is looped to the anode for hydrogen oxidation reaction. Theoretical calculations indicate an impressively low energy requirement ranging from 0.07 to 0.53 kWh/kg NaOH for established pH differences of 1.7 to 13.4. Experimentally, we achieved the alkalization with an energy consumption of 0.63 kWh/kg NaOH, which is only 38% of the theoretical energy requirements of the chlor-alkali process (1.64 kWh/kg NaOH). Further tests demonstrated the system’s potential of enduring high current densities (~20 mA/cm 2 ) and operating stability over an extended period (>110 h), showing its potential for future applications. Notably, the CO 2 adsorption tests performed with alkalized seawater exhibited remarkably improved CO 2 capture dictated by the production of hydroxide compared to the pristine seawater.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Recent developments in catalyst-related PEM fuel cell durability

Cost and durability remain the two major barriers to the widespread commercialization of polymer electrolyte membrane fuel cell (PEMFC)-based power systems, especially for the most impactful but challenging fuel cell electric vehicle (FCEV) application. Commercial FCEVs are now on the road; however, their PEMFC systems do not meet the cost targets established by the U.S. Department of Energy, primarily due to the high platinum loading needed on the cathode to achieve the requisite performance and lifetime. Furthermore, while the activities of a number of commercial Pt-based alloy cathode catalysts exceed the beginning-of-life (BOL) targets, these activities, and the overall cathode performance, degrade via a variety of mechanisms described herein. Degradation is mitigated in current FCEVs by utilizing a cathode catalyst with a lower BOL activity (e.g., much lower transition metal alloy content and larger BOL nanoparticle size), necessitating higher catalyst loadings, and through the utilization of system controls that avoid conditions known to exacerbate degradation processes, such as limiting the fuel cell stack voltage range. The design and development of active and robust materials and eliminating the need for vehicle mitigation strategies would greatly simplify the operating system, allowing for greater transient operation, avoiding large hybridization, and curtailing of fuel cell power. Although system mitigation strategies have provided the near-term pathway for FCEV commercialization, material-specific solutions are required to further reduce costs and improve operability and efficiency. Future material developments should focus on stabilization of the electrode structure and minimization of the catalyst particle susceptibility to dissolution caused by oxide formation and reduction over PEMFC cathode-relevant operating potentials plus minimization of support corrosion. Ex situ accelerated stress tests have provided insight into the processes responsible for material and performance degradation and will continue to provide useful information on the relative stability of materials and benchmarks for robust and stable materials-based solutions not requiring system mitigation strategies to achieve adequate lifetime.

25 ENERGY STORAGE↗
NASA NTRS1991

New Secondary Batteries Utilizing Electronically Conductive Polypyrrole Cathode

To gain a better understanding of the dynamic behavior in electronically conducting polypyrroles and to provide guidance toward designs of new secondary batteries based on these polymers, two mathematical models are developed; one for the potentiostatically controlled switching behavior of polypyrrole film, and one for the galvanostatically controlled charge/discharge behavior of lithium/polypyrrole secondary battery cell. The first model is used to predict the profiles of electrolyte concentrations, charge states, and electrochemical potentials within the thin polypyrrole film during switching process as functions of applied potential and position. Thus, the detailed mechanisms of charge transport and electrochemical reaction can be understood. Sensitivity analysis is performed for independent parameters, describing the physical and electrochemical characteristic of polypyrrole film, to verify their influences on the model performance. The values of independent parameters are estimated by comparing model predictions with experimental data obtained from identical conditions. The second model is used to predict the profiles of electrolyte concentrations, charge state, and electrochemical potentials within the battery system during charge and discharge processes as functions of time and position. Energy and power densities are estimated from model predictions and compared with existing battery systems. The independent design criteria on the charge and discharge performance of the cell are provided by studying the effects of design parameters.

Yeu, Taewhan↗
NASA NTRS1988

Emission current control system for multiple hollow cathode devices

An emission current control system for balancing the individual emission currents from an array of hollow cathodes has current sensors for determining the current drawn by each cathode from a power supply. Each current sensor has an output signal which has a magnitude proportional to the current. The current sensor output signals are averaged, the average value so obtained being applied to a respective controller for controlling the flow of an ion source material through each cathode. Also applied to each controller are the respective sensor output signals for each cathode and a common reference signal. The flow of source material through each hollow cathode is thereby made proportional to the current drawn by that cathode, the average current drawn by all of the cathodes, and the reference signal. Thus, the emission current of each cathode is controlled such that each is made substantially equal to the emission current of each of the other cathodes. When utilized as a component of a multiple hollow cathode ion propulsion motor, the emission current control system of the invention provides for balancing the thrust of the motor about the thrust axis and also for preventing premature failure of a hollow cathode source due to operation above a maximum rated emission current.

Beattie, John R.↗
DOE OSTI2023

Improving the Long-term Cycle Performance of xLi 2 MnO 3 ·(1-x)LiMeO 2 /Li 4 Ti 5 O 12 Cells via Prelithiation and Electrolyte Engineering

Toward the development of high energy density and long lifetime batteries for behind-the-meter storage (BTMS) applications, Li- and Mn-rich layered oxide cathode (xLi 2 MnO 3 ·(1-x)LiMeO 2 , Me = Ni, Mn, and etc., LMR-NM) and Li 4 Ti 5 O 12 (LTO) anode system was examined. To mitigate the major degradation mechanisms at each electrode (i.e., loss of Li inventory (LLI) at the anode and transition metal dissolution and oxygen release at the cathode), two approaches were taken—prelithiating the LTO electrode and varying the electrolyte solvent compositions. The effect of prelithiation and electrolyte engineering on the long-term cycle performance of LMR-NM/LTO cells were systematically evaluated via electrochemical analyses and post-mortem characterizations. By using a prelithiated LTO anode and supplying additional Li to the system, the capacity retention of LMR-NM/LTO system was improved. The degree of enhancement was dependent on the types of electrolytes used, as their decomposition products determined the level of LLI. With increased capacity retention, however, the cathode was utilized to a greater extent, resulting in more severe loss of the cathode active material. Thus, all degradation mechanisms should be considered comprehensively when designing high performance LMR-NM/LTO cells to account for their complex interplay.

25 ENERGY STORAGE↗
DOE OSTI2021

Electronic properties of Ir 3 Li and ultra-nanocrystalline lithium superoxide formation

Current lithium-oxygen (Li-O 2 ) batteries suffer from large charge overpotentials related to electronic resistivity of the insulating lithium peroxide (Li 2 O 2 ) discharge product. One potential solution to this challenge is the stabilization of the lithium superoxide (LiO 2 ) discharge intermediate, which has much higher electronic conductivity compared to Li 2 O 2 . Cathodes based on small iridium (Ir) nanoparticles have been recently used in a LiO 2 battery to successfully stabilize the LiO 2 product, however, the LiO 2 had a short lifetime. In the previous study, researchers found that the LiO 2 was stabilized on Ir 3 Li surfaces which were formed from Ir nanoparticles during battery operation. Little is known about the electronic properties of Ir 3 Li and its role in stabilizing LiO 2 product formation. This work provides the first study of the electronic properties of Ir 3 Li, which was thermally synthesized in bulk prior to implementation on the reduced graphene oxide (rGO) cathode of a Li-O 2 cell. Here, the bulk Ir 3 Li was found to have comparable electrical conductivity to Ir metal, possess metal-like magnetic properties, and has an affinity towards O 2 adsorption. The LiO 2 discharge product formed from the Li-O 2 battery discharge was characterized using Raman spectroscopy, titration, along with a comprehensive transmission electron microscopy (TEM) study. This analysis revealed the formation of ultra-nanocrystalline LiO 2 particles greater than 200 nm. This result was attributed to the use of large micron sized Ir 3 Li particles, which could stabilize larger LiO 2 particles compared to previous cathodes that utilized Ir nanoparticles that partially converted to Ir 3 Li during cycling. These results demonstrate that cathode properties can be modified to stabilize the bulk LiO 2 discharge product, which can be useful for the further development of LiO 2 -based Li-O 2 batteries.

25 ENERGY STORAGE↗
NASA NTRS1997

RHETT/EPDM Flight Hollow Cathode

Under the sponsorship of the BMDO Russian Hall Electric Thruster Technology program two xenon hollow cathodes, a flight unit and a flight spare were fabricated, acceptance tested and delivered to the Naval Research Laboratory for use on the Electric Propulsion Demonstration Module. These hollow cathodes, based on the International Space Station plasma contactor design, were fabricated at the NASA Lewis Research Center for use with a D-55 anode layer thruster in the first on-orbit operational application of this technology. The 2.2 Ampere nominal emission current of this device was obtained with a xenon flow rate of 0.6 mg/s. Ignition of the cathode discharge was accomplished through preheating the active electron emitter with a resistive heating element before application of a 650 volt ignition pulse between the emitter and an external starting electrode. The successful acceptance testing of the Electric Propulsion Demonstration Module utilizing these cathodes demonstrated the suitability of cathodes based on barium impregnated inserts in an enclosed keeper configuration for use with Hall thruster propulsion systems.

Manzella, David↗
DOE OSTI2024

Identifying point defects and ordering in the high-entropy layered oxide Li 1.5 MO 3-δ (M=Mn, Al, Fe, Co, Ni) for energy storage applications

High-entropy layered oxides (HELOs) represent a very promising class of next-generation battery cathodes, combining the well-studied properties of layered cathode materials such as LiCoO 2 with the chemical tunability and stability of high-entropy materials. HELO materials often form particles with complex defects and domain structures, complicating accurate characterization of structure and cation mixing. Understanding disorder and order in HELO materials is necessary for understanding their performance and utility as cathodes. Here we demonstrate the characterization of the HELO Li 1.5 MO 3-δ (M = Mn, Al, Fe, Co, Ni), wherein X-ray powder diffraction, transmission electron microscopy imaging, and electron diffraction patterns are analyzed to reveal the presence of ordering in the HELO, with imaging and diffraction simulation employed to compare experimental results to atomic modeling. Finally, without rigorous characterization at the atomic scale, important features such as defect ordering can be easily overlooked and therefore remain unconsidered when interpreting experimental results.

36 MATERIALS SCIENCE↗