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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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At least 559 records · Page 31

Design Principles to Govern Electrode Fabrication for the Lithium Trivanadate Cathode

A full depth of discharge mathematical model for the lithium trivanadate cathode, considering lithiation of the layered α-phase, phase change, and lithiation of the rock-salt like β-phase at lower potentials, is developed. The coupled electrode-scale and crystal-scale model is fit to electrochemical data, and additionally validated with operando EDXRD. There is good agreement between the simulated and measured spatial variation of the volume fraction of the β-phase. This mathematical model is used to guide electrode fabrication, accounting for both ionic and electronic transport effects. Values of three design parameters—electrode thickness, porosity, and volume fraction of conductor—are identified, and the sensitivity of the energy density to these design parameters is quantified. The model is also used to investigate electrode design to create electrodes that deliver the maximum achievable energy density under the constraint that the α to β-phase transition is avoided, since phase change has been demonstrated to reduce cycle life. The energy density sacrificed to avoid phase change decreases at higher discharge rates, but the target values for electrode fabrication remain the same as those when optimizing the electrode for the full depth of discharge.

25 ENERGY STORAGE↗

Thermodynamic Origin of Reaction Non-Uniformity in Battery Porous Electrodes and Its Mitigation

The development of non-uniform reaction current distribution within porous electrodes is a ubiquitous phenomenon during battery charging/discharging and frequently controls the rate performance of battery cells. Reaction inhomogeneity in porous electrodes is usually attributed to the kinetic limitation of mass transport within the electrolyte and/or solid electrode phase. In this work, however, we reveal that it is also strongly influenced by the intrinsic thermodynamic behavior of electrode materials, specifically the dependence of the equilibrium potential on the state of charge: the electrode reaction becomes increasingly non-uniform when the slope of the equilibrium potential curve is reduced. We employ numerical simulations and equivalent circuit model to elucidate such a correlation and show that the degree of reaction inhomogeneity and the resultant discharge capacity can be predicted by a dimensionless reaction uniformity number. For electrode materials that have equilibrium potentials insensitive to the state of charge and exhibit significant reaction non-uniformity, we demonstrate several approaches to spatially homogenizing the reaction current inside porous electrodes, including matching the electronic and ionic resistances, introducing graded electronic conductivity and reducing the surface reaction kinetics.

25 ENERGY STORAGE↗

Surfactant Effects in Porous Electrodes for Microemulsion Redox Flow Batteries

The effect of surfactant additives on electrochemical behavior in porous electrodes was investigated using vanadium redox flow battery half-cells and the dependence of volumetric kinetics and mass transport on electrolyte, surfactant, and electrode type was explored. Without surfactant added, carbon paper electrodes demonstrated greater kinetics and transport compared to carbon felt, for a given electrolyte. Additionally, posolyte kinetics are greater than negolyte kinetics by one to three orders of magnitude, depending on the electrode type. Addition of surfactant increased electrode wettability and possibly electrochemical surface area. However, this was accompanied by a decrease in volumetric mass transport, due to stronger electrolyte-electrode interactions. The presence of sodium dodecyl sulfate (SDS) influenced posolyte and negolyte kinetics differently. Kinetics showed a dependence on electrode type and surfactant. On carbon felt, volumetric kinetics decreased for both posolyte and negolyte with SDS addition. On carbon paper, SDS decreased volumetric kinetics for the posolyte but increased (>2X) kinetics for the negolyte! This kinetic enhancement depends on surfactant chemistry: cetyltrimethylammonium bromide, a cationic surfactant, failed to increase kinetics. Furthermore, SDS did not increase areal specific resistance. Furthermore, these findings show the superior performance of carbon paper compared to carbon felt and suggest SDS as a possible VRFB negolyte additive.

25 ENERGY STORAGE↗

Binder-Coated Carbon Cloth Electrodes for All-Vanadium Redox Flow Batteries

Vanadium redox flow batteries (VRFBs) are a promising solution for integrating intermittent renewable energy sources into the existing power grid. However, enhancing the electrochemical performance of VRFBs is critical for their widespread adoption in grid-scale energy storage. This study investigates the impact of adding a porous binder to a carbon-cloth electrode, with a focus on optimizing thermal activation conditions. The electrochemical performance of the binder-coated electrodes compared to uncoated electrodes is evaluated through electrochemical impedance spectroscopy, polarization curve measurements, and charge-discharge cycling. The surface morphology and structural integrity of the binder-coated electrodes at each activation stage are examined using various material characterization techniques to assess the effects of thermal activation. The results are benchmarked against the experiments using non-coated electrodes to determine the performance improvements offered by the binder coating. Notably, the study reveals that binder-coated electrodes exhibit significantly lower resistance and improved efficiency compared to their uncoated counterparts, with optimal activation conditions enhancing performance metrics crucial for VRFB applications. These findings provide valuable insights for further optimizing electrode design and activation strategies, advancing the development of more efficient VRFB systems for large-scale energy storage.

Caiado, Ashley A.↗

The Nature of Electrochemical Delithiation of Li-Mg Alloy Electrodes: Neutron Computed Tomography and Modeling of Li Diffusion and Delithiation Phenomenon

Li-Mg alloys are promising as positive electrodes (anodes) for Li-ion batteries due to the high Li storage capacity and the relatively lower volume change during the lithiation/delithiation process. They also present a unique opportunity to image the Li distribution through the electrode thickness at various delithiation states. In this work, spatial distributions of Li in electrochemically delithiated Li-Mg alloy electrodes have been quantitatively determined using neutron tomography. Specifically, the Li concentration profiles along thickness direction are determined. A rigorous analytical model to quantify the diffusion-controlled delithiation, accompanied by phase transition and boundary movement, has also been developed to explain the delithiation mechanism. The analytical modeling scheme successfully predicted the Li concentration profiles which agreed well with the experimental data. It is demonstrated that during discharge Li is removed by diffusion through the solid solution Li-Mg phases and this proceeds with β→α phase transition and the associated phase boundary movement through the thickness of the electrode. This is also accompanied by electrode thinning due to the change in molar volume during delithiation. In conclusion, following the approaches developed here, one can develop a rigorous and quantitative understanding of electrochemical delithiation in electrodes of electrochemical cells, similar to that in the present Li-Mg electrodes.

25 ENERGY STORAGE↗

Surface-Directed Fabrication of Integrated Membrane-Electrode Interfaces

In the past five years, we have established a research program to investigate the integration of electrode/catalyst support, gas diffusion pathways, and ionomer into a single network based on a bottom-up, surface-directed approach. Here, the porous electrode surface provides the common foundation for both catalyst deposition and ionomer growth to develop a highly controlled process. Our efforts have focused on (1) the preparation of surface-initiated ionomer that can be grown from electrodes of essentially any geometry and is chemisorbed to the active electrode surface, and (2) the integration of this ionomer with both planar and 3-D electrodes that are atomically modified by Pt catalysts. Figure 1 shows a schematic of a single pore of such an integrated cathode where a catalytic Pt atomic layer is supported along the pores of a nanoporous gold electrode. The catalyst layer is electronically accessible from the metal cathode and in contact with proton-conducting ionomer to yield extremely high utilization efficiencies of the catalyst (approaching 100%) with the ultralow loadings expected from atomic overlayers. We have introduced a new class of ionomer film that is grown from the catalyst/electrode interface to develop proton conducting pathways throughout the 3-D electrode and to the adsorbed catalyst particles. This ionomer is a comb polymer designed to contain sulfonate-lined channels for rapid proton conduction as well as hydrophobic domains (fluorocarbon or hydrocarbon) to promote O 2 solubility and transfer. This interfacial ionomer is designed to interface with a bulk membrane (such as Nafion) and an anode that could be engineered in a similar way. A key conclusion thus far is that ionomer and Pt catalyst can be integrated at a single interface (both 2-D and 3-D) to provide a high level of control over the construction of electrodes. To expand our efforts to date, we seek to utilize the materials chemistry we have developed to investigate how the depth-dependent structure of an ionomer film affects its performance in transferring protons and oxygen to accelerate the rate of the oxygen reduction reaction. By correlating structure and composition to performance and identifying barriers that limit efficiency, we seek to design ultra high performance ionomer films that are customized for the oxygen reduction reaction.

08 HYDROGEN↗

Final Scientific/Technical Report: Low Cost, Structurally Advanced Novel Electrode and Cell Manufacturing

This document is the final technical report from 24M Technologies on the project titled: Low Cost, Structurally Advanced Novel Electrode and Cell Manufacturing. All of the program milestones and deliverables were completed during the performance of the award. Specific accomplishments are 1) 24M demonstrated the processability and electrochemical performance of semi-solid electrodes with active volume contents increased by 10% relative to the program baseline; 2) electrode-level metrics, quality, and yield were demonstrated at an 80 cm 2 electrode footprint; 3) these electrodes were integrated into cells with consistent capacities and impedances, including cells delivered to Argonne National Laboratory for independent testing; 4) those processes were scaled to a large-format (> 260 cm 2 ) electrode footprint and quality and yield were demonstrated; 5) a high-volume manufacturing approach for large-format electrode fabrication was demonstrated; and 6) large-format cells (> 100 Ah capacity) were prototyped with consistent capacity and impedance, including cells which were delivered to Argonne National Laboratory for independent testing.

30 DIRECT ENERGY CONVERSION↗

Elucidating the Link Between Alkali Metal Ions and Reaction-Transport Mechanisms in Cathode Electrodes for Alkali-ion Batteries

Our long-term goal is to improve the reliability of electrode materials and their ability to transport and store various metal ions for electrochemical energy storage applications. The main objective of this work was to investigate the intrinsic relationship between the role of alkali metal ions and electrochemically driven mechanical stability and kinetic properties of battery materials. The overall question was “What is the role of alkali metal ions on the electrochemical and mechanical behavior of cathode electrodes? Our guiding hypothesis was that intercalation of larger alkali metal ions (Na and K) inevitably alters the coupled transport-reaction processes during battery operation in organic electrolytes, leading to more intensive chemo-mechanical instabilities in cathode electrodes, resulting in rapid capacity fade. To validate the hypothesis, we experimentally characterized the reaction-transport processes and governing forces driving the instability of electrode materials in different alkali metal-ion environments. The project had three main tasks. The first one was to investigate intercalation-induced strains and associated stress generation, and their impact on structural deformations in composite cathode electrodes. The second task focused on identifying potential-dependent dynamic changes in the electrode-electrolyte interface in alkali metal ion batteries. The last task was focused on determining how larger alkali metal ions with slower diffusivity affect the transport-mechanics coupling at faster scan rates, compared to smaller ions with faster diffusivity in electrodes. We shortly provided the outcome of each task in the accomplishment section. This project produced 10 peer-reviewed publications (9 research papers and one review manuscript) and supported two Ph.D. students, who graduated from Oklahoma State University.

25 ENERGY STORAGE↗

Long-Term Performance of Reference Electrodes in Alkaline Radioactive Waste Storage Environments

Accurate measurements of corrosion potential are important for assessing the likelihood of internal localized corrosion and stress corrosion cracking of carbon steel tanks used for storing radioactive wastes. Reference electrodes in underground radioactive waste storage tanks are challenging to deploy, and more difficult to extract and replace frequently due to radiological exposure and disposal constraints. Hence, electrodes that exhibit stable performance over long periods of immersion in these waste environments are desirable. The present study evaluates the stability of reference electrodes used in radioactive waste storage tanks over a much longer period than previously studied. Long-term tests on Ag/AgCl and Hg/HgO reference electrodes were performed in nonradioactive simulants formulated from wastes stored at the Hanford site. Electrode degradation, which was studied by various in situ and ex situ evaluation techniques, was correlated to changes in electrode fill chemistry from waste intrusion via the porous frit junction. An intentional contamination study was performed to better understand and predict contamination effects on electrode potential drift.

Materials Science↗

Readout electrode assembly for measuring biological impedance

The invention comprises of a pair of readout ring electrodes which are used in conjunction with apparatus for measuring the electrical impedance between different points in the body of a living animal to determine the amount of blood flow therebetween. The readout electrodes have independently adjustable diameters to permit attachment around different parts of the body between which it is desired to measure electric impedance. The axial spacing between the electrodes is adjusted by a pair of rods which have a first pair of ends fixedly attached to one electrode and a second pair of ends slidably attached to the other electrode. Indicia are provided on the outer surface of the ring electrodes and on the surface of the rods to permit measurement of the circumference and spacing between the ring electrodes.

Montgomery, L. D.↗

Snap-in compressible biomedical electrode

A replaceable, prefilled electrode enclosed in a plastic seal and suitably adapted for attachment to a reusable, washable cap having snaps thereon is disclosed. The apparatus is particularly adapted for quick positioning of electrodes to obtain an EEG. The individual electrodes are formed of a sponge body which is filled with a conductive electrolyte gel during manufacture. The sponge body is adjacent to a base formed of a conductive plastic material. The base has at its center a male gripper snap. The cap locates the female snap to enable the electrode to be positioned. The electrode can be stored and used quickly by attaching to the female gripper snap. The snap is correctly positioned and located by mounting it in a stretchable cap. The cap is reusable with new electrodes for each use. The electrolyte gel serves as the contact electrode to achieve a good ohmic contact with the scalp.

Frost, J. D., Jr.↗

Preparation and characterization of electrodes for the NASA Redox storage system

Electrodes for the Redox energy storage system based on iron and chromium chloride reactants is discussed. The physical properties of several lots of felt were determined. Procedures were developed for evaluating electrode performance in lab scale cells. Experimental procedures for evaluating electrodes by cyclic voltammetry are described which minimize the IR losses due to the high internal resistance in the felt (distributed resistance). Methods to prepare electrodes which reduced the coevolution of hydrogen at the chromium electrode and eleminate the drop in voltage on discharge occasionally seen with previous electrodes were discussed. Single cells of 0.3329 ft area with improved membranes and electrodes are operating at over 80% voltage efficiency and coulombic efficiencies of over 98% at current densities of 16 to 20 amp % ft.

Reid, M. A.↗

Positive Electrode Fabrication for Bi-polar Ni-h2 Cells

Bi-Polar nickel hydrogen design studies indicated a potential improvement in energy density and specific energy if positive electrodes could be manufactured in configurations of twice or more of the present normal thickness. Such electrodes would have to achieve similar active material loading, utilization, and cycle life to conventional 0.8mm I.P.U. nickel hydrogen electrodes. A capability for producing 1.0mm dry sinter and 1.5mm slurry sinter structures on production processes and equipment was demonstrated. The EPI/USAF electrochemical impregnation process proved capable of loading thick electrodes to 1.60 g/cubic centimeters void or higher. Sample electrodes incurred 2000 high rate stress cycles without significant structural or performance degradation. Formation regimes developed for thin plaque are not optimal for thick plaque and further investigation into electrode capacity build-up would seem warranted. Thick electrode technology development is continuing under other programs and shows promise of fulfilling the projected energy density and specific energy improvements.

Edgar, T. A.↗

Nickel hydrogen bipolar battery electrode design

The preferred approach of the NASA development effort in nickel hydrogen battery design utilizes a bipolar plate stacking arrangement to obtain the required voltage-capacity configuration. In a bipolar stack, component designs must take into account not only the typical design considerations such as voltage, capacity and gas management, but also conductivity to the bipolar (i.e., intercell) plate. The nickel and hydrogen electrode development specifically relevant to bipolar cell operation is discussed. Nickel oxide electrodes, having variable type grids and in thicknesses up to .085 inch are being fabricated and characterized to provide a data base. A selection will be made based upon a system level tradeoff. Negative (hydrpogen) electrodes are being screened to select a high performance electrode which can function as a bipolar electrode. Present nickel hydrogen negative electrodes are not capable of conducting current through their cross-section. An electrode was tested which exhibits low charge and discharge polarization voltages and at the same time is conductive. Test data is presented.

Puglisi, V. J.↗

Performance of textured carbon on copper electrode multistage depressed collectors with medium-power traveling wave tubes

Performance of multistage depressed collectors (MDCs) using textured carbon on copper substrate electrode surfaces was evaluated in conjunction with medium-power traveling wave tubes (TWTs). The MDC and TWT overall efficiencies for these electrodes were measured and compared with those obtained with the same TWT and a copper electrode MDC of identical design. Long-term stability of the carbon-coated copper electrode surfaces was investigated by periodic evaluation of TWT-MDC performance over an extended period of continuous wave (CW) operation. Application of textured carbon coating on copper MDC electrode surfaces produced a 13% improvement in both MDC and TWT overall efficiencies for the TWT-MDC tests. During 1600 hr of CW operation with a medium power TWT, no significant changes in MDC performance were noted. This indicated good stability of the textured carbon electrode surfaces. This stability was confirmed by scanning electron microscope examinations of the electrode surfaces before assembly of the MDC and after completion of the test program.

Ramins, Peter↗

Characterization and cycle tests of lightweight nickel electrodes

Development of a high specific energy nickel electrode is the main goal of the lightweight nickel electrode program at NASA Lewis Research Center. The approach was to improve the nickel electrode by continuing combined in-house and contract efforts to develop a more efficient and lighter weight electrode for the nickel-hydrogen battery. High energy nickel electrodes suffer from having shorter lives than state-of-the-art electrode. However, these lightweight electrodes appear to be favorable for missions requiring moderate cycle lives and depth-of-discharge.

Britton, Doris L.↗

Progress in the development of lightweight nickel electrode for aerospace applications

The NASA Lewis Research Center is currently developing nickel electrodes for nickel-hydrogen (Ni-H2) cells and batteries. These electrodes are lighter in weight and have higher specific energy than the heavy sintered state of the art nickel electrodes. In the present approach, lightweight materials or plaques are used as conductive supports for the nickel hydroxide active material. These plaques (fiber, felt, and nickel plated plastic) are fabricated into nickel electrodes by electrochemically impregnating them with active material. Initial performance tests include capacity measurements at five discharge levels, C/2, 1.0C, 1.37C, 2.0C, and 2.74C. The electrodes that pass the initial tests are life cycle tested at 40 and 80 percent depths of discharge (DOD). Different formulations of nickel fiber materials obtained from several manufacturers are currently being tested as possible candidates for nickel electrodes. Over 7,000 cycles of life cycle testing have been accumulated at 40 percent DOD, using the lightweight fiber electrode in a boiler plate Ni-H2 cell with stable voltage.

Britton, Doris L.↗

The effect of electrode temperature on the sparking voltage of short spark gaps

This report presents the results of an investigation to determine what effect the temperature of spark plug electrodes might have on the voltage at which a spark occurred. A spark gap was set up so that one electrode could be heated to temperatures up to 700 degrees C., while the other electrode and the air in the gap were maintained at room temperature. The sparking voltages were measured both with direct voltage and with voltage impulse from ignition coil. It was found that the sparking voltage of the gap decreased materially with increase of temperature. This change was more marked when the hot electrode was of negative polarity. The phenomena observed can be explained by the ionic theory of gaseous conduction, and serve to account for certain hitherto unexplained actions in the operation of internal combustion engines. These results indicate that the ignition spark will pass more readily when the spark-plug design is such as to make the electrodes run hot. This possible gain is, however, very closely limited by the danger of producing preignition. These experiments also show that sparking is somewhat easier when the hot electrode (which is almost always the central electrode) is negative than when the polarity is reversed.

Silsbee, F B↗