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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 901 records · Page 50

Rate-Dependent Aging Resulting from Fast Charging of Li-Ion Cells

The mass electrification of personal and service vehicles is reliant on the ability of battery packs to undergo extreme fast recharging. A central challenge is that the repeated exposure to high currents can trigger and/or accelerate mechanisms of performance degradation, such as lithium deposition, mechanical damage of active material particles, and impedance rise. Here, we investigate whether constraining high-rate charging to limited state-of-charge (SOC) ranges can mitigate these aging processes. Our experiments map the boundaries of lithium plating conditions, and also indicate that permanent losses of electrode capacity appear to be a function of cycle number, but not charging rate. Interestingly, we show that impedance rise appears to depend on charging rate alone, and not on the amount of charge passed at each cycle. This observation suggests that limiting fast charging to a narrow SOC range would only delay cell aging, but not fully prevent it from happening. We identify oxide-particle cracking as the likely mechanism for this impedance rise, suggesting that particle and electrode design are essential to enable fast charging. The findings of this work can inform the development of fast-charging protocols that are less damaging to cell health.

25 ENERGY STORAGE↗

A Review on Solid State Batteries: Life Cycle Perspectives

This report briefly reviews the characteristics of solid-state batteries (SSBs) and the life-cycle analysis (LCA) studies that have been completed for SSBs. Compared with conventional lithium-ion batteries (LIBs), SSBs offer improved safety and potentially higher energy density — both enabled by replacing liquid electrolytes with solid electrolytes and using lithium metal anodes. Several challenges impede the commercialization of SSBs, primarily related to the stability of the interface between the solid electrolyte and the electrodes. Several options are under consideration for SSB electrolyte and cathode chemistries. As a result, the production processes for these components and the corresponding battery packs are still under development and can differ significantly from those used for conventional LIB pack production. A robust comparison of SSBs with LIBs through LCA is important to analyze the environmental benefits and challenges associated with this alternative battery system. While the literature provides only a few LCA studies focused on SSBs, with significant uncertainty in their life-cycle inventories (LCIs), those studies collectively suggest that solid electrolyte manufacturing is the major environmental hotspot, followed by cathode and anode production.

25 ENERGY STORAGE↗

NASA thermionic-conversion program

Technological processes in out-of-core thermionic energy conversion are described. The emphasis was on high temperature electrode materials and system engineering of converter geometries to produce practical power densities.

Morris, J. F.↗

Crystalline Li(sub 3)PO(sub 4)/SiO(sub 4) solid solutions as an electrolyte for film batteries using sputtered cathode layers

Crystalline solid solutions of 1:1 Li3PO4/SiO4 were synthesized and tested electrochemically using thin film, physical vapor deposited electrodes. After cathode deposition, the electrolyte/cathode structures were annealed at 700 degrees Celsius for 2 hours, a process that resulted in cathode crystallization without encouraging deleterious interfacial reactions. Results indicate that the electrolyte functioned well in this configuration.

film battery↗

Phase-change Reconfigurable Optical WavEfront Synthesis System (PROWESS)

We report the design, fabrication, and testing of electrically tunable metasurface k-space filters based on the low-loss, high-contrast phase-change material GSST and a transparent Si electrode heating architecture. A 10x10 array of PCM elements integrated with Si heaters was fabricated via foundry processes, and used to actively control the crystallinity of a metasurface consisting of GSST nano antennae. By selectively varying the structural state of individual PCM elements, specific k-vectors of transmitted light can effectively be filtered out, resulting in improved imaging quality by reducing the scattered light that reaches a detector. Optimized doping profiles in the Si heaters allow for uniform, low power, reliable and repeatable switching of the GSST state. Compared to other k-space filters, this new architecture is completely transparent to the wavelength of interest and can be actively reconfigured in real time with high performance, low power consumption and a small footprint. The 10x10 array device is a proof-of-concept demonstration that can enable high-resolution arbitrary wavefront synthesis and correction in the future, with key applications in optical communications, beam steering, remote sensing, and adaptive optics.

phase change material↗

Corrosion Mitigation and Increased Discharge Capacity in Aqueous Processed Thick Cathodes using Phosphoric Acid Additives

Aqueous processed cathodes for lithium-ion batteries are favorable for both cost and environmental reasons; however, these electrodes still face significant problems with increasing areal capacities (i.e. thickness). Highly basic slurry conditions (pH in excess of 12) corrode the current collector surface and evolve hydrogen gas. Consequently, bubbling at the electrode interface causes substantial damage to the dried electrode. As the loading of these electrodes is increased, damage becomes severe and results in lack of adhesion and cohesion. Here introduction of phosphoric acid to combat the rise in pH and suppress the corrosion at the current collector surface is investigated. Phosphoric acid was added in increments of 0.5, 1.0, and 1.5 wt% and the subsequent effects on slurry rheology, particle size, adhesion, and electrochemical cycling were investigated. A technique is reported for obtaining thick (6-8 mAh/cm2) cathodes that exhibit reduced surface cracking and improved rate performance as compared to control samples.

Kukay, Alexander↗

Oxygen-Vacancy Abundant Nanoporous Ni/NiMnO 3 /MnO 2 @NiMn Electrodes with Ultrahigh Capacitance and Energy Density for Supercapacitors

High-performance energy storage devices (HPEDs) play a critical role in the realization of clean energy and thus enable the overarching pursuit of nonpolluting, green technologies. Supercapacitors are one class of such lucrative HPEDs; however, a serious limiting factor of supercapacitor technology is its sub-par energy density. Here, this report presents hitherto unchartered pathway of physical deformation, chemical dealloying, and microstructure engineering to produce ultrahigh-capacitance, energy-dense NiMn alloy electrodes. The activated electrode delivered an ultrahigh specific-capacitance of 2700 F/cm 3 at 0.5 A/cm 3 . The symmetric device showcased an excellent energy density of 96.94 Wh/L and a remarkable cycle life of 95% retention after 10,000 cycles. Transmission electron microscopy and atom probe tomography studies revealed the evolution of a unique hierarchical microstructure comprising fine Ni/NiMnO 3 nanoligaments within MnO 2 -rich nanoflakes. Theoretical analysis using density functional theory showed semimetallic nature of the nanoscaled oxygen-vacancy-rich NiMnO 3 structure, highlighting enhanced carrier concentration and electronic conductivity of the active region. Furthermore, the geometrical model of NiMnO 3 crystals revealed relatively large voids, likely providing channels for the ion intercalation/de-intercalation. The current processing approach is highly adaptable and can be applied to a wide range of material systems for designing highly efficient electrodes for energy-storage devices.

25 ENERGY STORAGE↗

Effect of structure on current and potential distributions in porous electrode

Porous electrodes generally contain constricted macropores and localized micropores. The effects of the macropore constrictions on the resistance of a capillary were studied and an analytical model was developed for predicting the current distribution in a constricted macropore which directly includes constriction effects and does not require an empirical tortuosity parameter. The current and concentration distributions in localized micropores were also investigated and it was shown that the microporous area is fully accessible to charge and mass transfer processes. From these analyses it was concluded that the micropores primarily affect the kinetics of the interfacial processes by contributing to the interfacial area, while the macropores impose ohmic and mass transport limitations through the volume of the porous electrode.

Lanzi, Oscar↗

Effect of Reverse Bias Stress on Leakage Currents and Breakdown Voltages of Solid Tantalum Capacitors

The majority of solid tantalum capacitors are produced by high-temperature sintering of a fine tantalum powder around a tantalum wire followed by electrolytic anodization that forms a thin amorphous Ta2O5 dielectric layer and pyrolysis of manganese nitrite on the oxide to create a conductive manganese dioxide electrode. A contact to tantalum wire is used as anode terminal and to the manganese layer as a cathode terminal of the device. This process results in formation of an asymmetric Ta -- Ta2O5 -- MnO2 capacitor that has different characteristics at forward (positive bias applied to tantalum) and reverse (positive bias applied to manganese cathode) voltages. Reverse bias currents might be several orders of magnitude larger than forward leakage currents so I-V characteristics of tantalum capacitors resemble characteristics of semiconductor rectifiers. Asymmetric I-V characteristics of Ta -- anodic Ta2O5 systems have been observed at different top electrode materials including metals, electrolytes, conductive polymers, and manganese oxide thus indicating that this phenomenon is likely related to the specifics of the Ta -- Ta2O5 interface. There have been multiple attempts to explain rectifying characteristics of capacitors employing anodic tantalum pentoxide dielectrics. A brief review of works related to reverse bias (RB) behavior of tantalum capacitors shows that the mechanism of conduction in Ta -- Ta2O5 systems is still not clear and more testing and analysis is necessary to understand the processes involved. If tantalum capacitors behave just as rectifiers, then the assessment of the safe reverse bias operating conditions would be a relatively simple task. Unfortunately, these parts can degrade with time under reverse bias significantly, and this further complicates analysis of the I-V characteristics and establishing safe operating areas of the parts. On other hand, time dependence of reverse currents might provide additional information for investigation of the processes under reverse bias conditions. In practice, there were instances when, due to unforeseen events, the system operated at conditions when capacitors experience periodically a relatively small reverse bias for some time followed by normal, forward bias conditions. In such a case an assessment should be made on the degree to which these capacitors are degraded by application of low-voltage reverse bias, and whether this degradation can be reversed by normal operating conditions. In this study, reverse currents in different types of tantalum capacitors were monitored at different reverse voltages below 15%VR and temperatures in the range from room to 145 C for up to 150 hours to get better understanding of the degradation process and determine conditions favorable to the unstable mode of operation. The reversibility of RB degradation has been evaluated after operation of the capacitors at forward bias conditions. The effect of reverse bias stress (RBS) on reliability at normal operating conditions was evaluated using highly accelerated life testing at voltages of 1.5VR and 2 VR and by analysis of changes in distributions of breakdown voltages. Possible mechanisms of RB degradation are discussed.

Teverovsky, Alexander A.↗

Resolving Graphite‐Electrolyte Interphase of Lithium‐Ion Batteries using Air‐Tight Ambient Mass Spectrometry

Abstract The formation of a stable solid electrolyte interphase (SEI) at graphite electrode is necessary for lithium‐ion batteries (LIB) to prevent excessive degradation of electrolytes. Until now, the exact organic composition of SEI has not been decisively determined with lithium ethylene mono‐carbonate (LEMC) being one of the debated components. An air‐tight ambient mass spectrometry (MS) platform is developed to directly characterize the air‐sensitive organic components present in SEI. Ionization occurs via a solvent‐free field‐induced process at atmospheric pressure. Our experimental data, based on tandem MS analysis, revealed LEMC to be the major organic component in SEI. This result resolves a long‐standing mystery surrounding the composition of native SEI in LIB, where no trace of the other debated compound, lithium ethylene dicarbonate, was detected. The energetics of fragmentation of LEMC and the corresponding stabilities of various ionic species detected during the air‐tight ambient MS analysis were calculated using density functional theory (DFT). Our findings confirmed favorable protonation energies and suggested the molecular structures for many of the detected species. Solvent (i. e., ethylene carbonate)‐induced stabilization effects observed during the ionization process were also confirmed by DFT. The reported study encourages the routine use of ambient mass spectrometry to characterize both anodic and cathodic electrodes of all battery types as well as to study other air‐sensitive materials in their native state.

25 ENERGY STORAGE↗

In situ x-ray photoelectron spectroscopy analysis of electrochemical interfaces in battery: Recent advances and remaining challenges

An in-depth understanding of charge transfer processes at the electrochemical interfaces is a critical knowledge gap impeding the design of energy storage materials. X-ray photoelectron spectroscopy plays an important role in analyzing electronic structures of heterogeneous interfaces, such as electrode-electrolyte interphases. Correspondingly, ex situ studies based on postmortem analysis of electrode materials using x-ray techniques are widely reported in the literature but often fail to capture intermediate and transient species, which are critical for a predictive understanding of the charge transfer process. The lack of extensive in situ/operando x-ray analysis of buried interfaces in energy storage systems can be mainly attributed to technical limitations, such as the requirement of high vacuum conditions. However, in the past decade, considerable efforts have been devoted to overcoming these technical barriers and enable investigation of the solid/solid and solid/liquid interfaces. This review catalogs some of the recent progresses and new experimental designs in the application of in situ and operando x-ray photoelectron spectroscopy toward characterizing interfacial processes and emergent properties, which can help build the design strategy for advanced batteries. The remaining challenges and future research directions are also discussed, as potential paths forward in this field.

Wi, Sungun↗

An Integrated, Layered-Spinel Composite Cathode for Energy Storage Applications

At low operating temperatures, commercially available electrode materials for lithium-ion batteries do not fully meet the energy and power requirements for NASA fs exploration activities. The composite cathode under development is projected to provide the required energy and power densities at low temperatures and its usage will considerably reduce the overall volume and weight of the battery pack. The newly developed composite electrode material can provide superior electrochemical performance relative to a commercially available lithium cobalt system. One advantage of using a composite cathode is its higher energy density, which can lead to smaller and lighter battery packs. In the current program, different series of layered-spinel composite materials with at least two different systems in an integrated structure were synthesized, and the volumetric and gravimetric energy densities were evaluated. In an integrated network of a composite electrode, the effect of the combined structures is to enhance the capacity and power capabilities of the material to levels greater than what is possible in current state-of-the-art cathode systems. The main objective of the current program is to implement a novel cathode material that meets NASA fs low temperature energy density requirements. An important feature of the composite cathode is that it has at least two components (e.g., layered and spinel) that are structurally integrated. The layered material by itself is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated, thereby delivering a large amount of energy with stable cycling. A key aspect of the innovation has been the development of a scalable process to produce submicronand micron-scale particles of these composite materials. An additional advantage of using such a composite electrode material is its low irreversible loss (.5%), which is primarily due to the unique activation of the composite. High columbic efficiency (greater than 99%) upon cycling may indicate the formation of a stable SEI (solid-electrolyte interface) layer, which can contribute to long cycle life. The innovation in the current program, when further developed, will enable the system to maintain high energy and power densities at low temperatures, improve efficiency, and further stabilize and enhance the safety of the cell.

Hagh, Nader↗

Roll to Roll (R2R) Manufacturing of Electrolysis Electrodes for Low Cost Hydrogen Production: Cooperative Research and Development Final Report, CRADA Number CRD-18-00780

NREL, Argonne National Laboratory (ANL) and Oak Ridge National Laboratory (ORNL), which are also referred to collectively herein as the "Contractors" will perform electrode ink development and characterization, focusing on 1) inks with appropriate properties for R2R (gravure and slot-die) coating onto PFSA membrane and 2) catalysts suitable for electrolysis. Participant will develop acceptance criteria and characterization methods for direct coating on the membrane. The purpose of this project is to show feasibility for cost reduction of the electrode through increased throughput and improved material utilization. Successful completion of this project will result in more affordable hydrogen production via proton exchange membrane (PEM) electrolysis by substantially reducing the anode precious metal content and catalyst-coated membrane processing costs. Assists laboratory in achieving programmatic scope, adds new capability to the laboratory's core competencies. This project uses and enhances the laboratory's core competencies, and enhances U.S. competitiveness by utilizing DOE developed intellectual property and/or capabilities. This project will benefit the Fuel Cell subprogram within the EERE Fuel Cell Technologies Office (FCTO) by actively developing materials, formulations, components, and processes for PEM electrolyzer stacks for overcoming critical technical barriers to widespread hydrogen production for zero-emission transportation applications. Through this JWS, NREL, ANL and ORNL are assisting a key domestic industry partner, Proton Energy Systems, Inc., in the area of low-cost electrolyzer electrode formulation and coating technology. After completion of this project, NREL, ANL and ORNL will be able to verify whether the direct deposit coating processes investigated are suitable for producing CCMs for PEM electrolyzers, which is of great interest and benefit to the DOE EERE Fuel Cell Technologies Office (FCTO) and H2@Scale missions.

08 HYDROGEN↗

A Symmetrical, Planar SOFC Design for NASA's High Specific Power Density Requirements

Solid oxide fuel cell (SOFC) systems for aircraft applications require an order of magnitude increase in specific power density (1.0 kW/kg) and long life. While significant research is underway to develop anode supported cells which operate at temperatures in the range of 650-800 C, concerns about Cr-contamination from the metal interconnect may drive the operating temperature down further, to 750 C and lower. Higher temperatures, 900-1000 C, are more favorable for SOFC stacks to achieve specific power densities of 1.0 kW/kg. Since metal interconnects are not practical at these high temperatures and can account for up to 75% of the weight of the stack, NASA is pursuing a design that uses a thin, LaCrO3-based ceramic interconnect that incorporates gas channels into the electrodes. The bi-electrode supported cell (BSC) uses porous YSZ scaffolds, on either side of a 10-20 microns electrolyte. The porous support regions are fabricated with graded porosity using the freeze-tape casting process which can be tailored for fuel and air flow. Removing gas channels from the interconnect simplifies the stack design and allows the ceramic interconnect to be kept thin, on the order of 50 -100 microns. The YSZ electrode scaffolds are infiltrated with active electrode materials following the high temperature sintering step. The NASA-BSC is symmetrical and CTE matched, providing balanced stresses and favorable mechanical properties for vibration and thermal cycling.

Cable, Thomas L.↗

Functionalization of Electrodes with Tunable [EMIM] x [Cl] x +1 – Ionic Liquid Clusters for Electrochemical Separations

Functionalization of electrodes with clusters of hydrophobic molecules may improve the energy efficiency and selectivity of electrochemical separations by modulating the desolvation process occurring at the interface. Ionic liquids (IL), which have a broad range of compositions and properties, are potential candidates for controlling the transport, desolvation, and adsorption of target ions at electrochemical interfaces. We report a joint experimental and theoretical investigation of the structure, stability, and selective adsorption properties of the IL clusters 1-ethyl-3-methylimidazolium chloride [EMIM] x [Cl] x+1 - (x = 1 – 10) and demonstrate their ability to adsorb and separate ions from solution. The structure and stability of the IL clusters are determined experimentally using high-mass-resolution electrospray ionization mass spectrometry, collision-induced dissociation, and negative ion photoelectron spectroscopy. Global optimization theory and ab initio molecular dynamics simulations provide molecular-level insight into the bonding and structural fluxionality of these species. Ion soft landing is used to selectively functionalize the surface of highly oriented pyrolytic graphite (HOPG) working electrodes with [EMIM] 1 [Cl] 2 - , [EMIM] 3 [Cl] 4 - , and [EMIM] 5 [Cl] 6 - clusters. Kelvin probe microscopy provides insight into the relative stability of the clusters on HOPG and their effect on the work function of IL-functionalized electrodes. Cyclic voltammetry measurements reveal irreversible adsorption of Fe(CN) 6 4-/3- anions during redox cycling, while electrochemical impedance spectroscopy indicates a substantial decrease in the electron transfer resistance of the IL-functionalized electrodes due to adsorption of Fe(CN) 6 4-/3- . Overall, our findings demonstrate that IL clusters with different size and stoichiometry may be used to increase the efficiency of electrochemical separations, opening new horizons in selective electrode functionalization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical processing of solid waste

The investigation into electrolysis as a means of waste treatment and recycling on manned space missions is described. The electrochemical reactions of an artificial fecal waste mixture was examined. Waste electrolysis experiments were performed in a single compartment reactor, on platinum electrodes, to determine conditions likely to maximize the efficiency of oxidation of fecal waste material to CO2. The maximum current efficiencies for artificial fecal waste electrolysis to CO2 was found to be around 50 percent in the test apparatus. Experiments involving fecal waste oxidation on platinum indicates that electrodes with a higher overvoltage for oxygen evolution such as lead dioxide will give a larger effective potential range for organic oxidation reactions. An electrochemical packed column reactor was constructed with lead dioxide as electrode material. Preliminary experiments were performed using a packed-bed reactor and continuous flow techniques showing this system may be effective in complete oxidation of fecal material. The addition of redox mediator Ce(3+)/Ce(4+) enhances the oxidation process of biomass components. Scientific literature relevant to biomass and fecal waste electrolysis were reviewed.

Bockris, J. OM.↗

Combining 3D printing of copper current collectors and electrophoretic deposition of electrode materials for structural lithium-ion batteries

Serving as a proof of concept, additive manufacturing and electrophoretic deposition are leveraged in this work to enable structural lithium-ion batteries with load-bearing and energy storage dual functionality. The preparation steps of a complex 3D printed copper current collector, involving the formulation of a photocurable resin formulation, as well as the vat photopolymerization process followed by a precursors-based solution soaking step and thermal post-processing are presented. Compression and microhardness testing onto the resulting 3D printed copper current collector are shown to demonstrate adequate mechanical performance. Electrophoretic deposition of graphite as a negative electrode active material and other additives was then performed onto the 3D printed copper collector, with the intention to demonstrate energy storage functionality. Half-cell electrochemical cycling of the 3D multi-material current collector/negative electrode versus lithium metal finally demonstrates that structural battery components can be successfully obtained through this approach.

25 ENERGY STORAGE↗