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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Temperature-dependent Battery Performance of a Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT Cathode and In-situ Heat Generation on Cycling

Excellent structural stability, high operating voltage, and high capacity have made Na 3 V 2 (PO 4 ) 2 F 3 a promising cathode material for sodium-ion batteries. However, high-temperature battery performances and heat generation measurements have not been systematically reported yet. Carbon-coated Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT (multi-walled carbon nanotube) samples are fabricated by a hydrothermal-assisted sol-gel method and the electrochemical performances are evaluated at three different temperatures (25, 45, and 55 °C). Furthermore, the well-crystallized Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT samples exhibit good cycling stability at both low and high temperatures; they deliver an initial discharge capacity of 120–125 mAhg -1 at a 1 C rate with a retention of 53 % capacity after 1,400 cycles with 99 % columbic efficiency. The half-cell delivers a capacity of 100 mAhg -1 even at a high rate of 10 C at room temperature. Furthermore, the Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT samples show good long-term durability; the capacity loss is an average of 0.05 % per cycle at a 1 C rate at 55 °C. Additionally, ionic diffusivity and charge transfer resistance are evaluated as functions of state of charge, and they explain the high electrochemical performance of the Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT samples. In-situ heat generation measurements reveal reversible results upon cycling owing to the high structural stability of the material. Excellent electrochemical performances are also demonstrated in the full-cell configuration with hard carbon as well as antimony Sb/C anodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Elucidating the Role of Single-Atom Pd for Electrocatalytic Hydrodechlorination

In this study, we loaded Pd catalysts onto a reduced graphene oxide (rGO) support in an atomically dispersed fashion [i.e., Pd single-atom catalysts (SACs) on rGO or Pd 1 /rGO] via a facile and scalable synthesis based on anchor-site and photoreduction techniques. The as-synthesized Pd 1 /rGO significantly outperformed the Pd nanoparticle (Pdnano) counterparts in the electrocatalytic hydrodechlorination of chlorinated phenols. Downsizing Pd nano to Pd 1 leads to a substantially higher Pd atomic efficiency (14 times that of Pdnano), remarkably reducing the cost for practical applications. The unique single-atom architecture of Pd 1 additionally affects the desorption energy of the intermediate, suppressing the catalyst poisoning by Cl – , which is a prevalent challenge with Pdnano. Characterization and experimental results demonstrate that the superior performance of Pd 1 /rGO originates from (1) enhanced interfacial electron transfer through Pd–O bonds due to the electronic metal–support interaction and (2) increased atomic H (H*) utilization efficiency by inhibiting H 2 evolution on Pd 1 . Furthermore, this work presents an important example of how the unique geometric and electronic structure of SACs can tune their catalytic performance toward beneficial use in environmental remediation applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Multisublattice cluster expansion study of short-range ordering in iron-substituted strontium titanate

Owing to the challenges in obtaining realistic atomic configurations in large chemical phase spaces, it is not straightforward to describe structure–property relations in materials exhibiting configurational disorder. One example is iron-substituted strontium titanate (SrTi 1–x Fe x O 3–d , STF), a promising perovskite-derivative cathode material in solid oxide fuel cells that exhibits full solid solubility 0 ≤ x ≤ 1 and a tendency to exhibit short-range order. Here we demonstrate a multisublattice cluster expansion (CE) framework and apply it to STF across the full composition range. The CE approach is distinct from more traditional CE formulations in that clusters are defined explicitly by the chemical species distributed among multiple sublattices, rather than via cluster functions of occupation variables with decoration. The modified CE approach makes it easy to distinguish meaningful chemical interactions that are harder to extract from conventional CE, since for the latter chemical identity in a cluster is expressed as a product of site occupations. The least absolute shrinkage and selection operator (LASSO) is implemented as a regression analysis tool to select key clusters and avoid overfitting. We demonstrate this formulation on STF, and show that it can accurately predict configurational energies in comparison to conventional CE. From the key clusters, we identify that short-range ordering between substitutional Fe and oxygen vacancies (V O ) results in the formation of Fe–VO strings. In addition, we consider the stability of STF through CE-based Monte Carlo (MC) simulations and confirm the presence of superstructures that were previously observed in transmission electron microscopy. In this work, analysis of atomic configurations from MC samples reveals variations in the oxidation state of Fe atoms, which can be explained by the ordering tendency of Fe and V O . The cluster description and selection formalism described here may be applied to other disordered multisublattice systems for accurate and efficient material modeling.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Utilizing Conjugated Imine Polymers to Stabilize Nanoparticle Silicon Anodes

Silicon anodes provide a compelling route towards delivering high-capacity lithium-ion batteries, however they are notoriously difficult to stabilize in conventional liquid electrolytes that are compatible with high performance cathodes. Furthermore, the drastic changes in volume that occur as silicon is lithiated and delithiated can lead to rapid cell failure and novel polymeric binders are known to help mitigate mechanical issues. We have recently developed a novel method to synthesize the conjugated polymer phenylmethylimine (polyPMI) using an imine metathesis reaction. We have demonstrated that this polymer can be used to stabilize silicon nanoparticles to produce a composite lithium-ion battery anode that is electrochemically stable for hundreds of lithiation and delithiation cycles with a Coulombic efficiency that is greater than 99.95% in a traditional carbonate liquid electrolyte. This work covers the structure and properties of polyPMI within the context of the unique mechanical and electrochemical requirements of nanoparticle silicon anodes. The electrochemical behavior of this polymer also offers new opportunities as an organic lithium-coordinating material that can be used to stabilize a variety of other battery electrodes. More broadly, we posit that this solution-processed, ionically conductive, and electronically conductive polymer is applicable for a variety of energy storage and conversion technologies. Finally, this work demonstrates how this novel polymer chemistry provides additional opportunities for tuning electrode architecture to target high energy full cells.

conjugated polymers↗
NASA NTRS1998

Potential for EMU Fabric Damage by Electron Beam and Molten Metal During Space Welding for the International Space Welding Experiment

As a consequence of preparations concerning the International Space Welding Experiment (ISWE), studies were performed to better understand the effect of molten metal contact and electron beam impingement with various fabrics for space suit applications. The question arose as to what would occur if the electron beam from the Ukrainian Universal Hand Tool (UHT) designed for welding in space were to impinge upon a piece of Nextel AF-62 ceramic cloth designed to withstand temperatures up to 1427 C. The expectation was that the electron beam would lay down a static charge pattern with no damage to the ceramic fabric. The electron beam is capable of spraying the fabric with enough negative charge to repel further electrons from the fabric before significant heating occurs. The static charge pattern would deflect any further charge accumulation except for a small initial amount of leakage to the grounded surface of the welder. However, when studies were made of the effect of the electron beam on the insulating ceramic fabric it was surprisingly found that the electron beam did indeed burn through the ceramic fabric. It was also found that the shorter electron beam standoff distances had longer burnthrough times than did some greater electron beam standoff distances. A possible explanation for the longer burnthrough times for the small electron beam standoff distance would be outgassing of the fabric which caused the electron beam hand-tool to cycle on and off to provide some protection for the cathodes. The electron beam hand tool was observed to cycle off at the short standoff distance of two inches likely due to vapors being outgassed. During the electron beam welding process there is an electron leakage, or current leakage, flow from the fabric. A static charge pattern is initially laid down by the electron beam current flow. The static charge makes up the current leakage flow which initially slightly heats up the fabric. The initially laid down surface charge leaks a small amount of current. The rate at which the current charge leaks from the fabric controls how fast the fabric heats up. As the ceramic fabric is heated it begins to outgass primarily from contamination/impurities atoms or molecules on and below the fabric surface. The contaminant gases ionize to create extra charge carriers and multiply a current of electrons. The emitted gas which ionized in the electron leakage flow promotes further leakage. Thus, the small leakage of charge from the fabric surface is enhanced by outgassing. When the electron beam current makes up the lost current, the incoming electrons heat the fabric and further enhance the outgassing. The additional leakage promotes additional heating up of the ceramic fabric. The electrons bound to the ceramic fabric surface leak off more and more as the surface gets hotter promoting even greater leakage. The additional electrons that result also gain energy in the field and produce further electrons. Eventually the process becomes unstable and accelerates to the point where a hole is burned through the fabric.

Fragomeni, James M.↗
NASA NTRS2011

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.↗
NASA NTRS2014

Evaluation of Polymer Hermetically Sealed Tantalum Capacitors

Polymer cathode tantalum capacitors have lower ESR (equivalent series resistance) compared to other types of tantalum capacitors and for this reason have gained popularity in the electronics design community. Their use allows improved performance of power supply systems along with substantial reduction of size and weight of the components used. However, these parts have poor thermal stability and can degrade in humid environments. Polymer hermetically sealed (PHS) capacitors avoid problems related to environmental degradation of molded case parts and can potentially replace current wet and solid hermetically sealed capacitors. In this work, PHS capacitors manufactured per DLA LAM DWG#13030 are evaluated for space applications. Several lots of capacitors manufactured over period from 2010 to 2014 were tested for the consistency of performance, electrical and thermal characteristics, highly accelerated life testing, and robustness under reverse bias and random vibration conditions. Special attention was given to analysis of leakage currents and the effect of long-term high temperature storage on capacitors in as is condition and after hermeticity loss. The results show that PHS capacitors might be especially effective for low-temperature applications or for system requiring a cold start-up. Additional screening and qualification testing have been recommended to assure the necessary quality of capacitors for space projects.

ferrite beads↗
NASA NTRS1992

Plasma contactor research - 1991

A report describing the operating principles of hollow-cathode-based plasma contactors emitting or collecting electrons from an ambient plasma is summarized. Preliminary experiments conducted to determine the noise generated by these plasma contactors in the emission-current return line and in the plasma near it are described. These noise data are measured as current fluctuations in the return line and to the Langmuir probe and then analyzed using a fast Fourier transform technique. The spectral compositions of the data are characterized using power spectral density plots which are examined to identify possible noise source(s) and production mechanism(s). The precautions taken in the construction and calibration of the instrumentation to assure adequate frequency response are described. Experimental results show that line-current noise levels are typically 2 percent of the electron current being emitted or collected. However, noise levels increase to as much as 20 percent of the electron current at a few electron-collection operating conditions. The frequencies associated with most of the noise were harmonics of the 60 Hz input to system power supplies. Plasma noise had characteristics similar in magnitude and frequency to those for the return-line noise, but they contained additional features at frequencies considered to be related to ion-acoustic instabilities. Also discussed is a new probe positioning system built to facilitate future plasma-contractor research.

Buchholtz, Brett↗
DOE OSTI2020

Evolution of lithium ordering with (de)-lithiation in β-LiVOPO 4 : insights through solid-state NMR and first principles DFT calculations

The lithium-ion battery cathode material β-VOPO 4 is capable of intercalating more than one Li ion per transition metal ion due to the accessibility of both the V 5+ /V 4+ and V 4+ /V 3+ redox couples at ~4.5 V and ~2.3 V vs. Li, respectively, giving a theoretical capacity greater than ~300 mA h g -1 . The ability to perform full and reversible two Li-ion intercalation in this material, however, has been a matter of debate and the poor crystallinity of the fully lithiated phase has thus far precluded its complete structural characterisation by conventional diffraction-based methods. In this work, 7 Li and 31 P NMR spectroscopy, in combination with first principles DFT calculations, indicate that chemical lithiation results in a single phase β-Li 2 VOPO 4 exhibiting a complex Li ordering scheme with lithium ions occupying multiple disordered environments. 2D NMR 7 Li correlation experiments were used to deduce the most likely Li ordering for the β-Li 2 VOPO 4 phase from amongst several DFT optimised structures. In contrast, electrochemically lithiated β-Li 2- x VOPO 4 discharged to 1.6 V exhibits, in addition to β-Li 2 VOPO 4 , a β-Li 1.5 VOPO 4 phase. Additionally, the existence of β-Li 1.5 VOPO 4 is not reflected in the flat galvanostatic charge and discharge curves nor is evident from diffraction-based methods due to the very close structural similarity between the β-Li 1.5 VOPO 4 phase and β-Li 2 VOPO 4 phases. We demonstrate that solid state NMR spectroscopy, in combination with DFT results, provides a powerful tool for identifying intermediate states formed during charge/discharge of these complex phosphates as these phases can be distinguished from the end member phases primarily by the nature of the lithium ordering.

25 ENERGY STORAGE↗
DOE OSTI2023

Development & Validation of Low-Cost, Highly-Durable, Spinel-Based Materials for SOFC Cathode-Side Contact (Final Report)

A cathode-side contact layer is required to provide and maintain stable electrical conduction paths between the interconnect and cathode in a solid oxide fuel cell (SOFC) stack assembly and thus minimize the ohmic resistance and stack power loss. Current cathode-interconnect contact materials are based on noble metals, electrically-conductive perovskites, their composite materials, etc. These materials are either too expensive or do not possess the overall balanced performance required for the cathode-side contact application. To achieve the DOE SOFC system cost and performance stability goals, a new generation of low-cost, high-performance contact materials needs to be developed. In this project, spinel-based materials thermally converted from the Fe-Ni and Co-Mn based alloy precursors were developed and validated for the cathode-side contact application. The precursor alloy compositions were optimized via a combination of composition screening in the (Ni,Fe) 3 O 4 and (Mn,Co) 3 O 4 spinel system, alloy design using physical metallurgy principles, and cost considerations. The alloy powders with the desired composition and particle size were manufactured via gas atomization. The optimal process parameters for thermal conversion of these alloy precursor layers to a spinel-based layer were identified, i.e., 900°C x 2h in air, which is close to the initial stack firing condition. The area-specific resistances (ASRs) of the interconnect/contact/cathode test assemblies with the developed contact layer were determined for various durations (up to 5000 h) under simulated cathodic operation conditions. Some of the alloy-derived spinel contacts exhibited the lowest ASR and ASR degradation rate. The in-stack performance of the most promising alloy-derived contact layer is currently being evaluated via stack testing. To reduce the stack cost, the Co-Mn based alloy powders were utilized as the precursor for synthesis of dense spinel-based interconnect coating. By optimizing both the initial powder size/distribution and the alloy powder composition, a dense (Mn,Co) 3 O 4 -based spinel coating was achieved. Furthermore, co-sintering of the coating/contact dual-layer structure under the initial stack firing condition was realized by utilizing the tailored Co-Mn alloy precursors. Cost analysis of the developed technology indicated a total stack cost reduction of around 10.6% with the implementation of co-sintering of the interconnect coating and the contact layer during initial stack firing. Since low-cost processes such as screen printing is utilized in the precursor application and no reduction heat treatment is needed for the coating formation, the developed technology can be readily implemented at the industrial partner’s manufacturing facilities with no additional capital investment needed.

08 HYDROGEN↗
NASA NTRSDate not supplied

Mixed-Domain Charge Transport in S-Se Alloys as a Li-S Battery Cathode Material

Lithium-sulfur batteries are emerging candidate systems for the next-generation long-range electric aircraft application owing to their potential to deliver high energy density per weight. Their cathodes are to be made primarily with sulfur, but sulfur by itself has much too low electron conductivity to serve as a useful cathode. An idea that has been suggested to overcome this bottleneck is to alloy sulfur with selenium in the hope that electron mobility, which is thought to improve charge transport at some expense of increased weight and reduced energy density. However, understanding of these alloy structures and their transport mechanism is insufficient, and electron mobility at varying degrees of selenium content is not well charted, which are critical for determining the optimum selenium content and testing whether this strategy is generally feasible. The difficulty of computationally characterizing these alloy systems is rooted in the structure. The structures of both sulfur and selenium exhibit eight-atom rings that pack together in various orientations to form their respective crystals. For one, because these crystals (and presumably their alloys as well) feature multiple polymorphs such that their structural coherence is rather unclear. Secondly, these are also relatively large systems (32 atoms per cell) with low-symmetry, which complicate computation both in terms of accuracy and efficiency. Thirdly, such semi-molecular, semi-crystalline structures lead to a combination of band-transport characteristics and hopping-transport characteristics, each of which is a domain with its own physics and set of computational, theoretical challenges. In addition, there is a general dearth of experimental transport data for sulfur-selenium alloys. In this study, we make a comprehensive attempt to tackle this problem using a wide array of first-principles methods. We generate special quasirandom structures to simulate alloy structures, and compute their first-principles Raman spectra for comparison with experimental data to ensure their structural soundness. We then proceed to use recently developed, state-of-the-art tool (AMSET) in order to efficiently compute electronic mobilities under band transport of pure sulfur, pure selenium, as well as their alloys of various compositions at a reasonable accuracy. We then sample numerous dimer configurations of nearest-neighbor eight-atom-ring-pairs and compute electronic hopping rates between them, which yields hopping mobility. A combination of these efforts lead to a general mapping of electron transport behaviors throughout the alloy range. Preliminary results show that introduction of selenium into sulfur initially damages electron mobility due to disorder but eventually improves it beyond that of pure sulfur with additional selenium content, ultimately peaking at the pure-selenium limit. Band transport dominates for holes in sulfur and electrons in selenium, but in all other cases, hopping transport is dominant. Ongoing efforts include determination of charge concentration and conductivity, as well as performing multiphysics modeling to determine the optimum selenium content for best tradeoff between conductivity and energy density for aircraft range.

Junsoo Park↗
NASA NTRS2014

Implementation and Initial Validation of a 100-Kilowatt Class Nested-Channel Hall Thruster

The X3 is a 100-kilowatt class nested-channel Hall thruster developed by the Plasmadynamics and Electric Propulsion Laboratory at the University of Michigan in collaboration with the Air Force Research Laboratory and NASA. The cathode, magnetic circuit, boron nitride channel rings, and anodes all required specific design considerations during thruster development, and thermal modeling was used to properly account for thermal growth in material selection and component design. A number of facility upgrades were required at the University of Michigan to facilitate operation of the X3. These upgrades included a re-worked propellant feed system, a completely redesigned power and telemetry break-out box, and numerous updates to thruster handling equipment. The X3 was tested on xenon propellant at two current densities, 37% and 73% of the nominal design value. It was operated to a maximum steady-state discharge power of 60.8 kilowatts. The tests presented here served as an initial validation of thruster operation. Thruster behavior was monitored with telemetry, photography and high-speed current probes. The photography showed a uniform plume throughout testing. At constant current density, reductions in mass flow rate of 18% and 26% were observed in the three-channel operating configuration as compared to the superposition of each channel running individually. The high-speed current probes showed that the thruster was stable at all operating points and that the channels influence each other when more than one is operating simultaneously. Additionally, the ratio of peak-to-peak AC-coupled discharge current oscillations to mean discharge current did not exceed 51% for any operating points reported here, and did not exceed 17% at the higher current density.

High Power↗
NASA NTRS2009

High-Efficiency Artificial Photosynthesis Using a Novel Alkaline Membrane Cell

A new cell designed to mimic the photosynthetic processes of plants to convert carbon dioxide into carbonaceous products and oxygen at high efficiency, has an improved configuration using a polymer membrane electrolyte and an alkaline medium. This increases efficiency of the artificial photosynthetic process, achieves high conversion rates, permits the use of inexpensive catalysts, and widens the range of products generated by this type of process. The alkaline membrane electrolyte allows for the continuous generation of sodium formate without the need for any additional separation system. The electrolyte type, pH, electrocatalyst type, and cell voltage were found to have a strong effect on the efficiency of conversion of carbon dioxide to formate. Indium electrodes were found to have higher conversion efficiency compared to lead. Bicarbonate electrolyte offers higher conversion efficiency and higher rates than water solutions saturated with carbon dioxide. pH values between 8 and 9 lead to the maximum values of efficiency. The operating cell voltage of 2.5 V, or higher, ensures conversion of the carbon dioxide to formate, although the hydrogen evolution reaction begins to compete strongly with the formate production reaction at higher cell voltages. Formate is produced at indium and lead electrodes at a conversion efficiency of 48 mg of CO2/kilojoule of energy input. This efficiency is about eight times that of natural photosynthesis in green plants. The electrochemical method of artificial photosynthesis is a promising approach for the conversion, separation and sequestration of carbon dioxide for confined environments as in space habitats, and also for carbon dioxide management in the terrestrial context. The heart of the reactor is a membrane cell fabricated from an alkaline polymer electrolyte membrane and catalyst- coated electrodes. This cell is assembled and held in compression in gold-plated hardware. The cathode side of the cell is supplied with carbon dioxide-saturated water or bicarbonate solution. The anode side of the cell is supplied with sodium hydroxide solution. The solutions are circulated past the electrodes in the electrochemical cell using pumps. A regulated power supply provides the electrical energy required for the reactions. Photovoltaic cells can be used to better mimic the photosynthetic reaction. The current flowing through the electrochemical cell, and the cell voltage, are monitored during experimentation. The products of the electrochemical reduction of carbon dioxide are allowed to accumulate in the cathode reservoir. Samples of the cathode solution are withdrawn for product analysis. Oxygen is generated on the anode side and is allowed to vent out of the reservoir.

Narayan, Sri↗
DOE OSTI2024

The role of Li doping in layered/layered Na x Li y Ni 0.4 Fe 0.2 Mn 0.4 O 2 intergrowth electrodes for sodium ion batteries

Here, the layered NaTMO 2 (TM = Ni, Fe, Mn) materials with the O3-type structure are attractive as positive electrodes for sodium ion batteries because of their high theoretical capacity. Additionally, Li doping in these materials has been shown to offer substantial enhancements to their electrochemical properties by promoting the formation of intergrowth structures, which are combinations of specific phases. However, the mechanism by which the intergrowth modifies the electrochemical properties is often unclear. Systematic variation of Li content in Na x Li y Ni 0.4 Fe 0.2 Mn 0.4 O 2 (NFM-Li y ) was conducted to identify its role in structural modification and electrochemical performance. Li contents of 0.15 and greater generate a layered/layered Na-O3/Li-O’3 intergrowth structure. 7 Li and 23 Na nuclear magnetic resonance and x-ray absorption spectroscopy identify that when the total solubility for alkali ions in the layered structure is exceeded, Li continues to form the Li-O’3 phase while the excess Na forms residual sodium compounds such as Na 2 O. Higher Li content is associated with improved capacity retention in the initial cycles from the superior stability of the mechanically linked NaO3/Li-O’3 structure that suppresses the P3 to OP2 phase transition during charge. However, high Li contents are associated with increased rates of parasitic side reactions that reduce long-term cycling stability. These side reactions are associated with the instability of the cathode-electrolyte interphase, which can be partially mitigated by atomic layer deposition (ALD) coating with alumina, which significantly enhances the capacity retention and Coulombic efficiency over many cycles. Overall, we find that the layered/layered Na-O3/Li-O’3 intergrowth structure is able to provide structural stability and suppress undesired phase transformations but is overwhelmed by the increased reactivity of the surface if not protected by surface coating.

25 ENERGY STORAGE↗
NASA NTRS2015

Testing of an Arcjet Thruster with Capability of Direct-Drive Operation

Electric thrusters typically require a power processing unit (PPU) to convert the spacecraft provided power to the voltage-current that a thruster needs for operation. Testing has been initiated to study whether an arcjet thruster can be operated directly with the power produced by solar arrays without any additional conversion. Elimination of the PPU significantly reduces system-level complexity of the propulsion system, and lowers developmental cost and risk. The work aims to identify and address technical questions related to power conditioning and noise suppression in the system and heating of the thruster in long-duration operation. The apparatus under investigation has a target power level from 400-1,000 W. However, the proposed direct-drive arcjet is potentially a highly scalable concept, applicable to solar-electric spacecraft with up to 100's of kW and beyond. A direct-drive electric propulsion system would be comprised of a thruster that operates with the power supplied directly from the power source (typically solar arrays) with no further power conditioning needed between those two components. Arcjet thrusters are electric propulsion devices, with the power supplied as a high current at low voltage; of all the different types of electric thruster, they are best suited for direct drive from solar arrays. One advantage of an arcjet over Hall or gridded ion thrusters is that for comparable power the arcjet is a much smaller device and can provide more thrust and orders of magnitude higher thrust density (approximately 1-10 N/sq m), albeit at lower I(sub sp) (approximately 800-1000 s). In addition, arcjets are capable of operating on a wide range of propellant options, having been demonstrated on H2, ammonia, N2, Ar, Kr, Xe, while present SOA Hall and ion thrusters are primarily limited to Xe propellant. Direct-drive is often discussed in terms of Hall thrusters, but they require 250-300 V for operation, which is difficult even with high-voltage solar arrays. The arcjet requires under 100 V, which is more in-line with what is easily possible with a solar array. Direct-drive of an electric propulsion system confers the advantage of reducing or eliminating the power processing unit (PPU) that is typically needed to convert the spacecraft-provided power to the voltage and current needed for thruster operation. Since the PPU is typically the most expensive piece of an electric thruster system, from both a fabrication and qualification standpoint, its elimination offers the potential for major reductions in system cost and risk. The design of the arcjet built for this effort was based on previous low power (1 kW class) arcjets. It has a precision machined 99.95% pure tungsten anode which also serves as the nozzle. The anode constrictor region is 1 mm (0.040-in) diameter and 1 mm (0.040-in) long. The cathode is a tungsten welding electrode doped with LaO2; its tip was precision ground to a 30◦ angle ending in a blunt end. The two electrodes are separated by a boron-nitride insulator which also serves as the propellant injection manifold; it ends in six small holes which introduce the propellant gas in the diverging section of the nozzle, directly adjacent to the cathode. The electrodes and insulator are housed in a stainless-steel outer-body, with a Macor insulator at the mid-plane to provide thermal isolation between the front and back halves of the device. The gas seals were made using Grafoil gaskets. Figure 1A shows the assembled thruster in the vacuum chamber; figure 1B shows the thruster in operation on argon at a flow rate of 676 sccm (20 mg/s). Initial testing was conducted in a 3.5-ft diameter vacuum chamber; the ultimate pressure reached during quasi-steady operation of the thruster was about 330 millitorr. The thruster was powered with a high-current, 0-100A, 15 kW power supply. The discharge was initiated with a high-voltage (approximately 10 kV) spark initiator that was isolated from the supply by a stack of diodes. The testing indicated that an operating point exists within the I-V characteristics that is compatible with direct-drive solar-electric operation; for a flow rate of 20 mg/s (argon) the arc could be sustained at a voltage of about 20 V and a current of 25 A (500W).

Martin, Adam K.↗
NASA NTRS2012

Near-Infrared Photon-Counting Camera for High-Sensitivity Observations

The dark current of a transferred-electron photocathode with an InGaAs absorber, responsive over the 0.9-to-1.7- micron range, must be reduced to an ultralow level suitable for low signal spectral astrophysical measurements by lowering the temperature of the sensor incorporating the cathode. However, photocathode quantum efficiency (QE) is known to reduce to zero at such low temperatures. Moreover, it has not been demonstrated that the target dark current can be reached at any temperature using existing photocathodes. Changes in the transferred-electron photocathode epistructure (with an In- GaAs absorber lattice-matched to InP and exhibiting responsivity over the 0.9- to-1.7- m range) and fabrication processes were developed and implemented that resulted in a demonstrated >13x reduction in dark current at -40 C while retaining >95% of the approximately equal to 25% saturated room-temperature QE. Further testing at lower temperature is needed to confirm a >25 C predicted reduction in cooling required to achieve an ultralow dark-current target suitable for faint spectral astronomical observations that are not otherwise possible. This reduction in dark current makes it possible to increase the integration time of the imaging sensor, thus enabling a much higher near-infrared (NIR) sensitivity than is possible with current technology. As a result, extremely faint phenomena and NIR signals emitted from distant celestial objects can be now observed and imaged (such as the dynamics of redshifting galaxies, and spectral measurements on extra-solar planets in search of water and bio-markers) that were not previously possible. In addition, the enhanced NIR sensitivity also directly benefits other NIR imaging applications, including drug and bomb detection, stand-off detection of improvised explosive devices (IED's), Raman spectroscopy and microscopy for life/physical science applications, and semiconductor product defect detection.

Jurkovic, Michael↗
DOE OSTI2021

High-Rate Long Cycle-Life Li-Air Battery Aided by Bifunctional InX3 (X = I and Br) Redox Mediators

Redox mediators (RMs) are solution-based additives that have been extensively used to reduce the charge potential and increase the energy efficiency of Li–oxygen (Li–O 2 ) batteries. However, in the presence of RMs, achieving a long cycle-life operation of Li–O 2 batteries at a high current rate is still a major challenge. In this study, we discover a novel synergy among InX 3 (X = I and Br) bifunctional RMs, molybdenum disulfide (MoS 2 ) nanoflakes as the air electrode, dimethyl sulfoxide/ionic liquid hybrid electrolyte, and LiTFSI as a salt to achieve long cycle-life operations of Li–O 2 batteries in a dry air environment at high charge–discharge rates. Our results indicate that batteries with InI3 operate up to 450 cycles with a current density of 0.5 A g –1 and 217 cycles with a current density of 1 A g –1 at a fixed capacity of 1 A h g –1 . Batteries with InBr 3 operate up to 600 cycles with a current density of 1 A g –1 . These batteries can also operate at a higher charge rate of 2 A g –1 up to 200 cycles (for InBr 3 ) and 160 cycles (for InI 3 ). Our experimental and computational results reveal that while X 3 – is the source of the redox mediator, LiX at the MoS 2 cathode, In 3+ reacts on the lithium anode side to form a protective layer on the surface, thus acting as an effective bifunctional RM in a dry air environment. This evidence for a simultaneous improvement in the current rates and cycle life of a battery in a dry air atmosphere opens a new direction for research for advanced energy storage systems.

25 ENERGY STORAGE↗
DOE OSTI2025

Scalable mechanochemical synthesis of high-quality Prussian blue analogues for high-energy and durable potassium-ion batteries

Prussian blue analogues (PBAs) are recognized as promising cathode materials for potassium-ion batteries (PIBs), particularly the low-cost and high-energy K 2 Mn[Fe(CN) 6 ](KMnF). However, conventional solution-based synthesis inevitably introduces [Fe(CN) 6 ] 4− defects and lattice water while suffering low synthesis efficiency, unfavorable to the improvement of electrochemical performance and scalability. Here, in this work, we report a simple solvent-free mechanochemical strategy for the synthesis of a wide variety of K 2 M[Fe(CN) 6 ] (M = Mn, Mg, Ca, etc.) with negligible defects and water, and it is unprecedented to achieve kilogram-level products of high-quality KMnF within just 10 minutes. The as-prepared KMnF delivers a high energy density of 590 Wh kg −1 at 0.2 C and exhibits an astonishing stability over 10 000 cycles and rate ability up to 50 C in a potassium metal half-cell. Encouragingly, a high-areal-capacity pouch cell with 2.2 mAh cm −2 (16.5 mg cm −2 ) exhibits a capacity retention of 80.7% after 500 cycles. Furthermore, systematic in situ characterization reveals underlying mechanism insights into structure–performance relationships. Specifically, the fully coordinated Mn–N 6 octahedral configuration effectively suppresses Mn 3+ Jahn–Teller distortion, enabling reversible phase transitions under both high-voltage and long-term cycling conditions. In addition, minimal defects provide sufficient redox centers, while the continuous three-dimensional framework facilitates rapid K + diffusion kinetics. This work provides a new opportunity for the ultrafast, universal and scalable synthesis of high-quality PBAs, facilitating the practical application of PIBs while enabling precise structural and compositional design of novel PBAs.

Mechanochemical method↗