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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 397 records · Page 22

Cathode Interface Compatibility of Amorphous LiMn 2 O 4 (LMO) and Li 7 La 3 Zr 2 O 12 (LLZO) Characterized with Thin-Film Solid-State Electrochemical Cells

Solid-state lithium-ion batteries are a hopeful successor to traditional Li-ion cells that use liquid electrolytes. While a growing body of work has characterized the interfaces between various solid electrolytes and the lithium metal, interfaces with common cathode intercalation compounds are comparatively less understood. In this contribution, the influence of polarization and temperature on interfacial stability between LiMn 2 O 4 (LMO) and Li 7 La 3 Zr 2 O 12 (LLZO) are investigated. Sputtered thin-film LMO electrodes are utilized to permit high-capacity cycling while retaining a large ratio of interfacial area to electrode bulk. Electrochemical impedance spectroscopy (EIS) is compared across a set of full (LMO|LLZO|Li) and symmetric (LMO|LLZO|LMO, Li|LLZO|Li, and Au|LLZO|Au) cells to delineate impedance features that are specific to the evolution of the cathode interface. Furthermore, additional X-ray photoelectron spectroscopy (XPS) provides evidence of a limited interfacial reaction between LMO and LLZO that coincides with an increase in the impedance of the LMO–LLZO interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modified Coal Char Materials with High Rate Performance for Battery Applications

Global energy consumption has been rising since the early 2000s, and most of the energy supply still comes from burning fossil fuels. Considering the detrimental environmental impacts of fossil fuels, such as CO 2 emissions, it is crucial to develop clean energy technologies, such as storage devices that can advance long-term reversible and sustainable energy resources. In this work, we demonstrate the direct use of coal char in anodes tailored for both lithium-ion and sodium-ion batteries. The findings show that acid treatment followed by high-temperature argon annealing results in coal char particles with the desired porous structure, surface properties, and turbostratic nanodomains that deliver high reversible capacity and maintain good electrochemical performance at high rates up to 10C. Long-term cycling stability for 500 cycles can be achieved in cells comprising NMC cathodes at 1C with 73.2% capacity retention. In conclusion, this study sheds light on potential energy storage use cases for coal char outside its traditional utilization.

25 ENERGY STORAGE↗

Suppressing strain propagation in ultrahigh-Ni cathodes during fast charging via epitaxial entropy-assisted coating

Surface reconstruction and the associated severe strain propagation have long been reported as the major cause of cathode failure during fast charging and long-term cycling. Despite tremendous attempts, no known strategies can simultaneously address the electro-chemomechanical instability without sacrificing energy and power density. Here we report an epitaxial entropy-assisted coating strategy for ultrahigh-Ni LiNi x Co y Mn 1-x-y O 2 (x ≥ 0.9) cathodes via an oriented attachment-driven reaction between Wadsley-Roth phase-based oxides and the layered-oxide cathodes. Further, the high anti-cracking and anti-corrosion tolerances as well as the fast ionic transport of the entropy-assisted surface effectively improved the fast charging/discharging capability, wide temperature tolerance and thermal stability of the ultrahigh-Ni cathodes. Comprehensive analysis from the primary and secondary particle level to the electrode level using multi-scale in situ synchrotron X-ray probes reveals greatly reduced lattice dislocations, anisotropic lattice strain and oxygen release as well as improved bulk/local structural stability, even when charging beyond the threshold state of charge (75%) of layered cathodes. Layered Ni-rich oxide cathodes are susceptible to challenges with surface reconstruction and strain propagation, limiting their cyclability. The authors propose a solution involving oriented attachment-driven reactions, utilizing Wadsley-Roth nanocrystals and layered oxide to induce an epitaxial entropy-assisted coating, effectively addressing these issues.

25 ENERGY STORAGE↗

Molybdenum Carbide Electrocatalysts for Electrochemical Synthesis of Ammonia from Nitrogen: Activity and Stability

Ammonia production has increased from few thousand tons in 1908 to above 200 million tons per year today, revolutionizing the fertilizer industry thanks to the Haber-Bosch (HB) process. However, the HB process is highly energy intensive consuming about 1.4% of fossil energy generated worldwide and releasing 1.87 tons of CO 2 per ton of ammonia produced. This further reduces ammonia’s scope as a carrier fuel for the hydrogen economy. Hence, finding alternative energy efficient ways to synthesize ammonia is important from more than one perspective. Ammonia synthesis from its constituent nitrogen and hydrogen gases is mainly hampered by the nitrogen reduction reaction (NRR) due to the strong N≡N bond (945 kJ mol −1 ). Electrochemical synthesis (ES) routes in this regard offer a milder approach. However, ES of ammonia under different temperatures, utilizing different electrolytes and catalysts has not yet reliably produced ammonia at viable rates and efficiencies. We report an origami-like Mo 2 C cathode catalyst for NRR that achieved a maximum synthesis rate of 2.16 × 10 −11 mol cm −2 s −1 and a faradaic efficiency of 1.8% at 30 °C using Nafion-212 as electrolyte. Origami-like morphology containing numerous kinks appears to improve electrocatalytic activity and show a promising route for fabricating NRR catalysts with higher catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development and fabrication of a high current, fast recovery power diode

A high voltage (VR = 1200 V), high current (IF = 150 A), fast recovery ( 700 ns) and low forward voltage drop ( 1.5 V) silicon rectifier was designed and the process developed for its fabrication. For maximum purity, uniformity and material characteristic stability, neutron transmutation n-type doped float zone silicon is used. The design features a hexagonal chip for maximum area utilization of space available in the DO-8 diode package, PIN diffused junction structure with deep diffused D(+) anode and a shallow high concentration n(+) cathode. With the high temperature glass passivated positive bevel mesa junction termination, the achieved blocking voltage is close to the theoretical limit of the starting material. Gold diffusion is used to control the lifetime and the resulting effect on switching speed and forward voltage tradeoff. For solder reflow assembly, trimetal (Al-Ti-Ni) contacts are used. The required major device electrical characteristics were achieved. Due to the tradeoff nature of forward voltage drop and reverse recovery time, a compromise was reached for these values.

Berman, A. H.↗

The TMI Regenerative Solid Oxide Fuel Cell

Energy storage and production in space requires rugged, reliable hardware which minimizes weight, volume, and maintenance while maximizing power output and usable energy storage. Systems generally consist of photovoltaic solar arrays which operate (during sunlight cycles) to provide system power and regenerate fuel (hydrogen) via water electrolysis and (during dark cycles) fuel cells convert hydrogen into electricity. Common configurations use two separate systems (fuel cell and electrolyzer) in conjunction with photovoltaic cells. Reliability, power to weight and power to volume ratios could be greatly improved if both power production (fuel cells) and power storage (electrolysis) functions can be integrated into a single unit. The solid oxide fuel cell (SOFC) based design integrates fuel cell and electrolyzer functions and potentially simplifies system requirements. The integrated fuel cell/electrolyzer design also utilizes innovative gas storage concepts and operates like a rechargeable 'hydrogen-oxygen battery'. Preliminary research has been completed on improved H2/H20 electrode (SOFC anode/electrolyzer cathode) materials for regenerative fuel cells. Tests have shown improved cell performance in both fuel and electrolysis modes in reversible fuel cell tests. Regenerative fuel cell efficiencies, ratio of power out (fuel cell mode) to power in (electrolyzer mode), improved from 50 percent using conventional electrode materials to over 80 percent. The new materials will allow a single SOFC system to operate as both the electolyzer and fuel cell. Preliminary system designs have also been developed to show the technical feasibility of using the design for space applications requiring high energy storage efficiencies and high specific energy. Small space systems also have potential for dual-use, terrestrial applications.

Cable, Thomas L.↗

Electrocatalytic Reduction of Carbon Dioxide to Methane

A room-temperature electrocatalytic process that effects the overall chemical reaction CO2 + 2H2O yields CH4 + 2O2 has been investigated as a means of removing carbon dioxide from air and restoring oxygen to the air. The process was originally intended for use in a spacecraft life-support system, in which the methane would be vented to outer space. The process may also have potential utility in terrestrial applications in which either or both of the methane and oxygen produced might be utilized or vented to the atmosphere. A typical cell used to implement the process includes a polymer solid-electrolyte membrane, onto which are deposited cathode and anode films. The cathode film is catalytic for electrolytic reduction of CO2 at low overpotential. The anode film is typically made of platinum. When CO2 is circulated past the cathode, water is circulated past the anode, and a suitable potential is applied, the anode half-cell reaction is 4H2O yields 2O2 + 8H(+) + 8e(-). The H(+) ions travel through the membrane to the cathode, where they participate in the half-cell reaction CO2 + 8H(+) + 8e(-) yields CH4 + 2H2O.

Sammells, Anthony F.↗

Revisiting Discharge Mechanism of CF x as a High Energy Density Cathode Material for Lithium Primary Battery

Lithium/fluorinated graphite (Li/CFx) primary batteries show great promise for applications in a wide range of energy storage systems due to their high energy density (>2100 Wh kg –1 ) and low self-discharge rate (<0.5% per year at 25 °C). While the electrochemical performance of the CF x cathode is indeed promising, the discharge reaction mechanism is not thoroughly understood to date. In this article, a multiscale investigation of the CF x discharge mechanism is performed using a novel cathode structure to minimize the carbon and fluorine additives for precise cathode characterizations. Titration gas chromatography, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, cross-sectional focused ion beam, high-resolution transmission electron microscopy, and scanning transmission electron microscopy with electron energy loss spectroscopy are utilized to investigate this system. Results show no metallic lithium deposition or intercalation during the discharge reaction. Crystalline lithium fluoride particles uniformly distributed with <10 nm sizes into the CF x layers, and carbon with lower sp2 content similar to the hard-carbon structure are the products during discharge. This article deepens the understanding of CF x as a high energy density cathode material and highlights the need for future investigations on primary battery materials to advance performance.

25 ENERGY STORAGE↗

Nonflammable Lithium Metal Full Cells with Ultra-high Energy Density Based on Coordinated Carbonate Electrolytes

Coupling thin Li metal anodes with high-capacity/high-voltage cathodes such as LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) is a promising way to increase lithium battery energy density. Yet, the realization of high-performance full cells remains a formidable challenge. Here, we demonstrate a new class of highly coordinated, nonflammable carbonate electrolytes based on lithium bis(fluorosulfonyl)imide (LiFSI) in propylene carbonate/fluoroethylene carbonate mixtures. Utilizing an optimal salt concentration (4 M LiFSI) of the electrolyte results in a unique coordination structure of Li + -FSI - -solvent cluster, which is critical for enabling the formation of stable interfaces on both the thin Li metal anode and high-voltage NCM811 cathode. Under highly demanding cell configuration and operating conditions (Li metal anode = 35 μm, areal capacity/charge voltage of NCM811 cathode = 4.8 mAh cm -2 /4.6 V, and anode excess capacity [relative to the cathode] = 0.83), the Li metal-based full cell provides exceptional electrochemical performance (energy densities = 679 Wh kg cell -1 /1,024 Wh L cell -1 ) coupled with nonflammability.

25 ENERGY STORAGE↗

A scalable membrane electrode assembly architecture for efficient electrochemical conversion of CO2 to formic acid

Abstract The electrochemical reduction of carbon dioxide to formic acid is a promising pathway to improve CO 2 utilization and has potential applications as a hydrogen storage medium. In this work, a zero-gap membrane electrode assembly architecture is developed for the direct electrochemical synthesis of formic acid from carbon dioxide. The key technological advancement is a perforated cation exchange membrane, which, when utilized in a forward bias bipolar membrane configuration, allows formic acid generated at the membrane interface to exit through the anode flow field at concentrations up to 0.25 M. Having no additional interlayer components between the anode and cathode this concept is positioned to leverage currently available materials and stack designs ubiquitous in fuel cell and H 2 electrolysis, enabling a more rapid transition to scale and commercialization. The perforated cation exchange membrane configuration can achieve >75% Faradaic efficiency to formic acid at <2 V and 300 mA/cm 2 in a 25 cm 2 cell. More critically, a 55-hour stability test at 200 mA/cm 2 shows stable Faradaic efficiency and cell voltage. Technoeconomic analysis is utilized to illustrate a path towards achieving cost parity with current formic acid production methods.

08 HYDROGEN↗

A highly active, CO 2 -tolerant electrode for the oxygen reduction reaction

One challenge facing the development of high-performance cathodes for solid oxide fuel cells (SOFC) is the fast degradation rate of cathodes due to poisoning by contaminants commonly encountered in ambient air such as CO 2 . In this paper we report a double perovskite PrBa 0.8 Ca 0.2 Co 2 O 5+δ (PBCC) cathode with excellent ORR activity and remarkable CO 2 tolerance under realistic operation conditions. When tested in a symmetrical cell in air with ~1 vol% CO 2 at 750 °C, the PBCC electrode shows an area specific resistance of ~0.024 Ω cm 2 , which increases to 0.028 Ω cm 2 after 1000 h operation. The degradation rate is ~1/24 of that of the state-of-the-art La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF) cathode under the same conditions. Impedance spectroscopy and in situ surface enhanced Raman spectroscopy analyses indicate that the surface of the PBCC electrode is much more active for oxygen exchange and more robust against CO 2 than that of LSCF, as confirmed by density functional theory calculations. The fast ORR kinetics and excellent durability of PBCC in air with CO 2 highlight the potential of PBCC as a highly promising material for devices involving oxygen electrochemistry such as solid oxide fuel cells, electrolysis cells, or gas separation membranes.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Irreparable Interphase Chemistry Degradation Induced by Temperature Pulse in Lithium‐Ion Batteries

Abstract While it is widely recognized that the operating temperature significantly affects the energy density and cycle life of lithium‐ion batteries, the consequence of electrode‐electrolyte interphase chemistry to sudden environmental temperature changes remains inadequately understood. Here, we systematically investigate the effects of a temperature pulse (T pulse) on the electrochemical performance of LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) pouch full cells. By utilizing advanced characterization tools, such as time‐of‐flight secondary‐ion mass spectrometry, we reveal that the T pulse can lead to an irreversible degradation of cathode‐electrolyte interphase chemistry and architecture. Despite negligible immediate impacts on the solid‐electrolyte interphase (SEI) on graphite anode, aggregated cathode‐to‐anode chemical crossover gradually degrades the SEI by catalyzing electrolyte reduction decomposition and inducing metallic dead Li formation because of insufficient cathode passivation after the T pulse. Consequently, pouch cells subjected to the T pulse show an inferior cycle stability to those free of the T pulse. This work unveils the effects of sudden temperature changes on the interphase chemistry and cell performance, emphasizing the importance of a proper temperature management in assessing performance.

Cui, Zehao↗

Defect and structural evolution under high-energy ion irradiation informs battery materials design for extreme environments

Understanding defect evolution and structural transformations constitutes a prominent research frontier for ultimately controlling the electrochemical properties of advanced battery materials. Herein, for the first time, we utilize in situ high-energy Kr ion irradiation with transmission electron microscopy to monitor how defects and microstructures evolve in Na- and Li-layered cathodes with 3d transition metals. Our experimental and theoretical analyses reveal that Li-layered cathodes are more resistant to radiation-induced structural transformations, such as amorphization than Na-layered cathodes. The underlying mechanism is the facile formation of Li-transition metal antisite defects in Li-layered cathodes. The quantitative mathematical analysis of the dynamic bright-field imaging shows that defect clusters preferentially align along the Na/Li ion diffusion channels ( a-b planes), which is likely governed by the formation of dislocation loops. Our study provides critical insights into designing battery materials for extreme irradiation environments and understanding fundamental defect dynamics in layered oxides.

25 ENERGY STORAGE↗

Metal-Supported Ceria Electrolyte-based SOFC Stack for Scalable, Low-Cost, High-Efficiency and Robust Stationary Power Systems (Final Report)

This is the end of project report for the DOE Project DE-FE-0027844 “Metal-Supported Ceria Electrolyte-based SOFC Stack for Scalable, Low-Cost, High-Efficiency and Robust Stationary Power Systems”. The objectives of the project were to develop several technologies required for the mass adoption of Solid Oxide Fuel Cell systems for medium to large power generation applications. The key achievements of this project were: 1) Development of fuel cells with complete internal fuel reforming capability. 2) Fuel cell power scale up with production of cells with larger active areas. 3) Assembly of an integrated 5 kW modular stack platform capable of installation into medium to large power systems. 4) Demonstration of a 10 kW Fuel Cell Power System utilizing the integrated 5 kW modular stack platform. 5) Cost modelling to show system cost of $1,500/kW are achievable at production volumes. 6) Development of cathode air poison getters for reduced degradation and extended fuel cell life. 7) Assessment of fuel poison on anode degradation, particularly poisons frequently produced from the process of gasification of coal. The Cummins led Voice of Customer (VOC) work identified several significant markets for natural gas powered fuel cell systems, where the end customer is interested in reducing energy consumption and emissions, or increasing reliability of electrical supply. Data centers and truck Auxiliary Power Units (APU) were highlighted as 2 key future markets for fuel cell systems.

30 DIRECT ENERGY CONVERSION↗

Document restoration by computer techniques

Technique utilizes automated electronic data-processing machine to successfully recover illegible information from faded or age distorted documents. Once recovered, information can be displayed on cathode-ray-tube screen or reproduced in any desired size.

Mogavero, L.↗

Inert gas ion thruster development

Two 12 cm magneto-electrostatic containment (MESC) ion thrusters were performance mapped with argon and xenon. The first, hexagonal, thruster produced optimized performance of 48.5to 79 percent argon mass utilization efficiencies at discharge energies of 240 to 425 eV/ion, respectively, Xenon mass utilization efficiencies of 78 to 95 percent were observed at discharge energies of 220 to 290 eV/ion with the same optimized hexagonal thruster. Changes to the cathode baffle reduced the discharge anode potential during xenon operation from approximately 40 volts to about 30 volts. Preliminary tests conducted with the second, hemispherical, MESC thruster showed a nonuniform anode magnetic field adversely affected thruster performance. This performance degradation was partially overcome by changes in the boundary anode placement. Conclusions drawn the hemispherical thruster tests gave insights into the plasma processes in the MESC discharge that will aid in the design of future thrusters.

Ramsey, W. D.↗

A high power lithium thionyl chloride battery for space applications

A high power, 28 V, 330 A h, active lithium thionyl chloride battery has been developed for use as main and payload power sources on an expendable launch vehicle. Nine prismatic cells, along with the required electrical components and a built-in heater system, are efficiently packaged resulting in significant weight savings over presently used silver-zinc batteries. The high rate capability is achieved by designing the cells with a large electrochemical surface area and impregnating an electrocatalyst, polymeric phthalocyanine, into the carbon cathodes. Passivation effects are reduced with the addition of sulfur dioxide into the thionyl chloride electrolyte solution. The results of conducting a detailed thermal analysis are utilized to establish the heater design parameters and the thermal insulation requirements of the battery. An analysis of cell internal pressure and vent characteristics clearly illustrates the margins of safety under different operating conditions. Performance of fresh cells is discussed using polarization scan and discharge data at different rates and temperatures. Self-discharge rate is estimated based upon test results on cells after storage. Results of testing a complete prototype battery are described.

Shah, Pinakin M.↗

Automatic Control of Arc Process for Making Carbon Nanotubes

An automatic-control system has been devised for a process in which carbon nanotubes are produced in an arc between a catalyst-filled carbon anode and a graphite cathode. The control system includes a motor-driven screw that adjusts the distance between the electrodes. The system also includes a bridge circuit that puts out a voltage proportional to the difference between (1) the actual value of potential drop across the arc and (2) a reference value between 38 and 40 V (corresponding to a current of about 100 A) at which the yield of carbon nanotubes is maximized. Utilizing the fact that the potential drop across the arc increases with the interelectrode gap, the output of the bridge circuit is fed to a motor-control circuit that causes the motor to move the anode toward or away from the cathode if the actual potential drop is more or less, respectively, than the reference potential. Thus, the system regulates the interelectrode gap to maintain the optimum potential drop. The system also includes circuitry that records the potential drop across the arc and the relative position of the anode holder as function of time.

Scott, Carl D.↗