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Results for “cobalt oxide”

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 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1987

Phase equilibria in the iron oxide-cobalt oxide-phosphorus oxide system

Two novel ternary compounds are noted in the present study of 1000 C solid-state equilibria in the Fe-Co-P-O system's Fe2O3-FePO4-Co3(Po4)2-CoO region: CoFe(PO4)O, which undergoes incongruent melting at 1130 C, and Co3Fe4(PO4)6, whose incongruent melting occurs at 1080 C. The liquidus behavior-related consequences of rapidly solidified cobalt ferrite formation from cobalt ferrite-phosphate melts are discussed with a view to spinel formation. It is suggested that quenching from within the spinel-plus-liquid region may furnish an alternative to quenching a homogeneous melt.

De Guire, Mark R.↗
DOE OSTI2024

Chemo-Mechanical Instabilities in Lithium Cobalt Oxide at Higher State-Of-Charge in Li-Ion Batteries

Transition metal oxide cathodes are widely used in commercial Li-ion batteries. However, their practical charge capacity is limited due to severe chemo-mechanical instabilities at higher charge voltage, and state-of-charge condition. Here, in situ stress and strain measurements were synchronized to probe mechanical deformations in the lithium cobalt oxide (LCO) cathode via a multi-beam stress sensor and digital image correlation, respectively. In situ mechanical measurements revealed how Li removal from the electrode structure induces deformations on the LCO composite cathodes during cycling. The structure and morphology of the LCO cathodes were further investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies. Two distinct electrochemical and mechanical behaviors were identified when the LCO was charged up to 4.65 V. The LCO undergoes a compressive stress generation when charged up to 4.2 V and surface fractures on the LCO particles were detected by SEM. LCO cathode experienced significantly large contractions (negative strains) when charged up to 4.65 V, where intergranular crack formation and phase transformation were detected on the LCO particles via SEM and XRD, respectively. Overall, the study bridges complicated structural deformations with in situ analysis of mechanical degradations in LCO cathodes charged at higher voltages. The correlation is vital to understanding instability mechanisms in transition metal oxides at high voltages for alkali metal ion batteries.

higher state-of-charge↗
DOE OSTI2023

High-Temperature Air Stability of Electrodeposited Copper Cobalt Oxide and Copper Manganese Oxide Absorber Coatings for Concentrating Solar Power

The solar absorptance of a thermal receiver surface significantly affects the photothermal conversion efficiency of concentrating solar power (CSP) plants. The stability of solar receivers and coatings applied to improve solar absorptance at high temperatures is critical for efficient and long-term operation. This study analyzes the high-temperature air stability of multiscale fractal textured electrodeposited copper manganese oxide and copper cobalt oxide solar receiver coatings over a range of temperatures. The study also investigates the effect of high temperature on phase stability, chemical and morphological evolution, and the optical properties of the two solar absorber materials. A computational model is developed to determine the absorptance of the textured absorbers and is shown to match the experimental measurements closely over a range of heat treatment temperatures from 450 °C to 850 °C and durations up to 100 h. Degradation curves and coating stability maps are developed from the study. Copper manganese oxide and copper cobalt oxide coatings exhibit good thermal stability up to ~815 °C and 630 °C, respectively, with minimal changes in their optical and structural properties with thermal efficiency greater than 90%. Furthermore, the study offers valuable insights into the high-temperature annealing effects on the optical and structural properties of multiscale copper alloyed coatings fabricated by electrodeposition and presents a means of designing the optimal temperature range for maximizing absorber efficiency in practical applications.

14 SOLAR ENERGY↗
NASA NTRS1980

Preliminary study of a solar selective coating system using black cobalt oxide for high temperature solar collectors

Black cobalt oxide coatings (high solar absorptance layer) were deposited on thin layers of silver or gold (low emittance layer) which had been previously deposited on oxidized (diffusion barrier layer) stainless steel substrates. The reflectance properties of these coatings were measured at various thicknesses of cobalt for integrated values of the solar and infrared spectrum. The values of absorptance and emittance were calculated from the measured reflectance values, before and after exposure in air at 650 C for approximately 1000 hours. Absorptance and emittance were interdependent functions of the weight of cobalt oxide. Also, these cobalt oxide/noble metal/oxide diffusion barrier coatings have absorptances greater than 0.90 and emittances of approximately 0.20 even after about 1000 hours at 650 C.

Mcdonald, G.↗
DOE OSTI2024

First-principles study of the structures and redox mechanisms of Ni-rich lithium nickel manganese cobalt oxides

To reduce the cobalt (Co) content in lithium-ion batteries, Ni-rich (high-Ni) lithium nickel manganese cobalt oxides (NMC) are pursued as one of the next-generation cathode materials. However, there is still debate on the crystal and electronic structures of the baseline, LiNiO 2 . Density Functional Theory (DFT) calculations were performed to provide a theoretical understanding of Ni-rich NMC. First, it was found that the commonly used $R\bar{3}m$ structure for LiNiO 2 is metallic, contrary to the experimentally reported mix-conducting behavior. Among the four different space groups, $R\bar{3}m$, C2/m, P2 1 /c, and P2/c, P2/c with charge disproportionation of Ni 2+ and Ni 4+ is the most energetically stable and semiconducting structure of LiNiO 2 . Therefore, the atomic structures of representative Ni-rich NMC were built by partially replacing Ni with Co or Mn in the P2/c LiNiO 2 to form Li x Ni y Mn z Co 1-y-z O 2 . In the fully lithiated (x=1.0) high Ni content NMC (y>0.5), the oxidation state of all Mn ions becomes 4+, while Co ions still maintain 3+, and part of the Ni ions become 3+ to compensate for the charge. Upon delithiation, the local environment shows more variation of the charge states on the transition metal (TM) ions. The average oxidation on each TM follows a sequence of losing electrons that starts from Ni 2+ to Ni 3+ , then oxidizing Ni 3+ and Co 3+ , while Mn 4+ remains electrochemically inactive till x=0. Finally, a general relationship for the oxidation state change in each TM as a function of x is derived and shows agreement with both modeling and experimental data.

25 ENERGY STORAGE↗
NASA NTRS1980

Preliminary study of a solar selective coating system using black cobalt oxide for high temperature solar collectors

Black cobalt oxide coatings were deposited on thin layers of silver or gold which had been deposited on oxidized stainless steel substrates. The reflectance properties of these coatings were measured at various thicknesses of cobalt oxide for integrated values of the solar and infrared spectrum. The values of absorptance and emittance were calculated from the measured reflectance values before and after exposure in air at 650 C for 1000 hours. Also, these cobalt oxide/noble metal/oxide diffusion barrier coatings have absorptances greater than 0.90 and emittances of approximately 0.20 even after about 1000 hours at 650 C.

Mcdonald, G.↗
DOE OSTI2021

Manipulating cobalt oxide on N-doped aligned electrospun carbon nanofibers towards instant electrochemical detection of dopamine secreted by living cells

A demand exists for the development of miniaturized biosensors with high sensitivity and a wide dynamic range for rapid detecting dopamine (DA) levels. Here, an electrochemical sensor is created by decorating closely packed cobalt oxide (Co 3 O 4 ) nanograins on nitrogen-doped electrospun carbon nanofibers (NECNFs) via a facile electrodeposition method. The carbon nanofiber matrix provides both a scaffold with ultrahigh surface area for homogeneous dispersion of cobalt oxide nanostructures and facilitates the electrochemical conductivity for the hybrid electrode. The sensing principle is based on the redox reaction between DA and DA quinone that generates electrical signal, which is detectable via differential pulse voltammetry (DPV) and chronoamperometry (CA). Owing to a high electroactive surface area and facilitating electron transfer between electrode surface and the target molecule, the electrical sensing platform exhibits superior sensitivity and selectivity toward DA, with an excellent limit of detection (9 nM) over a wide range of concentrations (0.01 to 100 μM). Moreover, based on its excellent sensing properties and biocompatibility, the sensor has been used for the real-time monitoring exogeneous DA released from pheochromocytoma (PC12) cells. This work demonstrates promise of a novel sensor technology that may render rapid point-of-care testing of DA towards early clinical diagnosis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Interfacial Charge Transfer and Substrate-Dependent Oxidation States Drive SMSI Enhancements in Cobalt Oxide Films

Here, we investigated the mechanisms underlying strong metal-support interactions in CO oxidation using model systems where noble metal crystals support reducible, monolayer-thick CoO x films. The effect of the Co oxidation state, film thickness, and substrate identity were studied in varying reaction conditions using ambient pressure X-ray photoelectron spectroscopy. At low O 2 pressures, the same oxide phase forms on both Pt(111) and Au(111) surfaces. But when heated at higher O 2 pressures, the oxide phase depends on the substrate. We found that CoO x /Pt is more active for the CO oxidation reaction than CoO x /Au, even when both surfaces stabilize the same oxide phase. DFT calculations on these and related noble-metal-supported CoO x films reveal an SMSI-induced reactivity enhancement that strongly depends on the oxide film thickness and which is mediated by charge transfer between the metal and oxide. Charge transfer is also found to correlate with the reaction energy and activation barrier for CO oxidation. This effect was found to be greatest for oxide films on Pt, decreasing on other noble metal supports in the order Pt > Pd > Au > Ag, in agreement with the experiments. The role of charge transfer in the activation barriers and reaction energies provides insight into the nature of SMSI-induced catalytic activity, and suggests that the noble metal work function can serve as an indicator for the strength of SMSI effects.

36 MATERIALS SCIENCE↗
DOE OSTI2026

The Influence of Mesoscale Particle Structure on the Electrode Degradation and Resultant Electrochemistry of Lithium Ion Cells With Nickel Rich Lithium Nickel Manganese Cobalt Oxide Positive Electrodes

Nickel-rich lithium nickel manganese cobalt oxide, NMC (LiNi x Mn y Co z O 2 ), materials are desirable positive electrodes in lithium ion batteries, providing high capacity and energy density. The mesoscale structure of NMC materials is commonly a polycrystalline aggregate, providing opportunity for short lithium ion transport distance of the small primary particles, yet facile material handling due to the larger secondary particles. On (de)lithiation the NMC unit cell changes volume, where the anisotropic strain can result in secondary particle fracture. This secondary particle fracture process during cycling has been associated with several degradation modes of NMC materials in LIBs. In this work, a milling process was determined whereby the secondary particles could be pre-fractured with retention of the parent primary particle crystallographic structure, crystallite size, and morphology, providing the ability to unambiguously determine the influence of NMC secondary particle size and mesostructure on resultant functional behavior. The bulk and interfacial properties and electrochemistry of as-received commercially obtained polycrystal NMC811 (LiNi 0.8 Mn 0.1 Co 0.1 O 2 , PC NMC) and its milled MPC NMC counterpart were compared. The smaller secondary particle size, higher surface area MPC NMC was found to result in 1) greater cathode tortuosity, 2) reduced surface Ni on the cycled MPC cathodes consistent with surface reconstruction, and 3) increased Ni deposition on the anodes from cathode-anode crosstalk. These factors manifested in unfavorable electrochemical behavior of MPC with lower functional capacity at both 1C and C/10 rates and higher impedance over extended moderate voltage (dis)charge cycling.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Efficient Leaching of Metal Ions from Spent Li-Ion Battery Combined Electrode Coatings Using Hydroxy Acid Mixtures and Regeneration of Lithium Nickel Manganese Cobalt Oxide

Extensive use of Li-ion batteries in electric vehicles, electronics, and other energy storage applications has resulted in a need to recycle valuable metals Li, Mn, Ni, and Co in these devices. In this work, an aqueous mixture of glycolic and lactic acid is shown as an excellent leaching agent to recover these critical metals from spent Li-ion laptop batteries combined with cathode and anode coatings without adding hydrogen peroxide or other reducing agents. An aqueous acid mixture of 0.15 M in glycolic and 0.35 M in lactic acid showed the highest leaching efficiencies of 100, 100, 100, and 89% for Li, Ni, Mn, and Co, respectively, in an experiment at 120 °C for 6 h. Subsequently, the chelate solution was evaporated to give a mixed metal-hydroxy acid chelate gel. Pyrolysis of the dried chelate gel at 800 °C for 15 h could be used to burn off hydroxy acids, regenerating lithium nickel manganese cobalt oxide, and the novel method presented to avoid the precipitation of metals as hydroxide or carbonates. The Li, Ni, Mn, and Co ratio of regenerated lithium nickel manganese cobalt oxide is comparable to this metal ratio in pyrolyzed electrode coating and showed similar powder X-ray diffractograms, suggesting the suitability of α-hydroxy carboxylic acid mixtures as leaching agents and ligands in regeneration of mixed metal oxide via pyrolysis of the dried chelate gel.

Electrochemistry↗
NASA NTRS1987

DC electrical, thermal, and spectroscopic properties of various condensation polyimides containing surface cobalt oxide

Doping polyimides with cobalt ion causes the room temperature direct current electrical resistivity to decrease relative to the polymer alone, the reduction being most pronounced for the air-side of the cobalt modified polyimides. At a constant electrical field, resistivity for the volume, air-side and glass-side modes decreases yet further with an increase in temperature as expected for semiconductors and insulators. X-ray photoelectron spectroscopy indicates the air-side of the cobalt modified polyimides is predominantly Co3O4. The bulk resistivity of the air-side and activation energy of conduction for this surface are comparable to high purity sintered Co3O4. Charging characteristics at room temperature indicate a substantial polymer matrix contribution to both the glass-side and volume mode measurements but a negligible contribution to the air-side electrical properties. Volume electrical resistivity for similar additive levels is reduced by increasing the molecular flexibility of the host polymer.

Rancourt, J. D.↗
NASA NTRS2005

Cobalt Oxide Hollow Nanoparticles Derived by Bio-Templating

We present here the first fabrication of hollow cobalt oxide nanoparticles produced by a protein-regulated site-specific reconstitution process in aqueous solution and describe the metal growth mechanism in the ferritin interior.

Kim, Jae-Woo↗
DOE OSTI2023

Engineering Active Surface Oxygen Sites of Cubic Perovskite Cobalt Oxides toward Catalytic Oxidation Reactions

Unraveling the role of surface oxygen sites in transition metal oxides during catalytic reactions has always been the focus of environmental and energy chemistry research. For this work, active surface oxygen sites of cubic perovskite cobalt oxide were engineered to comprehend their crucial role and catalytic mechanism at the molecular level. By removing those inert Sr/La–O termination layers, active oxygen sites were exposed on the Co terminated surface of Sr 0.6 La 0.4 CoO 3–δ that furnished the dominant catalytic process of CO oxidation via the Mars–van Krevelen (MvK) mechanism. The fabrication of five-coordinate cobalt ions and the enhanced covalency of Co–O bonds not only optimize the surface electronic structure of Co 3d–O 2p, but also supply active surface oxygen sites, which effectively oxidizes CO to CO 2 with a significantly improved oxidation performance and stability as evidenced by soft/hard XAS, XPS, and O 2 -TPD. Furthermore, online isotopic 18 O 2 mass spectrometry, in situ DRIFTS, and theoretical simulation demonstrate that the activity of surface oxygen sites enhances the kinetics of the MvK reaction, while unsaturated coordination sites from five-coordinate cobalt ions primarily contribute to the activated oxygen molecules and the stable catalytic cycle. The results reported here provide a deep insight into the comprehension of the relationships among active oxygen sites, surface electronic structure, and the reaction mechanism of transition metal oxides necessary for catalytic oxidation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Progress in direct recycling of spent lithium nickel manganese cobalt oxide (NMC) cathodes

With the widespread use of lithium-ion batteries (LIBs) in portable electronics and electric vehicles (EVs), the end-of-life (EOL) LIBs are projected to reach 1336 GWh by 2040 under the sustainable development scenario. Proper recycling is urgently needed to minimize the release of hazardous waste and reduce mining activities by reintroducing critical minerals into the supply chain. Lithium nickel manganese cobalt oxide (LiNi x Mn y Co z O 2 , NMCs) cathodes have become dominant in the LIB market, especially with the increasing production of EVs, which are also the most valuable components in EOL LIBs. Unlike pyrometallurgical and/or hydrometallurgical methods, which convert spent NMCs into metals or metal compounds, direct recycling technologies aim to maximize the value of spent cathodes by restoring their degraded structure and composition. Furthermore, this review summarizes direct recycling methods for NMC cathodes published in the last decade and provides insights into the challenges and future development of direct recycling techniques.

Cathode↗
DOE OSTI2025

Revealing Progressive Degradation of Cobalt Oxide Nanoparticles During Thermochemical Redox Cycling via Operando STEM-EELS

Metal oxides are promising materials for long-duration thermochemical energy storage. Efforts to characterize their reaction kinetics, conversion rate, and morphological evolution during thermochemical cycling have largely focused on bulk and microscale measurements. However, the design of nanostructured metal oxides could improve the reaction reversibility and kinetics, warranting the development of platforms to investigate how these materials behave at the nanoscale. Here, we demonstrate the use of correlative, time-resolved electron energy loss spectroscopy and imaging in an environmental transmission electron microscope for studying the thermochemical cyclability of cobalt oxide nanoparticles with high spatial and temporal resolution. The spectroscopic data reveal a striking decrease in reaction kinetics after the first cycle, resulting from sintering-driven nanostructural densification. Comparison between cycling in humid and dry air shows that atmospheric conditions can modulate reaction transition temperatures but have limited effects on sintering over multiple cycles, suggesting long-term durability will instead rely on synthetic and/or nanostructural modifications.

25 ENERGY STORAGE↗
DOE OSTI2025

Reciprocal Ternary Molten Salts Enable the Direct Upcycling of Spent Lithium‐Nickel‐Manganese‐Cobalt Oxide (NMC) Mixtures to Make NMC 622

Cathode active material is the most valuable component of spent lithium‐ion batteries, accounting for ≈30% of their overall value. Direct recycling of cathode materials involves recovering, regenerating, and reusing them without breaking down their chemical structure. This approach maximizes the added value of the cathode compound and reduces manufacturing costs by avoiding the need for virgin material production. However, one key challenge in scaling direct recycling from lab to industry is the requirement for highly purified cathode materials, contrasting with the low purity of black mass generated from battery shredding. No efficient separation process currently exists to isolate different lithium‐nickel‐manganese‐cobalt oxides (NMCs) from each other. Thus, direct recycling technologies that can operate with mixtures of multiple NMC stoichiometries will be best‐suited for industrial adoption. This study explores the direct recycling of NMC mixtures into NMC 622 using a “reciprocal ternary molten salts (RTMS)” system. Ionothermal relithiation and upcycling within the RTMS system successfully restore the layered structure, lithium content, and electrochemical performance of degraded NMCs, yielding results comparable to pristine NMC 622 (P‐NMC 622).

25 ENERGY STORAGE↗