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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Assessment of Bulk Oxygen Capacity and Transient Redox Behavior of Foamed Lanthanum Strontium Manganese Perovskites

Synthesis of solar thermochemical hydrogen (STCH) production redox materials with engineered structures, for example, replica foams, can enable efficient heat and mass transport and are critical for scaled-up systems. Prior work has motivated the use of lanthanum strontium manganese (LSM)-type perovskites as foamed STCH materials, but the effect of their morphology on bulk and kinetic behavior has not been reported. In this work, replica and direct foamed samples of La 0.65 Sr 0.35 MnO 3-δ (LSM35) were fabricated and compared to synthesized powders and dense monoliths, and similarly synthesized CeO 2-δ (ceria) foams, regarding their specific reaction rates and bulk oxygen capacity/H 2 yields. Changes in oxygen capacity (Δδ) and reaction rates were measured between 1200 °C and 1400 °C by using fixed ratios of steam and hydrogen during both reduction and oxidation steps, allowing for analysis under practical high conversion conditions. Results suggest bulk behavior and reaction rates of the foamed LSM materials are comparable to their powder analogues. Differences in reaction rates were observed only when replica foamed samples were subjected to rapid laser heating (emulating conditions expected in solar furnaces), which is expected but has not been demonstrated at such a small scale. Here, foamed samples were further subjected to 50 redox cycles at 1400 °C to evaluate their stability. Results show no statistically significant decrease in hydrogen production for any of the foamed samples, but the direct foamed samples became brittle with time. Together, these results demonstrate the viability of replica foamed LSM perovskites for integration in scaled-up STCH systems.

08 HYDROGEN↗
DOE OSTI2020

Genetic Redundancy in Iron and Manganese Transport in the Metabolically Versatile Bacterium Rhodopseudomonas palustris TIE-1

The purple nonsulfur bacterium Rhodopseudomonas palustris TIE-1 can produce useful biochemicals such as bioplastics and biobutanol. Production of such biochemicals requires intracellular electron availability, which is governed by the availability and the transport of essential metals such as iron (Fe). Because of the distinct chemical properties of ferrous [Fe(II)] and ferric iron [Fe(III)], different systems are required for their transport and storage in bacteria. Although Fe(III) transport systems are well characterized, we know much less about Fe(II) transport systems except for the FeoAB system. Iron transporters can also import manganese (Mn). We studied Fe and Mn transport by five putative Fe transporters in TIE-1 under metal-replete, metal-depleted, oxic, and anoxic conditions. We observed that by overexpressing feoAB, efeU, and nramp1AB, the intracellular concentrations of Fe and Mn can be enhanced in TIE-1 under oxic and anoxic conditions, respectively. The deletion of a single gene/operon does not attenuate Fe or Mn uptake in TIE-1 regardless of the growth conditions used. This indicates that genetically dissimilar yet functionally redundant Fe transporters in TIE-1 can complement each other. Relative gene expression analysis shows that feoAB and efeU are expressed during Fe and Mn depletion under both oxic and anoxic conditions. The promoters of these transporter genes contain a combination of Fur and Fnr boxes, suggesting that their expression is regulated by both Fe and oxygen availability. The findings from this study will help us modulate intracellular Fe and Mn concentrations, ultimately improving TIE-1’s ability to produce desirable biomolecules.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

The Sensitivity of Nickel Substitution in the Structural Design of Manganese-Based Layered and Lithiated Spinel Electrodes for Li-Ion Batteries

A concerted effort is being made at Argonne National Laboratory to explore and develop high-performance lithium-manganese-nickel-oxide cathode materials for the lithium battery industry. They are both energy- and cost-competitive relative to cobalt- and nickel-rich systems, such as LiCoO 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , and LiNi 0.8 Mn 0.1 Co 0.1 O 2 . The recent discovery of the structural versatility of LiNi 0.5 Mn 0.5 O 2 , has revealed that it can exist in three configurations: lithiated spinel, partially disordered layered, and completely disordered rock salt within a common cubic-close-packed oxygen array. This versatility opens up the possibility of designing structurally integrated electrode components with interlinking 2-D (layered) and 3-D (spinel) channels for Li-ion transport. This paper highlights the sensitivity of Ni substitution and synthesis temperature on the structural and electrochemical properties of LiNi 0.50 Mn 0.50 O 2 , LiNi 0.53 Mn 0.47 O 2 , LiNi 0.47 Mn 0.53 O 2 , and LiNi 0.25 Mn 0.75 O 2 electrodes, as well as a cobalt-containing composition, LiNi 0.333 Mn 0.333 Co 0.333 O 2 , when synthesized at a relatively low temperature of 400 °C.

25 ENERGY STORAGE↗
DOE OSTI2025

Cycling Performance and Structure Evolution of Co-Free Lithium- and Manganese-Rich Layered Oxides in Lithium-Ion Batteries

Lithium- and manganese-rich (LMR) layered oxides are high-capacity cathode materials that are being considered for electric vehicle (EV) lithium-ion batteries (LIBs). Here, we investigate the electrochemical cycling behavior of cells containing a cobalt-free LMR oxide, 0.3Li 2 MnO 3 ·0.7LiMn 0.5 Ni 0.5 O 2 , paired with either Li or graphite anodes. Two- and three-electrode cells are cycled under varying conditions to examine the effects of oxide activation, upper cutoff voltage, separator type, and electrolyte composition. Post-cycling characterization of harvested electrodes, with electrochemical, X-ray absorption spectroscopy, and solid-state 6 Li nuclear magnetic resonance spectroscopy techniques, are used to correlate cell performance changes with redox state evolution in the oxide and Li inventory shifts in the cell. Our results show that capacity fade and impedance rise primarily originate at the graphite anode and LMR cathode, respectively. Notably, while Ni undergoes reversible redox, Mn shows no evidence of bulk redox activity even in highly-aged electrodes: only relithiated LMR electrodes show some reduction of Mn. Graphite electrodes degrade due to particle isolation and SEI growth, exacerbated by Mn dissolution and deposition on graphite anodes. These findings highlight the coupled structural and electrochemical degradation mechanisms in LMR/graphite cells and underscore lithium inventory retention and electrode interfacial stability as critical factors for enhancing long-term performance.

Badami, Pavan P. [Argonne National Laboratory (ANL↗
DOE OSTI2025

Lithium-Ion Batteries with Lithium Manganese Iron Phosphate Cathodes and Lithium Titanate Anodes: Linking Electrode Dynamics to Cell Performance

This study examines the electrochemical performance, impedance behavior, and aging mechanisms of lithium-ion cells pairing lithium manganese iron phosphate (LiMn 0.6 Fe 0.4 PO 4 , LMFP64) cathodes with lithium titanate (Li 4 Ti 5 O 12 , LTO) anodes. LMFP64 half-cells display distinct Fe and Mn redox plateaus at ∼3.5 and ∼4.1 V, respectively, and deliver excellent rate capability. Three-electrode measurements show that LMFP64 dominates cell impedance, which changes sharply across the Fe–Mn redox transition and decreases with increasing temperature (30 °C–50 °C). Voltage hysteresis arises mainly from the cathode, with higher C-rates shortening redox plateaus and broadening the transition region. Elevated temperature lowers impedance, especially near the Mn-redox and transition regions, but accelerates capacity fade. Post-cycling analyses of electrodes confirm structural stability of LMFP64 and indicate loss of lithium inventory (LLI) as the source of capacity fade. This LLI causes potential slippage between the LMFP64 and LTO electrodes, which decreases the Fe-redox plateau width. Long-term cycling highlights the critical role of electrode overhang: cathode overhang mitigates capacity fade by buffering lithium loss, whereas anode overhang cells experience faster capacity decline due to uncompensated lithium depletion. These results clarify LMFP64/LTO battery impedance evolution, thermal effects, and degradation pathways and provide insights for their applications in electric vehicles.

Area Specific Impedance↗
DOE OSTI2026

Cobalt-Free Lithium and Manganese Rich Cathodes for Electric Vehicle Applications: Influence of Inherent Properties on Temperature-Dependent Performance

Lithium- and manganese-rich (LMR) oxides are attractive options as next-generation, earth-abundant cathodes. Despite inherent properties that result in less-than-ideal performance, advancements in this class of cathodes toward commercialization have been steady. Herein, we report a benchmark study on the influence these inherent properties exert on the discharge rate of Co-free, LMR//graphite (Gr) cells as a function of temperature. Because low-temperature performance is an essential consideration in the design of electric vehicle cells, understanding the limitations of current LMR systems is essential in understanding their current applicability as well as strategies for improvement. This work identifies two major limitations in the rate performance of LMR//Gr cells and suggests several areas of focus where practical strategies may provide improvements.

25 ENERGY STORAGE↗
DOE OSTI2020

Kinetics Data of Iron(II), Manganese(II), Dissolved Organic Carbon and Nitrate from Batch Incubation Experiments Using Hyporheic Sediments from the East River Watershed, Colorado.

Hyporheic zones act as critical ecological links between terrestrial and aquatic systems where redox-sensitive metals of iron (Fe) and manganese (Mn) significantly impact nutrient cycling and water quality. In order to understand the production, release and speciation of Fe(II) and Mn(II) in groundwater, we conducted batch incubation experiments using sediment samples from a hyporheic zone of the East River floodplain in Colorado. The East River is part of the Watershed Function Scientific Focus Area (WFSFA) located in the Upper Colorado River Basin, United States. Collection and processing of the data is described in the Methods, along with details of data file contents. There are 6 data files provided in two formats: 1 zip-folder of .csv (open source) files, and 1 zip-folder of .xlsx (Excel) files. The data tables provided in the two formats are the exact same.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Amorphous Mn2SiO4: A potential manganese phase in the stagnant slab

Abstract Tephroite (Mn2SiO4), together with some manganese (Mn)-rich mineral inclusions, has been found in ophiolite-hosted diamonds, possibly originating from Mn-nodules and sediments that were once deposited on the oceanic floor and later subducted into the deep mantle, which provides evidence for oceanic crustal recycling. However, the state and behavior of tephroite under high-pressure and high-temperature conditions remain poorly understood. In this study, we conducted in situ synchrotron single-crystal X-ray diffraction (XRD) and Raman spectroscopy of synthetic tephroite up to ~30 GPa and ~900 K. The XRD and Raman spectroscopy experiments in this study first show that tephroite undergoes a pressure-induced, irreversible, amorphous transformation above ~20 GPa. Temperature (<900 K) is found to be an insignificant factor governing the process of amorphous transformation. Amorphous tephroite may be a potential phase in a rapidly cooling oceanic lithospheric subduction slab stagnating at the bottom of the mantle transition zone.

Geochemistry & Geophysics↗
DOE OSTI2022

Evaluation of the Impact of Additional Manganese from the Recycle Collection Tank (RCT) Glycolate Destruction Process on Glass Properties

The Defense Waste Processing Facility (DWPF) is planning to implement glycolic acid as a reductant within the waste processing flowsheet. An assessment of the glycolic acid flowsheet has revealed the potential for thermolytic production of hydrogen in the Concentration, Storage and Transfer Facilities (CSTF) from glycolate entrained in the DWPF recycle stream. To mitigate this potential scenario, a glycolate destruction process utilizing sodium permanganate (NaMnO 4 ) is being developed for use in the DWPF Recycle Collection Tank (RCT). The RCT is fed by the Slurry Mix Evaporator Condensate Tank (SMECT) and the Off-Gas Condensate Tank (OGCT). The SMECT could receive glycolate via a foamover from the Sludge Receipt and Adjustment Tank (SRAT) or the Slurry Mix Evaporator (SME), and the OGCT could receive glycolate via carryover of sludge particles in the purge from the melter during surge conditions. The use of NaMnO 4 additions in the RCT will result in additional manganese (Mn) in the waste stream and needs to be evaluated.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

The In Situ Observation of Phase Transformations During Intercritical Annealing of a Medium Manganese Advanced High Strength Steel by High Energy X-Ray Diffraction

Microstructural changes during thermal processing of a medium manganese steel containing (in wt%) 0.19C and 4.39 Mn were evaluated in situ with a high energy X-ray diffraction system (HEXRD). Samples with an initial fully martensitic microstructure were heated to intercritical annealing (IA) temperatures of 600 or 650°C, held for 30 min, and cooled to room temperature. Diffraction data were analyzed to determine the variations in austenite and ferrite phase fractions and phase lattice constants throughout the ICA cycles. On heating, the 2 vol. pct of austenite present in the starting microstructure decomposed, and cementite precipitation then occurred. During isothermal holding, the austenite fraction increased, up to 20% for the sample annealed at 650°C. The measured austenite fractions were less than those calculated by Thermo-Calc for equilibrium conditions, indicating that the 30-min hold time was insufficient to achieve near-equilibrium conditions. Observed changes in lattice parameters during isothermal holding were interpreted to reflect composition changes due to redistribution of the C and Mn between austenite and ferrite. The results are discussed in relation to the potential for controlling austenite stability during ambient temperature deformation.

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

North America’s Potential for an Environmentally Sustainable Nickel, Manganese, and Cobalt Battery Value Chain

The Detroit Big Three General Motors (GMs), Ford, and Stellantis predict that electric vehicle (EV) sales will comprise 40–50% of the annual vehicle sales by 2030. Among the key components of LIBs, the LiNixMnyCo1−x−yO2 cathode, which comprises nickel, manganese, and cobalt (NMC) in various stoichiometric ratios, is widely used in EV batteries. This review reveals NMC cathodes from laboratory research. Furthermore, this study examines the environmental effect of NMC cathode production for EV batteries (including coating technologies), encompassing aspects such as energy consumption, water usage, and air emissions. Although gaps persist in NMC cathode environmental assessments (NMC111, NMC532, NMC622, and NMC811), limited life cycle assessments “(LCA)” have been conducted. Most available data originate from Asia (primarily China), accounting for 85% of the production of EV LIB cathode materials. The concept of battery passports for data collection on LIB components has been proposed to facilitate material traceability as a system for ensuring a sustainable supply chain for critical minerals. The automotive industry’s shift to electrification necessitates a sustainable supply chain from mine to vehicle end-of-life. As the critical mineral supply moves from Asia to North America, environmentally friendly industrial methods must be studied to provide this supply chain direction.

25 ENERGY STORAGE↗
DOE OSTI2021

Supplemental Data for the Manuscript: Quantification of Manganese for ChemCam Mars and Laboratory Spectra Using a Multivariate Model

This dataset includes all of the data needed to validate and/or reproduce the manganese calibration model described in the manuscript. The reference database contains metadata for the new Mn-bearing standards, minerals, and mixtures that are > 2.9 wt.% MnO. In addition, the files include the MnO composition data for all standards used, non-normalized spectral data, mean peak area spectrum, results of outlier determination, RMSECV data, regression vectors, and Test Set predictions.

58 GEOSCIENCES↗
DOE OSTI2021

Pt Catalysts Modified with Manganese Oxide through Atomic Layer Deposition for CO Oxidation: Establishing a Coating Layer above or below Pt

The effect of atomic layer deposition (ALD) of manganese oxide on CO oxidation over Pt/Al2O3 is investigated. Two types of catalysts with a thin MnOx layer coated on or under the Pt nanoparticles (NPs) are prepared, and a pristine Pt/Al2O3 catalyst is used as a reference sample. The addition of the ALD layers improves the catalyst durability and both catalysts with MnOx exhibit greater stability after thermal aging at 1073-K. Besides, MnOx promotes CO oxidation through active Pt-MnOx interfacial sites, showing a reaction rate up to 35-fold faster than that of unmodified Pt. Interestingly, the CO adsorption ability of the Pt catalysts with MnOx overcoats is greatly suppressed after the high-temperature calcination; however, the reaction rate of CO oxidation is still excellent. This phenomenon is because the uniformly covered MnOx with two atomic layers diminishes the exposed Pt surface, but the reaction near the Pt-MnOx interfacial site still occurs. Our results guide the effective use of ALD, which is actively applied to heterogeneous catalysis, and provide a novel direction to control metal-assisted interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Manganese-cobalt spinel oxide nanowire arrays

Manganese-cobalt (Mn—Co) spinel oxide nanowire arrays are synthesized at low pressure and low temperature by a hydrothermal method. The method can include contacting a substrate with a solvent, such as water, that includes Mn04- and Co2 ions at a temperature from about 60° C. to about 120° C. The method preferably includes dissolving potassium permanganate (KMn04) in the solvent to yield the Mn04- ions. the substrate is The nanoarrays are useful for reducing a concentration of an impurity, such as a hydrocarbon, in a gas, such as an emission source. The resulting material with high surface area and high materials utilization efficiency can be directly used for environment and energy applications including emission control systems, air/water purifying systems and lithium-ion batteries.

Gao, Pu-Xian↗
DOE OSTI2022

Alternate Synthesis Method for High-Performance Manganese Rich Cation Disordered Rocksalt Cathodes

Cation-disordered rocksalt (DRX) cathodes have recently emerged as a promising class of cobalt-free, high-capacity cathodes for lithium-ion batteries. To facilitate their commercialization, the development of scalable synthesis techniques providing control over composition and morphology is critical. To this end, a sol-gel synthesis route to prepare Mn-rich DRX cathodes with high capacities is presented here. Several compositions with varied Mn content and nominal F doping are successfully prepared using this technique. In-situ X-ray diffraction measurements demonstrate that DRX formation proceeds at moderate temperature (800 °C) through the sol-gel route, which enables intimate mixing among reactive intermediate phases that form at lower temperatures. All synthesized compositions possess cation short-range order, as evidenced by neutron pair distribution function and electron diffraction analysis. These DRX materials demonstrate promising electrochemical performance with reversible capacities up to 275 mAh g. Compared to the baseline oxide (Li 1.2 Mn 0.4 Ti 0.4 O 2 ), the Mn-rich compositions exhibit improved cycling stability, with some showing an increase in capacity upon cycling. Finally, this study demonstrates the feasibility of preparing high-capacity DRX cathodes through a sol-gel based synthesis route, which may be further optimized to provide better control over the product morphology compared to traditional synthesis methods.

25 ENERGY STORAGE↗
DOE OSTI2020

Structural Stabilization of P2-type Sodium Iron Manganese Oxides by Electrochemically Inactive Mg Substitution: Insights of Redox Behavior and Voltage Decay

Layered P2-type Na 0.8 Mn 0.5 Fe 0.5 O 2 cathode material is a promising candidate for next-generation sodium-ion batteries due to the economical and environmentally benign characteristics of Mn and Fe. The poor cycling stability of the material, however, is still a problem that must be solved. To address the problem, here, electrochemically inactive Mg 2+ was introduced into the structure by substituting some of the Fe ions. It was shown that Mg substitution led to a smoother voltage profile with improved cycling performance and rate capability. These observations were attributed to the suppressed structural changes during electrochemical processes. Detailed redox mechanisms, associated local structural changes, and phase transitions were investigated by X-ray absorption spectroscopy and X-ray diffraction. From the detailed analysis of electrochemical behaviors, it was also identified how the redox reactions and structural disordering occurred in the high-and low-voltage regions and how Mg substitution stabilized the structure.

25 ENERGY STORAGE↗