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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 559 records · Page 31
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Spectroscopic and dielectric response of zinc bismuth phosphate glasses as a function of chromium content

Graphical abstract: 20ZnF{sub 2}–(20 − x)Bi{sub 2}O{sub 3}–60P{sub 2}O{sub 5}:xCr{sub 2}O{sub 3} (0 ≤ x ≤2 mol%) glasses are prepared by melt quenching technique. The optical absorption spectra of present glasses are analyzed as a function of chromium content. The absorption bands are assigned to {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 1g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 2g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 2}T{sub 1g}(G) and {sup 4}A{sub 2g}(F) ⟶ {sup 2}E{sub g}(G) transitions of Cr{sup 3+} ions. - Highlights: • ZnF{sub 2}–Bi{sub 2}O{sub 3}–P{sub 2}O{sub 5}:Cr{sub 2}O{sub 3} glasses were prepared by melt quenching and annealing. • Spectroscopic and dielectric properties of chromium ions were investigated. • ESR and optical absorption spectra indicate the co-existence of Cr{sup 6+} ions with Cr{sup 5+} ions and Cr{sup 3+} ions. • Cr{sup 3+} ions act as modifiers and influence the semiconducting nature of the glass system. - Abstract: 20ZnF{sub 2}–(20 − x)Bi{sub 2}O{sub 3}–60P{sub 2}O{sub 5}:xCr{sub 2}O{sub 3} (0 ≤ x ≤2 mol%) glasses are prepared by melt quenching technique. Amorphous nature of these samples is confirmed by X-ray diffraction (XRD) analysis. FTIR study reveals bands due to CrO{sub 6}(o{sub d}) and CrO{sub 4}{sup 2−}(T{sub d}) units along with conventional phosphate groups. The optical absorption and ESR studies of present glasses are analyzed as a function of chromium content. The absorption bands are assigned to {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 1g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 2g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 2}T{sub 1g}(G) and {sup 4}A{sub 2g}(F) ⟶ {sup 2}E{sub g}(G) transitions of Cr{sup 3+} ions. The highest concentration of Cr{sup 3+} ions (in octahedral sites, with network modifying positions) is found in the sample with 2.0 mol% of Cr{sub 2}O{sub 3}. The analysis of dielectric properties indicates a gradual increase in semiconducting character with increase in the concentration of Cr{sub 2}O{sub 3} from 0.2 to 2.0 mol%. The studies on dielectric breakdown strength identify the highest insulating strength for lowest mol% of Cr{sub 2}O{sub 3} in the present samples.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Photoluminescence properties of cerium oxide nanoparticles as a function of lanthanum content

Highlights: • CeO{sub 2} nanoparticles were obtained by microwave-hydrothermal method. • Rietveld refinement reveals a cubic structure. • KOH mineralizer agent exhibit weak agglomeration at low temperature and shorter time. - Abstract: The structural and photoluminescent properties at room temperature of CeO{sub 2} and La-doped CeO{sub 2} particles were undertaken. The obtained particles were synthesized by a microwave-assisted hydrothermal method (MAH) under different lanthanum contents. X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Fourier transform Raman (FT-Raman), Ultra-violet spectroscopy (UV–vis) and photoluminescence (PL) measurements were carried out. XRD revealed that the powders are free of secondary phases and crystallize in the cubic structure. Raman data show that increasing La doping content increase oxygen vacancies due to lattice expansion. The UV/vis absorption spectroscopy suggested the presence of intermediate energy levels in the band gap of structurally ordered powders. Lanthanum addition creates oxygen vacancies and shifts the photoluminescence in the low energy range leading to intense PL emission.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Preservation of higher Fe[II] content in borosilicate glass by microwave irradiation in air

Highlights: • Higher Fe[II] absorption within 1000–1200 nm in UV-vis-NIR spectra in microwave (MW) melted glass. • Spectrophotometric methods confirm higher Fe-redox ratio in MW melted glass. • Thermogravimetric analysis (TGA) recorded more weight gain signifying higher stabilisation of Fe[II] in MW melted glass. • Fe 2p{sub 3/2} peak in XPS demonstrates presence of higher FeO concentration in MW glass. • Slow conversation of Fe[II] to Fe[III] in MW heating influencing retention of higher Fe[II]. - Abstract: Existence of high Fe[II] content in glass is a perquisite for achieving high heat absorption property in glass. Present study investigates the capability of microwave (MW) irradiation in retention of higher Fe[II] in glass eliminating the stringent reducing atmosphere requirements in conventional heating. Stabilisation of higher Fe[II] in glass under influence of MW irradiation has been demonstrated, measuring absorbance at >1000 nm in UV–vis-NIR spectra, maintaining identical conditions in MW and in conventional heating. Spectrophotometric methods developing color complex of Fe{sup 2+} with ferrozine and 1, 10 ortho-phenanthroline are used to confirm higher content of Fe[II]. Further, more weight gain in thermo gravimetric analysis, higher isomer shift (>0.89 mm/s) with more relative absorption (% area) for Fe[II] in Mössbauer spectroscopy, and shifting of Fe 2p{sub 3/2} peak in X-ray photoelectron spectroscopy towards lower binding energy further confirm retention of higher FeO under MW irradiation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

First determination of the CP content of D → π + π – π 0 and D → K + K – π 0

Quantum-correlated Ψ(3770) → DD¯ decays collected by the CLEO-c experiment are used to perform first measurements of F + , the fractional CP-even content of the self-conjugate decays D → π + π – π 0 and D → K + K – π 0 . Values of 0.968 ± 0.017 ± 0.006 and 0.731 ± 0.058 ± 0.021 are obtained for π + π – π 0 and K + K – π 0 , respectively. It is demonstrated how modes of this sort can be cleanly included in measurements of the unitarity triangle angle γ using B → DK decays. The high CP-even content of D → π + π – π 0 , in particular, makes this a promising mode for improving the precision on γ.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Rheological effects of moisture content on the anatomical fractions of loblolly pine (Pinus taeda)

Here, this study focused on assessing the influence of moisture content on the rheological properties of different anatomical fractions of pine residue using the FT4 powder rheometer. Moisture content exhibited some influence on the 2 mm bark and needle fractions, increasing their cohesion, angle of internal friction, unconfined yield strength, and major principal stress. Stem and whole, on the other hand, presented minimal changes upon moisture introduction. All 4 mm fractions did not show many changes in their rheological properties with moisture introduction, which can be due to less particle-particle interactions and consequently reducing any liquid bridging the particles might undergo; however, they were shown to have a more unpredictable behavior compared to the 2 mm analogues (i.e., higher standard deviation) which can be due to a higher degree of particle-interlocking. Out of the three fractions, needle presented the poorest rheological properties for flowability in addition to being susceptible by moisture, unlike other fractions.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Effects of defined mixtures of persistent organic pollutants (POPs) on multiple cellular responses in the human hepatocarcinoma cell line, HepG2, using high content analysis screening

Persistent organic pollutants (POPs) are toxic substances, highly resistant to environmental degradation, which can bio-accumulate and have long-range atmospheric transport potential. Most studies focus on single compound effects, however as humans are exposed to several POPs simultaneously, investigating exposure effects of real life POP mixtures on human health is necessary. A defined mixture of POPs was used, where the compound concentration reflected its contribution to the levels seen in Scandinavian human serum (total mix). Several sub mixtures representing different classes of POPs were also constructed. The perfluorinated (PFC) mixture contained six perfluorinated compounds, brominated (Br) mixture contained seven brominated compounds, chlorinated (Cl) mixture contained polychlorinated biphenyls and also p,p’-dichlorodiphenyldichloroethylene, hexachlorobenzene, three chlordanes, three hexachlorocyclohexanes and dieldrin. Human hepatocarcinoma (HepG2) cells were used for 2 h and 48 h exposures to the seven mixtures and analysis on a CellInsight™ NXT High Content Screening platform. Multiple cytotoxic endpoints were investigated: cell number, nuclear intensity and area, mitochondrial mass and membrane potential (MMP) and reactive oxygen species (ROS). Both the Br and Cl mixtures induced ROS production but did not lead to apoptosis. The PFC mixture induced ROS production and likely induced cell apoptosis accompanied by the dissipation of MMP. Synergistic effects were evident for ROS induction when cells were exposed to the PFC + Br mixture in comparison to the effects of the individual mixtures. No significant effects were detected in the Br + Cl, PFC + Cl or total mixtures, which contain the same concentrations of chlorinated compounds as the Cl mixture plus additional compounds; highlighting the need for further exploration of POP mixtures in risk assessment. - Highlights: • High content analysis (HCA) is a novel approach for determining toxicity of complex mixtures. • Multiple cytotoxic endpoints were investigated for defined mixtures of persistent organic pollutants (POPs). • POP mixtures are based on levels relevant to human exposure. • POP mixtures can increase ROS induction and impact mitochondrial health, which could result in apoptosis. • HCA can detect pre-lethal and reversible signs of cellular stress.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2015

PAHs content of sewage sludge in Europe and its use as soil fertilizer

Highlights: • Sewage sludge contamination by PAHs may restrict its use as soil fertilizer. • Long term data concerning sewage sludge contamination by PAHs is lacking. • Literature review for EU countries and monitoring data for Italy is presented. • Focus PEARL model was used to simulate B(a)Pyr, the most toxic PAH, fate in soil. • The simulated B(a)Pyr soil concentration was much lower than its LOEC for soil organisms. - Abstract: The European Commission has been planning limits for organic pollutants in sewage sludge for 14 years; however no legislation has been implemented. This is mainly due to lack of data on sewage sludge contamination by organic pollutants, and possible negative effects to the environment. However, waste management has become an acute problem in many countries. Management options require extensive waste characterization, since many of them may contain compounds which could be harmful to the ecosystem, such as heavy metals, organic pollutants. The present study aims to show the true European position, regarding the polycyclic aromatic hydrocarbons (PAHs) content of sewage sludge, by comparing the Italian PAHs content with European Union countries, and at assessing the suitability of sewage sludge as soil fertilizer. The FOCUS Pearl model was used to estimate the concentration of benzo [a] pyrene (B(a)Pyr), the most toxic PAH in soil, and its exposure to organisms was then evaluated. The simulated B(a)Pyr and PAHs, expressed as B(a)Pyr, concentrations in soil were much lower than the B(a)Pyr’s most conservative lowest observable effect concentration (LOEC) for soil organisms. Furthermore, the results obtained indicate that it is more appropriate to apply 5 t ha{sup −1} sewage sludge annually than 15 t ha{sup −1} triennially. Results suggest, the EU maximum recommended limit of 6 mg kg{sup −1} PAHs in sewage sludge, should be conservative enough to avoid groundwater contamination and negative effects on soil organisms.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Rare earth elements and critical metal content of extracted landfilled material and potential recovery opportunities

Highlights: • Samples from multiple core drills were obtained from 4× landfill sites in the UK. • Each sample analysed for rare earth elements, critical metals and valuable metals. • Two stage microwave digestion method ensuring high yield. • High quantities of copper and aluminium were observed in the soil layers of landfill. • Across 4× landfills aluminium and copper present has a value of around $400 million. - Abstract: Rare earth elements (REEs), Platinum group metals (PGMs) and other critical metals currently attract significant interest due to the high risks of supply shortage and substantial impact on the economy. Their uses in many applications have made them present in municipal solid waste (MSW) and in commercial and industrial waste (C&I), since several industrial processes produce by-products with high content of these metals. With over 4000 landfills in the UK alone, the aim of this study was to assess the existence of these critical metals within landfills. Samples collected from four closed landfills in UK were subjected to a two-step acid digestion to extract 27 metals of interest. Concentrations across the four landfill sites were 58 ± 6 mg kg{sup −1} for REEs comprising 44 ± 8 mg kg{sup −1} for light REEs, 11 ± 2 mg kg{sup −1} for heavy REEs and 3 ± 1 mg kg{sup −1} for Scandium (Sc) and 3 ± 1.0 mg kg{sup −1} of PGMs. Compared to the typical concentration in ores, these concentrations are too low to achieve a commercially viable extraction. However, content of other highly valuable metals (Al and Cu) was found in concentrations equating to a combined value across the four landfills of around $400 million, which increases the economic viability of landfill mining. Presence of critical metals will mainly depend on the type of waste that was buried but the recovery of these metals through landfill mining is possible and is economically feasible only if additional materials (plastics, paper, metallic items and other) are also recovered for reprocessing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Performance evaluation of a novel anaerobic digestion operation process for treating high-solids content chicken manure: Effect of reduction of the hydraulic retention time at a constant organic loading rate

Highlights: • A novel feeding strategy, keeping constant OLR but reducing HRT{sub CM} was adopted. • The effect of reducing HRT{sub CM} on CH{sub 4} fermentation of chicken manure was studied. •High content of ammonia was the main inhibition factor at HRT{sub CM} of 52 days. • Reduce in HRT{sub CM} relaxed the inhibition of high ammonia at OLR of 6.0 gVS/L/d. • The performance deterioration occurred as HRT{sub CM} decreased to 10 days. - Abstract: A novel feeding strategy was adopted in this study and the effect of reduction in hydraulic retention time (HRT) on the anaerobic digestion of chicken manure (CM) with a constant organic loading rate of 6.0 gVS/L/d was investigated. The lab-scale CSTR was operated at 38 °C and HRT{sub CM} was reduced from 52 days to 5 days. At HRT{sub CM} of 20–45 days, the reactor was relatively stable in terms of the volumetric biogas production rates and specific biogas production (SBP), which were 2.2–2.4 L/L/d and 338.3–418.7 mL/gVS{sub added}, respectively. However, process instability and VFA accumulation occurred when the HRT{sub CM} was reduced to 10 days due to excess microbes washout. The reduction in HRT{sub CM} to 5 days caused SBP to decrease to 198.7 mL/gVS{sub added} and the acetic acid content to exceed 6000 mg/L. The biomass balance model showed that the biomass concentration at HRT{sub CM} of 20–52 days (0.473–0.615 gVSS/L) was notably higher than that at HRT{sub CM} of 5–10 days (0.173 gVSS/L).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Critical material content in modern conventional U.S. vehicle electronics

Critical materials (CM) are vital to modern technology. Components of modern vehicles can be recycled to recover and reuse the CMs to help ensure a supply of these materials. Electronic components from a 2015 GMC Sierra truck (21 components) and 2016 Toyota Camry sedan (10 components) were analyzed for CMs. The components were processed via size reduction, aqua regia leaching and dissolution, and final solutions were analyzed for metal content. It was found that most electronic components of both vehicles contain CM. The most concentrated CM in the components were Sn, Nb, and Tb. Nd and Co were found in several of the magnetic components. CM economic value was found to be low compared to the overall value of the components, and the CM content would not allow for a viable pathway for recycling. Remanufacturing of components may be a more economic option of reuse in the future.

2015 GMC Sierra↗
DOE OSTI2015

Dynamic heterogeneity of DNA methylation and hydroxymethylation in embryonic stem cell populations captured by single-cell 3D high-content analysis

Cell-surface markers and transcription factors are being used in the assessment of stem cell fate and therapeutic safety, but display significant variability in stem cell cultures. We assessed nuclear patterns of 5-hydroxymethylcytosine (5hmC, associated with pluripotency), a second important epigenetic mark, and its combination with 5-methylcytosine (5mC, associated with differentiation), also in comparison to more established markers of pluripotency (Oct-4) and endodermal differentiation (FoxA2, Sox17) in mouse embryonic stem cells (mESC) over a 10-day differentiation course in vitro: by means of confocal and super-resolution imaging together with 3D high-content analysis, an essential tool in single-cell screening. In summary: 1) We did not measure any significant correlation of putative markers with global 5mC or 5hmC. 2) While average Oct-4 levels stagnated on a cell-population base (0.015 lnIU/day), Sox17 and FoxA2 increased 22-fold and 3-fold faster, respectively (Sox17: 0.343 lnIU/day; FoxA2: 0.046 lnIU/day). In comparison, global DNA methylation levels increased 4-fold faster (0.068 lnIU/day), and global hydroxymethylation declined at 0.046 lnIU/day, both with a better explanation of the temporal profile. 3) This progression was concomitant with the occurrence of distinct nuclear codistribution patterns that represented a heterogeneous spectrum of states in differentiation; converging to three major coexisting 5mC/5hmC phenotypes by day 10: 5hmC{sup +}/5mC{sup −}, 5hmC{sup +}/5mC{sup +}, and 5hmC{sup −}/5mC{sup +} cells. 4) Using optical nanoscopy we could delineate the respective topologies of 5mC/5hmC colocalization in subregions of nuclear DNA: in the majority of 5hmC{sup +}/5mC{sup +} cells 5hmC and 5mC predominantly occupied mutually exclusive territories resembling euchromatic and heterochromatic regions, respectively. Simultaneously, in a smaller subset of cells we observed a tighter colocalization of the two cytosine variants, presumably delineating chromatin domains in remodeling. We conclude that 1) 5mC emerges as the most differential marker in our model system. 2) However, the combined enrollment of the two DNA modifications provided higher-definition screening and lead to the identification of cell subpopulations based on differential 5hmC/5mC phenotypes corresponding to different 5hmC/5mC ratios. The results encourage: a) assessing the regenerative potential of early-endodermal cells enriched for the three DNA methylation/hydroxymethylation categories, and b) exploring the universality of this type of epigenetic phenotyping across other lineage-specific differentiations. - Highlights: • First reported single-molecule super-resolution 3D-visualization of 5mC/5hmC sites in cells. • Identification of cells with differential 5mC/5hmC nuclear codistribution phenotypes. • Application of principle component and robust regression analyses for evaluation of 3D high-content-screening data. • Global 5mC constitutes a highly differential spatiotemporal in situ marker in early endodermal cell differentiation.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

High-content image informatics of the structural nuclear protein NuMA parses trajectories for stem/progenitor cell lineages and oncogenic transformation

Stem and progenitor cells that exhibit significant regenerative potential and critical roles in cancer initiation and progression remain difficult to characterize. Cell fates are determined by reciprocal signaling between the cell microenvironment and the nucleus; hence parameters derived from nuclear remodeling are ideal candidates for stem/progenitor cell characterization. Here we applied high-content, single cell analysis of nuclear shape and organization to examine stem and progenitor cells destined to distinct differentiation endpoints, yet undistinguishable by conventional methods. Nuclear descriptors defined through image informatics classified mesenchymal stem cells poised to either adipogenic or osteogenic differentiation, and oligodendrocyte precursors isolated from different regions of the brain and destined to distinct astrocyte subtypes. Nuclear descriptors also revealed early changes in stem cells after chemical oncogenesis, allowing the identification of a class of cancer-mitigating biomaterials. To capture the metrology of nuclear changes, we developed a simple and quantitative “imaging-derived” parsing index, which reflects the dynamic evolution of the high-dimensional space of nuclear organizational features. A comparative analysis of parsing outcomes via either nuclear shape or textural metrics of the nuclear structural protein NuMA indicates the nuclear shape alone is a weak phenotypic predictor. In contrast, variations in the NuMA organization parsed emergent cell phenotypes and discerned emergent stages of stem cell transformation, supporting a prognosticating role for this protein in the outcomes of nuclear functions. - Highlights: • High-content analysis of nuclear shape and organization classify stem and progenitor cells poised for distinct lineages. • Early oncogenic changes in mesenchymal stem cells (MSCs) are also detected with nuclear descriptors. • A new class of cancer-mitigating biomaterials was identified based on image informatics. • Textural metrics of the nuclear structural protein NuMA are sufficient to parse emergent cell phenotypes.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2015

Electronic and Electrochemical Properties of Li 1– x Mn 1.5 Ni 0.5 O 4 Spinel Cathodes As a Function of Lithium Content and Cation Ordering

The electronic and electrochemical properties of the high-voltage spinel LiMn 1.5 Ni 0.5 O 4 as a function of cation ordering and lithium content have been investigated. Conductivity and activation energy measurements confirm that charge transfer occurs by small polaron hopping and the charge carrier conduction is easier in the Ni:3d band than in the in Mn:3d band. Seebeck coefficient data reveal that the Ni 2+ / 3+ . and Ni 3+ / 4+ redox couples are combined in a single,3d band, and that maximum charge carrier concentration occurs where the average Ni oxidation state is close to 3+, corresponding to x = 0.5 in Li Li 1-x Mn 1.5 Ni 0.5 O 4 . Furthermore, maximum electronic conductivity is found at x = 0.5, regardless of cation ordering. The thermodynamically stable phases formed during cycling were investigated by recording the X-ray diffraction (XRD) of chemically delithiated powders. The more ordered spinels maintained two separate two-phase regions upon lithium extraction, while the more disordered samples exhibited a solid-solubility region from LiMn 1.5 Ni 0.5 O 4 to Li 0.5 Mn 1.5 Ni 0.5 O 4 . The conductivity and phase-transformation data of four samples with varying degrees of cation ordering were compared to the electrochemical data collected with lithium cells. Only the most ordered spinel showed inferior rate performance, while the sample annealed for a shorter time performed comparable to the unannealed or disordered samples. Our results challenge the most common beliefs about high-voltage spinel: (i) low Mn 3+ content is responsible for poor rate performance and (ii) thermodynamically stable solid-solubility is critical for fast kinetics.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Structure–Thermodynamic Relationship of a Polysaccharide Gel (Alginate) as a Function of Water Content and Counterion Type (Na vs Ca)

Biofilms are the predominant mode of microbial life on Earth, and so a deep understanding of microbial communities-and their impacts on environmental processes-requires a firm understanding of biofilm properties. Because of the importance of biofilms to their microbial inhabitants, microbes have evolved different ways of engineering and reconfiguring the matrix of extracellular polymeric substances (EPS) that constitute the main non-living component of biofilms. This ability makes it difficult to distinguish between the biotic and abiotic origins of biofilm properties. An important route toward establishing this distinction has been the study of simplified models of the EPS matrix. This study builds on such efforts by using atomistic simulations to predict the nanoscale (≤10 nm scale) structure of a model EPS matrix and the sensitivity of this structure to interpolymer interactions and water content. To accomplish this, we use replica exchange molecular dynamics (REMD) simulations to generate all-atom configurations of ten 3.4 kDa alginate polymers at a range of water contents and Ca–Na ratios. Simulated systems are solvated with explicitly modeled water molecules, which allows us to capture the discrete structure of the hydrating water and to examine the thermodynamic stability of water in the gels as they are progressively dehydrated. Our primary findings are that (i) the structure of the hydrogels is highly sensitive to the identity of the charge-compensating cations, (ii) the thermodynamics of water within the gels (specific enthalpy and free energy) are, surprisingly, only weakly sensitive to cation identity, and (iii) predictions of the differential enthalpy and free energy of hydration include a short-ranged enthalpic term that promotes hydration and a longer-ranged (presumably entropic) term that promotes dehydration, where short and long ranges refer to distances shorter or longer than ~0.6 nm between alginate strands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Degradation in Ni-Rich LiNi 1– x – y Mn x Co y O 2 /Graphite Batteries: Impact of Charge Voltage and Ni Content

Ni-rich LiNi 1– x–y Mn x CoyO 2 (NMC) materials are attractive as cathodes for Li-ion batteries due to their high energy density and low Co content. However, these materials may display poor electrochemical reversibility relating to structural and interfacial instabilities. The influence of Ni content and level of delithiation during charge on degradation mechanisms and relevance to electrochemical cycling behavior are probed for LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode materials in a full cell configuration under two upper voltage limits (4.1 and 4.3 V). The combined use of dQ/dV analysis of electrochemical voltage profiles, operando XRD, and postcycling scanning electron microscopy (SEM) measurements indicates that a major contributor to capacity fade is the large anisotropic volume change from an H2 $\leftrightarrows$ H3 phase transition and associated mechanical degradation particularly for NMC811. Notably, transition metal dissolution and deposition on the negative electrode are found to correlate with the structural changes occurring in the cathode under high voltage charge. X-ray photoelectron spectroscopy (XPS) analyses of the cycled cathodes reveal a more organic-rich cathode–electrolyte interphase (CEI) when cycling to 4.3 V with lower relative amounts of LiF. Surface reconstruction is not a significant factor under these cycling conditions as determined by soft X-ray absorption spectroscopy (sXAS) analysis. The results emphasize the opportunity to match the electrochemical test parameters with the specific NMC active material to mitigate degradation and extend cycle life.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Impact of Anions and Water Content on [Li–Al] Layered Double-Hydroxide Stability

[Li–Al] layered double hydroxides (LDHs) are compounds with potential as sorbents for lithium extraction from brine solutions. Here, in this work, heat capacities were measured from approximately 2.5 to 300 K for six [Li–Al] LDHs with differing anions (Cl – , OH – , and SO 4 2– ) and water content (denoted A for air-dried and O for oven-dried). These measurements were used to calculate the standard entropy at 298.15 K, and the results were combined with previously performed enthalpy measurements to calculate Gibbs energies of formation from the binary compounds. The calculated order of stability based on Gibbs energies of formation was Cl-LDH-O > OH-LDH-O > Cl-LDH-A > SO 4 -LDH-O > SO 4 -LDH-A > OH-LDH-A. Results support previous findings that higher water content generally raises the Gibbs energy of the LDH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Yttrium Contenting Compositionally Complex Medium-Entropy Li-Garnet Electrolyte with Improved Ionic Conductivity

The compositionally complex medium/high-entropy design concept can greatly expand the categories and affect the properties of the materials. With such a designing concept, a medium-entropy Li-garnet electrolyte with appropriate yttrium content (formula Li 6.6 La 3 ZrNb 0.3 Ta 0.3 Hf 0.3 Y 0.1 O 12 ) shows a record-high ionic conductivity of ∼5.7 × 10 –4 S/cm, the highest reported for any single-site substituted high/medium-entropy Li-garnet. The assembled Li metal symmetric cells also show stable long-term cycling (0.1 mA/cm 2 for over 200 h). Neutron powder diffraction and Rietveld refinement results indicate that a competing conduction mechanism between (1) occupancy on high mobility of 96h sites and (2) the associated site vacancies and the bond length requires an appropriate content of Y for enhanced ionic conductivity. Li-ion hopping through the bottleneck can also contribute to the conductivity. Finally, density functional theory and Born–Oppenheimer molecular dynamics simulations also indicate the high mobility and number of hopping transitions of Li ions, contributing to the high ionic conductivity.

Li-garnet↗
DOE OSTI2025

Revisiting the Effects of Seed Liquid Water Content on Isoprene Secondary Organic Aerosol Growth

Aerosol liquid water content (LWC) has been shown to enhance partitioning of water-soluble oxygenated organic vapors into the aerosol particles and facilitate aqueous chemistry, impact SOA formation, composition, and physicochemical properties. Here, this study examines the effect of aerosol liquid water content (LWC) on isoprene SOA formation using effloresced and deliquesced ammonium sulfate ((NH 4 ) 2 SO 4 ) and sodium chloride (NaCl) seed particles in an environmental chamber with photo-oxidation extending over hours under moderate relative humidity (50%-60%). Our findings indicate that isoprene SOA mass yield is not significantly influenced (p value >> 0.05) by the phase state or the chemical identity of the seed particles within a 3–4-hour reaction time scale. Detailed molecular analysis using advanced high resolution mass spectrometry indicates that while both effloresced and deliquesced seed types produced similar molecular formula distributions, deliquesced (NH 4 ) 2 SO 4 slightly favored the production of less volatile compounds. Depth-profiling analysis by single particle mass spectrometry confirmed that isoprene SOA predominantly located on the surfaces of particles with core-shell morphologies, with partial dissolution of the effloresced inorganic salt observed even below the deliquescence relative humidity (DRH) of salt. This finding suggests that assuming dry salt core particles do not interact with SOA coatings, based on salt deliquescence points, may overlook important aqueous chemistry. These results emphasize the critical role of reaction time scale and mixing state on SOA formation and call for further research to understand LWC effects on SOA from different precursors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗