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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

Partitioning of siderophile and chalcophile elements between sulfide, olivine, and glass in a naturally reduced basalt from Disko Island, Greenland

Major and trace elements in coexisting glass, olivines, and metal-sulfide spherules from a chilled margin sample of a strongly reduced basaltic dike from Disko Island, Greenland have been investigated. Three sets of partition coefficients are obtained, olivine/silicate liquid and metal-sulfide liquid/silicate liquid partition coefficients established at magmatic temperatures, and FeNi/FeS partition coefficients at lower temperatures. High metal-sulfide liquid/silicate liquid partition coefficients are found for Ni, Sb, As, Mo, Cu, Co, and W. The significance of the present results for planetary evolution and the formation of metal-rich or sulfide-rich metal cores is considered in terms of P, W, and Mo abundances in the mantles of the earth, moon, the Shergotty parent body, and the Eucrite parent body.

Klock, W.↗
NASA NTRS1997

Partitioning of Moderately Siderophile Elements Among Olivine, Silicate Melt, and Sulfide Melt: Constraints on Core Formation in the Earth and Mars

This study investigates the effects of Variations in the fugacities of oxygen and sulfur on the partitioning of first series transition metals (V, Cr, Mn, Fe, Co, Ni. and Cu) and W among coexisting sulfide melt, silicate melt, and olivine. Experiments were performed at 1 atm pressure, 1350 C, with the fugacities of oxygen and sulfur controlled by mixing CO2, CO, and SO2 gases. Starting compositions consisted of a CaO-MgO-Al2O3-SiO2-FeO-Na2O analog for a barred olivine chondrule from an ordinary chondrite and a synthetic komatiite. The f(sub O2)/f(sub S2), conditions ranged from log of f(sub O2) = -7.9 to - 10.6, with log of f(sub S2) values ranging from - 1.0 to -2.5. Our experimental results demonstrate that the f(sub O2)/f(sub S2) dependencies of sulfide melt/silicate melt partition coefficients for the first series transition metals arc proportional to their valence states. The f(sub O2)/f(sub S2) dependencies for the partitioning of Fe, Co, Ni, and Cu are weaker than predicted on the basis of their valence states. Variations in conditions have no significant effect on olivine/melt partitioning other than those resulting from f(sub O2)-induced changes in the valence state of a given element. The strong f(sub O2)/f(sub S2) dependence for the olivine/silicate melt partitioning of V is attributable to a change of valence state, from 4+ to 3+, with decreasing f(sub O2). Our experimentally determined partition coefficients are used to develop models for the segregation of sulfide and metal from the silicate portion of the early Earth and the Shergottite parent body (Mars). We find that the influence of S is not sufficient to explain the overabundance of siderophile and chalcophile elements that remained in the mantle of the Earth following core formation. Important constraints on core formation in Mars are provided by our experimental determination of the partitioning of Cu between silicate and sulfide melts. When combined with existing estimates for siderophile element abundances in the Martian mantle and a mass balance constraint from Fe, the experiments allow a determination of the mass of the Martian core (approx. 17 to 22 wt% of the planet) and its S content (approx.0.4 wt%). These modeling results indicate that Mars is depleted in S, and that its core is solid.

Gaetani, Glenn A.↗
NASA NTRS1986

Competition for sulfide among colorless and purple sulfur bacteria in cyanobacterial mats

The vertical zonation of light, O2, H2S, pH, and sulfur bacteria was studied in two benthic cyanobacterial mats from hypersaline ponds at Guerrero Negro, Baja California, Mexico. The physical-chemical gradients were analyzed in the upper few mm at < or = 100 micrometers spatial resolution by microelectrodes and by a fiber optic microprobe. In mats, where oxygen produced by photosynthesis diffused far below the depth of the photic zone, colorless sulfur bacteria (Beggiatoa sp.) were the dominant sulfide oxidizing organisms. In a mat, where the O2-H2S interface was close to the photic zone, but yet received no significant visible light, purple sulfur bacteria (Chromatium sp.) were the dominant sulfide oxidizers. Analysis of the spectral light distribution here showed that the penetration of only 1% of the incident near-IR light (800-900 nm) into the sulfide zone was sufficient for the mass development of Chromatium in a narrow band of 300 micromoles thickness. The balance between O2 and light penetration down into the sulfide zone thus determined in micro-scale which type of sulfur bacteria became dominant.

NASA Center ARC↗
NASA NTRS2008

Crystallinity of Fe-Ni Sulfides in Carbonaceous Chondrites

The main long-term goal of this research is to understand the physical conditions in the early solar nebula through the detailed characterization of a key class of mineral present in all primitive materials: Fe-Ni sulfides [1&2]. Fe-Ni sulfides can take dozens of structures, depending on the temperature of formation, as well as other physico-chemical factors which are imperfectly understood. Add to this the additional varying factor of Ni content, and we have a potentially sensitive cosmothermometer [3]. Unfortunately, this tool requires exact knowledge of the crystal structure of each grain being considered, and there have been few (none?) studies of the detailed structures of sulfides in chondritic materials. We report here on coordinated compositional and crystallographic investigation of Fe-Ni sulfides in diverse carbonaceous chondrites, initially Acfer 094 (the most primitive CM2 [4]) Tagish Lake (a unique type C2 [5]), a C1 lithology in Kaidun [6], Bali (oxidized CV3 [7]), and Efremovka (reduced CV3 [7]).

Zolensky, Michael E.↗
NASA NTRS2013

FIB-TEM Investigations of Fe-NI-Sulfides in the CI Chondrites Alais and Orgueil

The CI chondrites are primitive meteorites with bulk compositions matching the solar photosphere for all but the lightest elements. They have been extensively aqueously altered, and are composed primarily of fine-grained phyllosilicate matrix material which is host to carbonates, sulfates, sulfides, and minor amounts of olivine and pyroxene. The alteration, while extensive, is heterogeneous. For example, CI-chondrite cubanite and carbonate grains differ on mm to sub-mm scales, demonstrating multiple aqueous episodes. CI-chondrite variability is also evidenced by degree of brecciation, abundance and size of coarse-grained phyllosilicates, olivine and pyroxene abundance, as well as Ni-content and size of sulfide grains. Our previous work revealed Orgueil sulfide grains with variable Ni-contents, metal:S ratios, crystal structures and textures. We continue to explore the variability of CI-chondrite pyrrhotite (Po, (FeNi)1-xS) and pentlandite (Pn, (Fe,Ni)9S8) grains. We investigate the microstructure of sulfides within and among CI-chondrite meteorites in order to place constraints on the conditions under which they formed.

Berger, Eve L.↗
DOE OSTI2024

Tailoring Binder Molecular Weight to Enhance Slurry-Cast NMC Cathodes for Sulfide Solid-State Batteries

We demonstrate for the first time the critical influence of binder molecular weight on the performance of slurry-cast lithium nickel manganese cobalt oxide (NMC) cathodes in sulfide-based all-solid-state batteries (SSBs). SSBs are increasingly recognized as a safer and potentially more efficient alternative to traditional Li-ion batteries, owing to the superior ionic conductivities and inherent safety features of sulfide solid electrolytes. However, the integration of high-voltage NMC cathodes with sheet-type sulfide solid electrolytes presents significant fabrication challenges. Our findings reveal that higher molecular weight binders not only enhance the discharge capacity and cycle life of these cathodes but also ensure robust adhesion and structural integrity. By optimizing binder molecular weights, we effectively shield the active materials from degradation and mechanical stress, significantly boosting the functionality and longevity of SSBs. These results underscore the paramount importance of binder properties in advancing the practical application of high-performance all-solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

High-performance LiNi 0.8 Mn 0.1 Co 0.1 O 2 cathode by nanoscale lithium sulfide coating via atomic layer deposition

The commercialization of nickel-rich LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) has been hindered by its continuous loss of practical capacity and reduction in average working voltage. To address these issues, surface modification has been well-recognized as an effective strategy. Different from the coatings reported in literature to date, in this work, we for the first time report a sulfide coating, amorphous Li 2 S via atomic layer deposition (ALD). Here, our study revealed that the conformal nano-Li 2 S coating shows exceptional protection over the NMC811 cathodes, accounting for the dramatically boosted capacity retention from ~11.6% to ~71% and the evidently mitigated voltage reduction from 0.39 to 0.18 V after 500 charge–discharge cycles. In addition, the Li 2 S coating remarkably improved the rate capability of the NMC811 cathode. Our investigation further revealed that all these beneficial effects of the ALD-deposited nano-Li 2 S coating lie in the following aspects: (i) maintain the mechanical integrity of the NMC811 electrode; (ii) stabilize the NMC electrode/electrolyte interface; and (iii) suppress the irreversible phase transition of NMC structure. Particularly, this study also has revealed that the nano-Li 2 S coating has played some unique role not associated with traditional non-sulfide coatings such as oxides. In this regard, we disclosed that the Li 2 S layer has reacted with the released O 2 from the NMC lattices, and thereby has dramatically mitigated electrolyte oxidation and electrode corrosion. Thus, this study is significant and has demonstrated that sulfides may be an important class of coating materials to tackle the issues of NMCs and other layered cathodes in lithium batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Utilizing metal cation reactions with carbonyl sulfide to remove isobaric interferences in tandem inductively coupled plasma mass spectrometry analyses

Carbonyl sulfide (OCS) was used as a reaction gas to investigate gas phase metal (M + ) ion-molecule reactions using the Agilent 8900 inductively coupled plasma tandem mass spectrometer (ICP-MS/MS) to yield insight on how this gas may be used to remove isobaric interferences in analytical measurements. The experimental work was paired with density functional theory (DFT) calculations of the reaction enthalpy to predict whether M + will react with OCS. A multi-element standard containing 46 elements ranging from 9 to 208 u was analyzed in the presence and absence of OCS. When a reaction was observed, the dominant product was the sulfide (MS + ). Oxide products were also observed for many M + but formation was less efficient with OCS than previously observed with other reaction gases. This is likely due to the weaker OC-S bond that makes MS + formation more favorable. Increasing the flow rate from 0.1 to 0.2 mL/min (corresponding to a change in reaction gas pressure from 0.35 to 0.53 Pa (2.6 to 4.0 mTorr)) generally resulted in greater MS + production, including the secondary product MS 2 + for a few cations. The early lanthanide series ions (La + , Ce + , Pr + and Nd + ) produced greater quantities of MO + at the higher pressure, although MS + products were still the dominant product. The DFT-predicted reaction enthalpies were consistent with the observed sulfide formation, with an accuracy >90%; however, model predictions were less accurate for the minor and higher order products (< 77% for MO + ). Finally, the work presented here continues a systematic study of ion-molecule reactions in ICP-MS/MS to understand and develop new and novel ways to analyze complex mixtures with minimal pre-analysis treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Investigating dry room compatibility of sulfide solid-state electrolytes for scalable manufacturing

All-solid-state batteries (ASSBs) are viewed as promising next-generation energy storage devices, due to their enhanced safety by replacing organic liquid electrolytes with non-flammable solid-state electrolytes (SSEs). The high ionic conductivity and low Young's modulus of sulfide SSEs make them suitable candidates for commercial ASSBs. Nevertheless, sulfide SSEs are generally reported to be unstable in ambient air. Moreover, instead of gloveboxes used for laboratory scale studies, large scale production of batteries is usually conducted in dry rooms. Thus, this study aims to elucidate the chemical evolution of a sulfide electrolyte, Li 6 PS 5 Cl (LPSCl), during air exposure and to evaluate its dry room compatibility. When LPSCl is exposed to ambient air, hydrolysis, hydration, and carbonate formation can occur. Moreover, hydrolysis can lead to irreversible sulfur loss and therefore LPSCl cannot be fully recovered in the subsequent heat treatment. During heat treatment, exposed LPSCl undergoes dehydration, decomposition of carbonate species, and reformation of the LPSCl phase. Lastly, LPSCl was found to exhibit good stability in a dry room environment and was subject to only minor conductivity loss due to carbonate formation. The dry room exposed LPSCl sample was tested in a LiNi 0.8 Co 0.1 Mn 0.1 O 2 |LiIn half-cell, exhibiting no significant loss of electrochemical performance compared with the pristine LPSCl, proving it to be compatible with dry room manufacturing processes.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Sulfidation kinetics of titanium and Ti-6Al-4V with elemental sulfur

The sulfidation kinetics of titanium and Ti-6Al-4V (Ti64) using elemental sulfur were studied by measuring the amount of metal consumed instead of the change in mass or scale thickness. Here this metal consumption approach combines the parabolic oxidation law, Arrhenius equation, and Pilling-Bedworth ratio to determine the apparent activation energy and the pre-exponential factor of consumption of Ti64 during sulfidation. The estimations of apparent activation energy and pre-exponential factor were 110.4 kJ·mol -1 and 1.3×10 -9 m 2 s -1 for the titanium-sulfur, and 116.2 kJ·mol -1 and 1.2×10 -9 m2s -1 for the Ti64-sulfur system. Finally, a material removal predictor was developed to predict the amount of Ti64 consumed for a given sulfidation temperature and time.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Efficient passivation of n-type and p-type silicon surface defects by hydrogen sulfide gas reaction

An efficient surface defect passivation is observed by reacting clean Si in a dilute hydrogen sulfide-argon gas mixture (< 5% H2S in Ar) for both n-type and p-type Si wafers with planar and textured surfaces. Surface recombination velocities of 1.5 and 8 cm/s are achieved on n-type and p-type Si wafers, respectively, at an optimum reaction temperature of 550oC that are comparable to the best surface passivation quality used in high efficiency Si solar cells. Surface chemical analysis using x-ray photoelectron spectroscopy shows that sulfur is primarily bonded in a sulfide environment, and synchrotron-based soft x-ray emission spectroscopy of the adsorbed sulfur atoms suggests the formation of S-Si bonds. Furthermore, the sulfur surface passivation layer is unstable in air, attributed to surface oxide formation and a simultaneous decrease of sulfide bonds. However, the passivation can be stabilized by a low-temperature (300oC) deposited amorphous silicon nitride (a-Si:NX:H) capping layer.

14 SOLAR ENERGY↗
DOE OSTI2025

Microbial ecology of acidic, biogenic gypsum: community structure and distribution of extremophiles on freshly formed and relict sulfate deposits in a hydrogen sulfide-rich cave

Sulfate minerals are abundant on the Martian surface, and many of these evaporite deposits are thought to have precipitated from acidic fluids. On Earth, gypsum (CaSO 4 •2H 2 O) and other sulfates sometimes form under acidic conditions, so exploring the extremophilic life that occurs in these mineral environments can help evaluate the astrobiological potential of acid sulfate depositional settings. Here, we characterized the microbial communities associated with acidic gypsum deposits in a sulfuric acid cave, where sulfate precipitation is driven by sulfide-oxidizing bacteria and archaea. We used 16S rRNA gene sequencing and cell counts to characterize gypsum-associated microorganisms in freshly formed and relict deposits throughout the cave, to test how microbial community composition and abundance would vary with distance from the sulfidic water table and with the concentration of H 2 S(g) and other gases in the cave atmosphere. We found that actively forming gypsum in the lower cave levels was colonized by low-diversity communities that have few cells compared to other environments in the cave. The most abundant taxa were Acidithiobacillus, Metallibacterium, Mycobacteria, and three different Thermoplasmatales-group archaea, which occupied distinct niches based on proximity to sulfidic streams and the concentration of gases in the cave air. By contrast, deposits in older cave levels had more diverse communities that were distinct from those associated with freshly formed gypsum and likely represent a community reliant on different energy resources. These findings show that acidic sulfate deposits serve as habitats for extremophilic microorganisms and broaden our knowledge of the life associated with terrestrial sulfates.

58 GEOSCIENCES↗
DOE OSTI2023

Scaling from Flux Towers to Ecosystem Models: Regional Constraints on Carbon Cycle Processes from Atmospheric Carbonyl Sulfide (Final Report)

DOE supported research suggests that gross primary productivity (GPP) is largely underestimated by global earth system models [Welp et al., 2011], reflecting the persistent challenge in extrapolating from local-scale GPP observations to global-scale earth system models. This poor understanding of GPP at large spatial scales is of particular concern in tropical forests. In tropical forests, some earth systems models forecast a powerful feedback between a warming climate and a decline in GPP resulting in forest dieback. While this simulated feedback is intensely debated, we lack robust large-scale constraints on GPP that are needed to resolve this debate. In particular, carbon dioxide measurements provide valuable information on net carbon flux, but not on the gross flux associated with GPP. Here we conducted a study of regional-to-global scale GPP using atmospheric carbonyl sulfide to provide a new constraint on GPP mechanisms in earth system models. Our project activities integrated modeling, in situ measurement, and remote sensing techniques to resolve GPP for the Amazon as well as global scale trends. The results of this work included initiating airborne carbonyl sulfide monitoring in the Amazon, training for postdocs and graduate students at a Hispanic Serving Institution, fundamental advances in carbonyl sulfide budgets [e.g. Hilton et al., Nature Climate Change, 2017], and high-profile publications that focused on GPP trends for the Amazon [Stinecipher et al., GRL, 2022] and global historical GPP trends [Campbell, et al., Nature, 2017]. Based on the suggestion of our DOE program manager, we published a state-of-the-science commentary to the scientific community on GPP monitoring with COS [Campbell et al., EOS, 2017] which was selected as the cover story. DOE support was acknowledged in all reports. The importance of this research to understanding climate change was communicated to the general public through community seminars (Rotary, Public Libraries, State Parks), an op-ed (SF Chronicle), and interviews in the mass media including two stories in the New York Times (4/5/17; 7/30/18), one of which was especially widely read after it was featured in the New York Time’s Quote of the Day.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Cathode–Sulfide Solid Electrolyte Interfacial Instability: Challenges and Solutions

All-solid-state batteries are a candidate for next-generation energy-storage devices due to potential improvements in energy density and safety compared to current battery technologies. Due to their high ionic conductivity and potential scalability through slurry processing routes, sulfide solid-state electrolytes are promising to replace traditional liquid electrolytes and enable All-solid-state batteries, but stability of cathode-sulfide solid-state electrolytes interfaces requires further improvement. Herein we review common issues encountered at cathode-sulfide SE interfaces and strategies to alleviate these issues.

25 ENERGY STORAGE↗
DOE OSTI2024

A Sulfide‐Based Solid Electrolyte With High Humid Air Tolerance for Long Lifespan All‐Solid‐State Sodium Batteries

Abstract Sulfide‐based superionic conductors present great promise to achieve high energy density and safety for all‐solid‐state sodium batteries (ASSSBs). However, the poor electrolyte/electrode interface compatibility and humid air stability seriously hinder their deployment in ASSSBs. Herein, a series of high‐performance Na 3‐□ Sb 1‐4x (SnWCaTi) x S 4 sulfide‐based solid electrolytes (SSEs) are reported by coupling the vacancy effect with configurational entropy, which displays an excellent interface stability against sodium metal and an extraordinary tolerance toward the moist atmosphere, even for water. The optimized electrolyte effectively inhibits the detrimental mixed ion‐electron conducting interphase formation, achieving the ultra‐stable operation of Na–Na symmetric cell up to 1000 h. Furthermore, the Na + diffusion kinetics is obviously enhanced by increasing the Na sites local anisotropy and Na vacancies. Eventually, the assembled TiS 2 //Na 5 Sn ASSSBs deliver a remarkable reversible capacity of 211.6 mAh g −1 at 0.5C with a long‐term cycling performance of 450 cycles at room temperature. More importantly, it achieves a steady running up to 100 cycles at 1C even if this electrolyte is placed in the air with a dew temperature of 13.8 °C for 30 min, the highest values in the state‐of‐the‐art sulfide‐based ASSSBs. The well‐designed SSEs open a new avenue for realizing the advanced and powerful ASSSBs.

Guo, Yayu↗
DOE OSTI2025

Sequential Infiltration Synthesis of Cadmium Sulfide Discrete Atom Clusters

Abstract Exposure of soft material templates to alternating volatile chemical precursors can produce inorganic deposition within the permeable template (e.g. a polymer thin film) in a process akin to atomic layer deposition (ALD). While such sequential infiltration synthesis (SIS) processes have now been demonstrated for many metal oxides, we report an SIS process for a transition metal sulfide – CdS. Gas phase dimethyl cadmium and hydrogen sulfide precursors infiltrated into poly(4‐vinylpyridine) thin films result in the 3D‐nucleation of clusters consistent with a cubane‐type Cd 4 S 4 core that are variably terminated with methyl, thiol and hydroxy capping ligands. First principles models and simulation of few‐atom Cd‐based clusters are consistent with electronic and vibrational spectroscopy and grazing‐incidence total X‐ray scattering measurements of 3D‐cluster‐arrays synthesized at 80 °C. The direct synthesis of few‐atom transition metal sulfide clusters within polymer thin films will provide a versatile new route to precision architectures for light‐absorbing materials including solar energy harvesting and conversion applications.

Jayaweera, Nuwanthaka P. [Material Science Divisio↗
DOE OSTI2025

Sequential Infiltration Synthesis of Cadmium Sulfide Discrete Atom Clusters

Exposure of soft material templates to alternating volatile chemical precursors can produce inorganic deposition within the permeable template (e.g. a polymer thin film) in a process akin to atomic layer deposition (ALD). While such sequential infiltration synthesis (SIS) processes have now been demonstrated for many metal oxides, we report an SIS process for a transition metal sulfide – CdS. Gas phase dimethyl cadmium and hydrogen sulfide precursors infiltrated into poly(4-vinylpyridine) thin films result in the 3D-nucleation of clusters consistent with a cubane-type Cd 4 S 4 core that are variably terminated with methyl, thiol and hydroxy capping ligands. First principles models and simulation of few-atom Cd-based clusters are consistent with electronic and vibrational spectroscopy and grazing-incidence total X-ray scattering measurements of 3D-cluster-arrays synthesized at 80 °C. The direct synthesis of few-atom transition metal sulfide clusters within polymer thin films will provide a versatile new route to precision architectures for light-absorbing materials including solar energy harvesting and conversion applications.

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

Photooxidation of Organic Sulfide Enhanced by Heavy Atom Effect in Porphyrin Metal–Organic Frameworks with a Sea Topology

The photoactivity of three porphyrin-based metal-organic frameworks (PMOFs) incorporating Al, Ga, and In nodes was systematically evaluated using the photooxidation of an organic sulfide (2-chloroethyl ethyl sulfide, or CEES; a mustard gas simulant). Faster photodegradation of CEES was observed for PMOFs with heavier metal nodes, placing In-PMOF as the most efficient photocatalyst in the series. Guided by this insight, we developed CSLA-10, a MOF integrating In nodes and Sn-doped porphyrin linker to synergistically amplify heavy-atom effects at both the nodes and ligand levels. CSLA-10 exhibited the fastest reported CEES photooxidation to date, achieving a half-life of 38 s in methanol under blue LED irradiation. When grafted onto textiles, CSLA-10 enabled solvent-free CEES degradation in air/O 2 with a half-life of 2.7 min and complete conversion within 7 min, representing the most rapid full degradation reported under solvent-free conditions. Furthermore, this work establishes a dual heavy-atom strategy for enhancing intersystem crossing and singlet oxygen generation in porphyrin MOFs, providing a rational design principle for next-generation photocatalysts for the degradation of toxic organic sulfides.

Metal-organic frameworks↗