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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Effect of Synthesis Method Using Varying Types of Micropore Level Sulfur Infiltration on Electrochemical Performance in Lithium–Sulfur Batteries

The role of physically restrained, noncrystalline sulfur species in rechargeable lithium–sulfur batteries is examined by electrochemical and high‐resolution material characterizations. Carbon–sulfur composites are created by melting and sublimation of sulfur in an isochoric reactor via the autogenic process. These noncrystalline sulfur cathodes demonstrate a high specific capacity of ≈1000 Ah kg −1 after 100 cycles with a gravimetric current of 557 A kg −1 . Interestingly, this high‐performance sulfur allotrope lacks a long‐range structural order: high‐resolution X‐ray diffraction, performed at the Advanced Photon Source, indicates the lack of crystalline (i.e., orthorhombic or monoclinic) sulfur in the nanoscale domain. Electrochemical and material characterizations suggest that noncrystalline sulfur is a consequence of synthesis and not necessarily evidence of electrochemical efficacy. Rather, a high rate capacity depends on sulfur distribution, in turn, controlled by synthesis pathway. At higher sulfur content, the performance of carbon–sulfur composites is limited by the available surface area in which crystalline sulfur coincides with reduced gravimetric capacity and greater charge transport impedance, suggesting suboptimal sulfur containment.

Dysart, Arthur Dence↗
DOE OSTI2015

Direct Observation of Sulfur Radicals as Reaction Media in Lithium Sulfur Batteries

Lithium sulfur (Li-S) battery has been regaining tremendous interest in recent years because of its attractive attributes such as high gravimetric energy, low cost and environmental benignity. However, it is still not conclusively known how polysulfide ring/chain participates in the whole cycling and whether the discharge and charge processes follow the same pathway. Herein, we demonstrate the direct observation of sulfur radicals by using in situ electron paramagnetic resonance (EPR) technique. Based on the concentration changes of sulfur radicals at different potentials and the electrochemical characteristics of the cell, it is revealed that the chemical and electrochemical reactions in Li-S cell are driving each other to proceed through sulfur radicals, leading to two completely different reaction pathways during discharge and charge. The proposed radical mechanism may provide new perspectives to investigate the interactions between sulfur species and the electrolyte, inspiring novel strategies to develop Li-S battery technology.

25 ENERGY STORAGE↗
DOE OSTI2017

Effective strategies for stabilizing sulfur for advanced lithium–sulfur batteries

The lithium-ion battery, with a relatively small energy density of similar to 250 W h kg(-1), has dominantly powered many devices requiring small energy demands. However, there remains a need for a cheaper and smaller type of battery with higher energy density for energy-intensive storage purposes in the automotive, aircraft, and household energy sectors. With its higher specific capacity (1675 mA h g(-1)) and lower costs, the lithium-sulfur (Li-S) battery represents the most promising next generation battery. The main focus of scientific inquiry surrounding Li-S batteries lies at the cathode, where sulfur chemically bonds to lithium. Current challenges pertaining to the high performance cathode such as the dissolution of sulfur into the electrolyte and electrode volume changes are highlighted. This review focuses on recent developments in the last three years of various sulfur integration methods at the cathode that result in improved electrochemical performance, increased energy density, cyclic stability, and a higher capacity over the mainstream lithium-ion battery. In particular, the most recent approaches were systematically examined and compared including the use of carbon and non-carbon composites to stabilize sulfur. Ideal material hosts for sulfur atoms in the cathode for outstanding Li-S batteries were outlined and thoroughly discussed. Critical understanding and relevant knowledge were summarized aiming to provide general guidance for rational design of high-performance cathodes for advanced Li-S batteries.

Ogoke, Ogechi↗
DOE OSTI2018

Formation of Multilayer Graphene Domains with Strong Sulfur-Carbon Interaction and Enhanced Sulfur Reduction Zones for Lithium-Sulfur Battery Cathodes

A newly designed sulfur/graphene computational model emulates the electrochemical behavior of a Li–S battery cathode, promoting the S–C interaction through the edges of graphene sheets. A random mixture of eight-membered sulfur rings mixed with small graphene sheets is simulated at 64 wt%sulfur loading. Structural stabilization and sulfur reduction calculations are performed with classical reactive molecular dynamics. This methodology allowed the collective behavior of the sulfur and graphene structures to be accounted for. The sulfur encapsulation induces ring opening and the sulfur phase evolves into a distribution of small chain-like structures interacting with C through the graphene edges. This new arrangement of the sulfur phase not only leads to a less pronounced volume expansion during sulfur reduction but also to a different discharge voltage profile, in qualitative agreement with earlier reports on sulfur encapsulation in microporous carbon structures. The Li 2 S phase grows around ensembles of parallel graphene nanosheets during sulfur reduction. No diffusion of sulfur or lithium between graphene nanosheets is observed, and extended Li 2 S domains bridging the space between carbon ensembles are suppressed. The results emphasize the importance of morphology on the electrochemical performance of the composite material. Finally, the sulfur/graphene model outlined here provides new understanding of the graphene effects on the sulfur reduction behavior and the role that van der Waals interactions may play in promoting formation of multilayer graphene ensembles and small Li 2 S domains during sulfur reduction.

25 ENERGY STORAGE↗
DOE OSTI2020

Sulfurized Polyacrylonitrile for High-Performance Lithium–Sulfur Batteries: In-Depth Computational Approach Revealing Multiple Sulfur’s Reduction Pathways and Hidden Li + Storage Mechanisms for Extra Discharge Capacity

Like no other sulfur host material, polyacrylonitrile-derived sulfurized carbon (SPAN) promises improved electrochemical performance for lithium–sulfur batteries, based on its compatibility with carbonate solvents and ability to prevent self-discharge and shuttle effect. However, a complete understanding of the SPAN’s lithiation mechanism is still missing because its structural features vary widely with synthesis conditions, and its electrochemical performance deviates from elemental sulfur. This study continues our research on the elucidation of the SPAN’s structural characteristics and lithiation mechanisms via computational approaches. Here, our models reproduce most experimental data regarding carbon’s graphitization level and conjugated ordering, sulfur–carbon covalent bonding, sulfur loading, and elemental composition. Our simulations emulate the discharge voltage observed in experiments for the first discharge, which reveals that sulfur follows multiple reduction pathways based on its interaction with the carbon backbone. Sulfur reduction takes place above 1.0 V vs Li/Li + mostly in the SPAN-like material, with no long-chain lithium polysulfide formation. Below 1.0 V vs Li/Li + , the backbone’s electrochemical activity occurs via multiple C–Li and N–Li interactions, mostly with edge carbon atoms and pyridinic nitrogen. Moreover, we identify Li + binding sites throughout the graphitized backbone that might lead to prohibited energy costs for Li + deintercalation, which may explain the irreversible capacity loss between the first and second discharges. This work improves understanding of lithiation mechanisms in sulfurized carbon, which is useful for rationally designing SPAN synthesis pathways tailored to increase sulfur loading and enhanced electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2017

Gel based sulfur cathodes with a high sulfur content and large mass loading for high-performance lithium–sulfur batteries

A significantly improved conductive matrix design for the sulfur electrode is essential to solve several problems related to sulfur electrochemistry toward the development of practical lithium–sulfur batteries (LSBs). Great progress has been made by using a variety of carbon-based nanostructures for physically and chemically confining soluble polysulfides as well as providing conductive paths. However, most of these electrode designs have a low sulfur content or a low sulfur loading, leading to a low specific capacity or low areal capacity at the electrode level. Herein, intrinsically N- and O-doped carbon nanoribbon (CNR) aerogels, obtained by pyrolysis of bacterial cellulose (BC) aerogels, were employed to form gel-based sulfur cathodes, simultaneously achieving both a high sulfur content and a high sulfur loading. With a sulfur loading of 6.4 mg cm−2 and a sulfur content of 90% at the whole electrode (including the current collector) level, a capacity as high as 943 mA h g−1 was achieved, which corresponds to an areal capacity of 5.9 mA h cm−2. The outstanding cell performance is attributed to the gel based cathode structure, which can strongly hold a large amount of the catholyte and relieve the shuttle effect of lithium polysulfides.

Li, Shiqi↗
DOE OSTI2025

Revisiting the Impact of Anion Selection on Sulfur Redox Reaction Kinetics for High Sulfur Loading Lithium–Sulfur Batteries

Lithium bis(trifluoromethane)sulfonimide (LiTFSI) is widely used in lithium–sulfur (Li–S) battery electrolytes due to its stability with lithium polysulfides (LiPSs) and moderate compatibility with lithium metal anodes. However, LiTFSI presents environmental concerns due to its association with per- and polyfluoroalkyl substances (PFAS), which are environmentally persistent and potentially toxic, raises sustainability concerns. This research also reveals that LiTFSI limits sulfur redox reactions (SRRs), making it less effective than other lithium salts. Additionally, some salts previously considered incompatible with Li-S systems due to their reactivity with LiPSs are demonstrated to perform effectively. For the first time, a protective, porous cathode electrolyte interphase (CEI) formed in situ through reactions between salt anions and LiPS is reported. The cells delivered a high specific capacity of 1230.8 mAh g −1 at 0.05 C with a sulfur loading of ≈6 mg cm −2 , limited lithium anode, maintaining a capacity retention of 76.2% after 100 cycles at 0.1 C. Under harsh conditions, such as high sulfur loading, lean electrolyte conditions (3 µL mg −1 ), and in anode-free cells, the cells continued to deliver outstanding capacity. This work provides valuable guidelines for understanding and selecting lithium salts to advance electrolyte design for Li–S batteries.

high loading batteries↗
NASA NTRS2011

Radiolysis of Sulfuric Acid, Sulfuric Acid Monohydrate, and Sulfuric Acid Tetrahydrate and Its Relevance to Europa

We report laboratory studies on the 0.8 MeV proton irradiation of ices composed of sulfuric acid (H2SO4), sulfuric acid monohydrate (H2SO4 H2O), and sulfuric acid tetrahydrate (H2SO4 4H2O) between 10 and 180 K. Using infrared spectroscopy, we identify the main radiation products as H2O, SO2, (S2O3)x, H3O+, HSO4(exp -), and SO4(exp 2-). At high radiation doses, we find that H2SO4 molecules are destroyed completely and that H2SO4 H2O is formed on subsequent warming. This hydrate is significantly more stable to radiolytic destruction than pure H2SO4, falling to an equilibrium relative abundance of 50% of its original value on prolonged irradiation. Unlike either pure H2SO4 or H2SO4 H2O, the loss of H2SO4 4H2O exhibits a strong temperature dependence, as the tetrahydrate is essentially unchanged at the highest irradiation temperatures and completely destroyed at the lowest ones, which we speculate is due to a combination of radiolytic destruction and amorphization. Furthermore, at the lower temperatures it is clear that irradiation causes the tetrahydrate spectrum to transition to one that closely resembles the monohydrate spectrum. Extrapolating our results to Europa s surface, we speculate that the variations in SO2 concentrations observed in the chaotic terrains are a result of radiation processing of lower hydration states of sulfuric acid and that the monohydrate will remain stable on the surface over geological times, while the tetrahydrate will remain stable in the warmer regions but be destroyed in the colder regions, unless it can be reformed by other processes, such as thermal reactions induced by diurnal cycling.

Loeffler, M. J.↗
DOE OSTI2015

Reduction mechanism of sulfur in lithium-sulfur battery: From elemental sulfur to polysulfide

In this study, the polysulfide ions formed during the first reduction wave of sulfur in Li–S battery were determined through both in-situ and ex-situ derivatization of polysulfides. By comparing the cyclic voltammetric results with and without the derivatization reagent (methyl triflate) as well as the in-situ and ex-situ derivatization results under potentiostatic condition, in-situ derivatization was found to be more appropriate than its ex-situ counterpart, since subsequent fast chemical reactions between the polysulfides and sulfur may occur during the timeframe of ex-situ procedures. It was found that the major polysulfide ions formed at the first reduction wave of elemental sulfur were the S 4 2– and S 5 2– species, while the widely accepted reduction products of S 8 2– and S 6 2– for the first reduction wave were in low abundance.

25 ENERGY STORAGE↗
DOE OSTI2013

Multi-model Mean Nitrogen and Sulfur Deposition from the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP): Evaluation of Historical and Projected Future Changes

We present multi-model global datasets of nitrogen and sulfate deposition covering time periods from 1850 to 2100, calculated within the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP). The computed deposition fluxes are compared to surface wet deposition and ice-core measurements. We use a new dataset of wet deposition for 2000-2002 based on critical assessment of the quality of existing regional network data. We show that for present-day (year 2000 ACCMIP time-slice), the ACCMIP results perform similarly to previously published multi-model assessments. The analysis of changes between 1980 and 2000 indicates significant differences between model and measurements over the United States, but less so over Europe. This difference points towards misrepresentation of 1980 NH3 emissions over North America. Based on ice-core records, the 1850 deposition fluxes agree well with Greenland ice cores but the change between 1850 and 2000 seems to be overestimated in the Northern Hemisphere for both nitrogen and sulfur species. Using the Representative Concentration Pathways to define the projected climate and atmospheric chemistry related emissions and concentrations, we find large regional nitrogen deposition increases in 2100 in Latin America, Africa and parts of Asia under some of the scenarios considered. Increases in South Asia are especially large, and are seen in all scenarios, with 2100 values more than double 2000 in some scenarios and reaching >1300 mgN/m2/yr averaged over regional to continental scale regions in RCP 2.6 and 8.5, ~30-50% larger than the values in any region currently (2000). Despite known issues, the new ACCMIP deposition dataset provides novel, consistent and evaluated global gridded deposition fields for use in a wide range of climate and ecological studies.

ACCMIP↗
DOE OSTI2014

Toward Understanding the Effect of Low-Activity Waste Glass Composition on Sulfur Solubility

The concentration of sulfur in nuclear waste glass melter feed must be maintained below the point where salt accumulates on the melt surface. The allowable concentrations may range from 0.37 to over 2.05 weight percent (of SO3 on a calcined oxide basis). If the amount of sulfur exceeds its tolerance level a molten salt will accumulate and upset melter operations and potentially shorten melter useful life. Therefore relatively conservative limits have been placed on sulfur loading in melter feed which in-turn significantly impacts the amount of glass that will be produced, in particular at the Hanford site. Crucible-scale sulfur solubility data and scaled melter sulfur tolerance data have been collected on simulated Hanford waste glasses over the last 15 years. These data were compiled and analyzed. A model was developed to predict the solubility of SO3 in glass based on 312 individual glass compositions. This model was shown to well represent the data, accounting for over 80% of the variation in data and was well validated. The model was also found to accurately predict the tolerance for sulfur in melter feed based on 19 scaled melter tests. The model is appropriate for control of waste glass processing which includes uncertainty quantification. The model also gives quantitative estimates of component concentration effects on sulfur solubility. The components that most increase sulfur solubility are Li2O > V2O5 ≈ TiO2 < CaO < P2O5 ≈ ZnO. The components that most decrease sulfur solubility are Cl > Cr2O3 > SiO2 ≈ ZrO2 > Al2O3.

Borosilicate↗
DOE OSTI2016

Proteome Remodeling in Response to Sulfur Limitation in “ Candidatus Pelagibacter ubique”

“ Ca . Pelagibacter ubique” is a key driver of marine biogeochemistry cycles and a model for understanding how minimal genomes evolved in free-living anucleate organisms. This study explores the unusual sulfur acquisition strategy that has evolved in these cells, which lack assimilatory sulfate reduction and instead rely on reduced sulfur compounds found in oxic marine environments to meet their cellular quotas. Our findings demonstrate that the sulfur acquisition systems are constitutively expressed but the enzymatic steps leading to the essential sulfur-containing amino acid methionine are regulated by a unique array of riboswitches and genes, many of which are encoded in a rapidly evolving genome region. These findings support mounting evidence that streamlined cells have evolved regulatory mechanisms that minimize transcriptional switching and, unexpectedly, localize essential sulfur acquisition genes in a genome region normally associated with adaption to environmental variation.

Smith, Daniel P.↗
DOE OSTI2016

Effect of solvents on the electrochemical properties of binder-free sulfur cathode films in lithium–sulfur batteries

Highlights: • The binder-free sulfur electrode with high sulfur contents of 75 wt.% was fabricated. • The binder-free sulfur electrode using NMP solvents showed 784 mAh g{sup −1} after 40 cycles. • The solvent affect the electrochemical properties of binder-free sulfur electrode films. - Abstract: The effects of solvents on the preparation of sulfur cathodes were investigated by fabricating binder-free sulfur electrode films using three different solvents: 1-methyl-2-pyrrolidinone (NMP), acetonitrile, and deionized water. These solvents are commonly employed to dissolve binders used to prepare sulfur cathodes for lithium–sulfur batteries. The sulfur electrode fabricated with NMP had a higher discharge capacity and longer cycle life than the ones fabricated with acetonitrile and deionized water. Better adhesion between the current collector and the sulfur electrode accounted for the improved capacity and cycle life of the battery. In addition, the stability of the electrode in the electrolyte was a result of the solubility of sulfur in the solvent. We thus concluded that the solvents used in the fabrication of sulfur electrodes had a positive influence on the electrochemical properties of Li–S batteries.

36 MATERIALS SCIENCE↗