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At least 199 records · Page 11

A chemically stabilized sulfur cathode for lean electrolyte lithium sulfur batteries

Lithium sulfur batteries (LSBs) are promising next-generation rechargeable batteries due to the high gravimetric energy, low cost, abundance, nontoxicity, and high sustainability of sulfur. However, the dissolution of high-order polysulfide in electrolytes and low Coulombic efficiency of Li anode require excess electrolytes and Li metal, which significantly reduce the energy density of LSBs. Quasi-solid-state LSBs, where sulfur is encapsulated in the micropores of carbon matrix and sealed by solid electrolyte interphase, can operate under lean electrolyte conditions, but a low sulfur loading in carbon matrix (<40 wt %) and low sulfur unitization (<70%) still limit the energy density in a cell level. Here, we significantly increase the sulfur loading in carbon to 60 wt % and sulfur utilization to ∼87% by dispersing sulfur in an oxygen-rich dense carbon host at a molecular level through strong chemical interactions of C–S and O–S. In an all-fluorinated organic lean electrolyte, the C/S cathode experiences a solid-state lithiation/delithiation reaction after the formation of solid electrolyte interphase in the first deep lithiation, completely avoiding the shuttle reaction. The chemically stabilized C/S composite retains a high reversible capacity of 541 mAh⋅g −1 (based on the total weight of the C/S composite) for 200 cycles under lean electrolyte conditions, corresponding to a high energy density of 974 Wh⋅kg −1 . The superior electrochemical performance of the chemical bonding-stabilized C/S composite renders it a promising cathode material for high-energy and long-cycle-life LSBs.

25 ENERGY STORAGE↗

Solvent selection criteria for temperature-resilient lithium–sulfur batteries

All-climate temperature operation capability and increased energy density have been recognized as two crucial targets, but they are rarely achieved together in rechargeable lithium (Li) batteries. Herein, we demonstrate an electrolyte system by using monodentate dibutyl ether with both low melting and high boiling points as the sole solvent. Its weak solvation endows an aggregate solvation structure and low solubility toward polysulfide species in a relatively low electrolyte concentration (2 mol L −1 ). These features were found to be vital in avoiding dendrite growth and enabling Li metal Coulombic efficiencies of 99.0%, 98.2%, and 98.7% at 23 °C, −40 °C, and 50 °C, respectively. Pouch cells employing thin Li metal (50 μm) and high-loading sulfurized polyacrylonitrile (3.3 mAh cm −2 ) cathodes (negative-to-positive capacity ratio = 2) output 87.5% and 115.9% of their room temperature capacity at −40 °C and 50 °C, respectively. This work provides solvent-based design criteria for a wide temperature range Li-sulfur pouch cells.

25 ENERGY STORAGE↗

Vadose Zone Soil Flushing for Chromium Remediation: A Laboratory Investigation to Support Field‐scale Application

Cr(VI) flushing from the vadose zone to the groundwater (with subsequent Cr(VI) removal in groundwater by pump-and-treat system) is a promising remedial technique that has recently been used at field scale. This laboratory study was conducted to provide the technical basis to design a field soil flushing strategy. The objectives were to (1) quantify the relationship between sediment Cr(VI) and Cr(III) mass and release rates and subsequent Cr(VI) leaching; (2) investigate different methodologies to maximize Cr(VI) leaching, and (3) investigate methods to minimize leaching of remaining residual Cr. Characterization of Cr-contaminated sediments (Hanford Site, WA) exhibited Cr(VI) showed that leach rates that were correlated to different Cr surface phases. Sediments with low leachable Cr(VI) (<2 μg/g) leached Cr rapidly, so slow infiltration of water in a single pulse was sufficient to leach most Cr. In contrast, sediments with high Cr (2 to 200 μg/g) released some Cr(VI) quickly but 10 to 50% Cr(VI) slowly (tens to hundreds of hours). Efficient unsaturated leaching of these sediments required a different infiltration strategy that includes: multiple slow leach pulses with time between flushing cycles; the use of a surfactant to increase Cr leaching from low-permeability zones, and the use of a reductant (Na-dithionite or Ca-polysulfide) in the final leach water was highly effective at decreasing residual Cr leaching. This study clearly demonstrated that the methodology of basing laboratory Cr flushing on parameters such as Cr release mass and rates could be used to improve the efficiency of soil flushing at field scale.

Accelerated Cr Flushing↗

Hybrid Li-S pouch cell with a reinforced sulfide glass solid-state electrolyte film separator

Here, in this paper, sulfide glass electrolyte powder with a nominal composition of (Li 2 S) 60 (SiS 2 ) 28 (P 2 S 5 ) 12 is hot pressed at a 330°C and 12 MPa into separator films using non-woven fiberglass reinforcement. The reinforced separator films are 93% dense, bendable, and have an ionic conductivity of 0.7 mS/cm at room temperature. When integrated into hybrid Li-S coin cells with liquid electrolyte, these reinforced glass separators blocked the parasitic polysulfide shuttle sufficiently to enable reversible cycling without LiNO 3 co-salt. Furthermore, the scalability of the reinforced glass separator technology is demonstrated by assembling and testing a hybrid single-layer pouch cell.

25 ENERGY STORAGE↗

Fundamental mechanistic insights into the catalytic reactions of Li-S redox by Co single-atom electrocatalysts via operando methods

Lithium-sulfur batteries represent an attractive option for energy storage applications. A deeper understanding of the multistep lithium-sulfur reactions and the electrocatalytic mechanisms are required to develop advanced, high-performance batteries. We have systematically investigated the lithium-sulfur redox processes catalyzed by a cobalt single-atom electrocatalyst (Co-SAs/NC) via operando confocal Raman microscopy and x-ray absorption spectroscopy (XAS). The real-time observations, based on potentiostatic measurements, indicate that Co-SAs/NC efficiently accelerates the lithium-sulfur reduction/oxidation reactions, which display zero-order kinetics. Under galvanostatic discharge conditions, the typical stepwise mechanism of long-chain and intermediate-chain polysulfides is transformed to a concurrent pathway under electrocatalysis. In addition, operando cobalt K-edge XAS studies elucidate the potential-dependent evolution of cobalt’s oxidation state and the formation of cobalt-sulfur bonds. Our work provides fundamental insights into the mechanisms of catalyzed lithium-sulfur reactions via operando methods, enabling a deeper understanding of electrocatalysis and interfacial dynamics in electrical energy storage systems.

36 MATERIALS SCIENCE↗

Lithium-Sulfur Batteries with a Block Copolymer Electrolyte Analyzed by X-ray Microtomography

Most of the work on Lithium-sulfur (LiS) batteries use liquid electrolytes that have limited stability when coupled with Li metal anodes. We have studied LiS batteries with a solid block copolymer electrolyte which exhibits improved stability against Li anodes. Additionally, the electrolyte comprises a polystyrene-b-poly(ethylene oxide) (SEO) copolymer doped with a Li salt. Hollow carbon nanospheres impregnated with sulfur were used to build a composite cathode. Two types of sulfur-impregnated functionalized carbon nanospheres were used: One with carboxylic acid groups and the other with short lithium poly(4-styrenesulfonyl(trifluoromethylsulfonyl)imide) (PSTFSI-Li) chains. Cells with Li S dissolved in the SEO based electrolyte served as the baseline. After cycling, the reason for capacity fade was determined by imaging the batteries using synchrotron hard X-ray microtomography. It is generally assumed that LiS cells fail due to dissolution of polysulfide into the liquid electrolyte, i.e., the main problems related to the cathode. In our all-solid cells, failure was primarily due to delamination of the Li foil from the polymer electrolyte layer. Delamination is also observed at the sulfur cathode. It is likely that the large changes in volume of the active materials during cycling induce delamination in all-solid LiS cells. 2 8

25 ENERGY STORAGE↗

Lithiation of Sulfur-Graphene Compounds Using Reactive Force-Field Molecular Dynamics Simulations

We performed molecular dynamics simulations of lithium-sulfur-graphene compounds using reactive force fields, providing a time scale to observe atomistic features relevant to the microscopic behavior of the of the bulk of sulfur-based cathodes to be used beyond our present Li-ion batteries. The samples we used were set to realistic geometries through sophisticated protocols to simulate ultrafast reactions that occur within the picosecond range, thus allowing us to get some insights into the characteristics of the bulk material in working cathodes of Li–S batteries, which are mixed with carbon to increase the poor electronic conductivity of S. We report chemical speciation and geometrical data at atomistic levels. We observed that slowly lithiated cathodes were more stable and with higher density than those that were suddenly fully-lithiated. We did not observe molecular Li 2 S formation; however, we observed an amorphous solid arrangement with the same stoichiometry of Li and S, with S–Li–S angles of ~111° and smaller ones due to the interaction between polysulfides that did not reacted totally. In addition, graphene keeps its planar shape; however, S8 changes its shape from rings to chains. Lithiated structures are more stable with lower energies, and more close-packed structures than structures with Li already inserted.

25 ENERGY STORAGE↗

Elucidating Sodium-Sulfur Battery Chemistry using Operando Transmission X-ray Microscopy and X-ray Absorption Spectroscopy

Room-temperature sodium-sulfur (Na-S) batteries offer a beneficial and cost-effective solution for powering modern electric grids and devices. However, Na-S batteries suffer from performance decay during battery cycling due to the sluggish kinetics and polysulfide shuttling. Revealing the conversion mechanism of the Na-S chemistry is critical to designing high-capacity and stable Na-S batteries. In this study, we employed operando X-ray microscopy and operando X-ray absorption spectroscopy to elucidate the sulfur conversion in a carbon host using an ether-based electrolyte. We reveal the structural and chemical evolution of the sulfur cathode during cycling, which results in volume expansion and the dissolution of active material, ultimately affecting the battery performance. Our work provides fundamental insight into the sulfur reaction scheme, addressing the lingering challenges before establishing inexpensive Na-S batteries for broad applications, including portable electronics and large-scale energy storage.

Jagadeesan, Sathya Narayanan [SLAC National Accele↗

Structural and Kinetic Characterization of Hyperthermophilic NADH-Dependent Persulfide Reductase from Archaeoglobus fulgidus

NADH-dependent persulfide reductase (Npsr) has been proposed to facilitate dissimilatory sulfur respiration by reducing persulfide or sulfane sulfur-containing substrates to H2S. The presence of this gene in the sulfate and thiosulfate-reducing Archaeoglobus fulgidus DSM 4304 and other hyperthermophilic Archaeoglobales appears anomalous, as A. fulgidus is unable to respire S0 and grow in the presence of elemental sulfur. To assess the role of Npsr in the sulfur metabolism of A. fulgidus DSM 4304, the Npsr from A. fulgidus was characterized. AfNpsr is specific for persulfide and polysulfide as substrates in the oxidative half-reaction, exhibiting k cat / K m on the order of 104 M-1 s-1, which is similar to the kinetic parameters observed for hyperthermophilic CoA persulfide reductases. In contrast to the bacterial Npsr, AfNpsr exhibits low disulfide reductase activity with DTNB; however, similar to the bacterial enzymes, it does not show detectable activity with CoA-disulfide, oxidized glutathione, or cystine. The 3.1 Å X-ray structure of AfNpsr reveals access to the tightly bound catalytic CoA, and the active site Cys 42 is restricted by a flexible loop (residues 60-66) that is not seen in the bacterial homologs from Shewanella loihica PV-4 and Bacillus anthracis. Unlike the bacterial enzymes, AfNpsr exhibits NADH oxidase activity and also shows no detectable activity with NADPH. Models suggest steric and electrostatic repulsions of the NADPH 2 ′ -phosphate account for the strong preference for NADH. The presence of Npsr in the nonsulfur-reducing A. fulgidus suggests that the enzyme may offer some protection against S0 or serve in another metabolic role that has yet to be identified.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multifunctional, Self-Healing Polyelectrolyte Gels for Long-Cycle-Life, High-Capacity Sulfur Cathodes in Li-S Batteries (FY2020 Final Report)

The project aims to develop polyelectrolyte gels consisting of partially crosslinked ionomer, interpenetrated with self-healing/polysulfide-trapping chains and swelled with a mixture of room temperature ionic liquid (RTIL) and lithium salt. To our knowledge, no other sulfur-based cathode design has combined self-healing behavior, polysulfide containment, and lithium dendrite suppression into a single design. We have demonstrated the benefits of multifunctional ionomer gel polyelectrolytes / gel cathodes with self-healing properties, as well as chemical modification of mesoporous carbons for S/C composite cathodes. Success of the proposed program of study would have wide ranging impact on the electric vehicle industry and society as a whole. A Li-S battery system with the capability of doubling lithium-ion energy density would enable the production of lighter, longer range electric vehicles at a cost that is affordable to the average U.S. household. The availability of such vehicles should lead to wide-ranging adoption over the coming years which, in combination with increased renewable electricity generation, will drastically decrease carbon emissions across the country and reduce U.S. dependency on fossil fuel sources.

25 ENERGY STORAGE↗

Combined Technologies for In Situ Remediation of Tc-99 and U in Subsurface Sediments

In this study, combinations of chemical remedies were tested in bench-scale batch experiments to evaluate a two-step reduction-sequestration approach to effectively stabilize high concentrations of inorganic contaminant mixtures. Bench tests simulated contaminant and geochemical conditions of a perched aquifer located within the Central Plateau at the Hanford Site, located in southeastern Washington State (USA). Pairwise combinations of a reductant [e.g., zero valent iron, sulfur modified iron (SMI), or calcium polysulfide] and a sequestering agent [e.g., calcite, apatite, or dilute alkaline solution (e.g., NaOH)] were evaluated for immobilization and stabilization of technetium (Tc) (50,000 pCi/L), uranium (U) (150 mg/L), and nitrate (NO 3 ) (200 mg/L) in high ionic strength groundwater. The results of these batch studies demonstrated that reduction by SMI and sequestration in apatite or calcite are the most effective combination for these contaminant mixtures and conditions. Aqueous concentrations of Tc and U decreased by 95.6% ± 2.5% and 101.1% ± 5.2%, respectively, with SMI-apatite and 98.3% ± 0.0% and 101.2% ± 5.2%, respectively, with SMI-calcite. Sequential extractions showed that sequestered contaminants had limited capacity for re-oxidation; in fact, less than 10% of immobilized Tc and U was recovered by selective extraction of mineral phases most susceptible to oxidation. In addition, X-ray absorption near edge structure analysis of the sediment samples treated with SMI-calcite showed the presence of only U(IV), while both U(IV) and U(VI) were present in the SMI apatite combination [ratio of 0.43 U(IV):0.59 U(VI)].This study describes preliminary results that a two-step approach for stabilizing contaminant mixtures of long-lived radionuclides can be effective at reducing contaminant fluxes to groundwater from vadose and perched water zones.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Design, Processing, and Integration of Pouch-Format Cell for High-Energy Lithium-Sulfur Batteries

This project objective was to develop and demonstrate a lithium-sulfur (Li-S) battery in a pouch-format cell capable of achieving an energy density ≥ 500 Wh/kg while achieving a 1,000 cycle life. The research focused on cell optimization and fabrication addressing different technical barriers and challenges including: 1) thin lithium anode optimization; 2) current collector and tab attachment design; 3) cathode porosity control; 4) electrolyte to sulfur ratio control; 5) cell design; and 6) cell fabrication. The project developed and demonstrated various technologies to address these technical barriers and challenges. The project demonstrated a thin lithium anode by vapor deposition, a collector design and validation of laser welding of tab attachment method, a cathode porosity control strategy by binder optimization, a calendaring process control and surface/interface treatment, and an electrolyte to sulfur ratio control with influence on cell energy density. The sulfur cathode was optimized by tuning the formulation, optimizing the calendaring process, and introducing a novel electrode fabrication process. To address the electrolyte performance issue, the electrolyte optimization was achieved with additive and formulation tuning and the introduction of a dual-phase electrolyte system. In addition to the demonstration of the optimized electrode with a novel fast-curing coating process and dual-phase electrolyte, a coating separator was further developed to address the polysulfide shuttling issue. The resulting new cell design with these optimized cell components was demonstrated in the 1 Ah pouch cell with medium sulfur loading and moderate porosity (~ 4.5 mAh cm-2, 65% porosity) and showed an energy density of > 400 Wh/kg (with E/S ratio of 2.8). The Li-SPAN cell configuration was also evaluated in combination with a new dual-phase electrolyte system. Initial coin cell performance demonstrated cycle stability of >300 cycles with an estimated energy density of 300 Wh/kg at the pouch format level. The corresponding 1 Ah pouch format SPAN cells with the new polymer electrolyte were developed which has shown a stable capacity at 800-900 mAh for ~40 cycles so far.

25 ENERGY STORAGE↗

The Role of Metal Oxides in Li-S Batteries: A High-Areal-Capacity Sulfur Composite Cathode Investigation

Compared to lithium-ion batteries (LIB), lithium-sulfur (Li-S) batteries have low cost and high theoretical specific energy (2510 Wh/kg or about 10 times of the LIB). However, Li-S batteries have several challenges, including large volume expansion, poor utilization of the end products, sluggish kinetics of polysulfides, and crossover, so-called the "shuttle effect". To address these issues, we have introduced metal oxides to the Li-S electrode to develop a metal-oxide-sulfur composite electrode. We aim to use metal oxides to assist the Li-S formation (dissociation) during discharge (charge) cycles. We elect to focus on LIB-based metal oxides to ensure that the added material can contribute storage capacity to the battery. Our cathodes are fabricated by both the conventional slurry casting and air-controlled electrospray. LIB electrode materials, such as Li(Ni 0.6 Mn 0.6 Co 0.2 )O 2 , LiMn 2 O 4 , Li 2 TiO 3 , etc, were incorporated with the sulfur-carbon composite and their charge-discharge performances are compared. We found that the presence of metal oxides increased sulfur utilization with stable cycling performance, even in cells with high areal capacities. To unveil the interactions between lithium metal oxides and sulfur, the cathodes were analyzed by various characterization techniques, including scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, and electrochemistry. The analysis of the role of the oxides will be presented along with the reaction mechanism.

25 ENERGY STORAGE↗

Synergy of Graphene Nanoribbons and Graphene Sheets for High-Rate Lithium-Sulfur Batteries

According to the increasing demands for shortening the battery charging time, high current rate (C-rate) performances become more significant in practical applications. With a higher theoretical capacity, lithium-sulfur batteries are treated as promising candidates for the next-generation batteries. In this work, the utilization of graphene nanoribbons (GNRs) exhibits the benefits in conductivity and other electrochemical performances, especially for high-rate applications. With air-controlled electrospray as the method, carbon encapsulated sulfur particles, poly(acrylic acid), reduced graphene oxide (rGO) sheets, and GNRs are mixed and directly deposited onto the carbon coated aluminum collector, to employ as the cathode. The scanning electron microscopy (SEM) imaging exhibits that the two-dimensional structure of GNRs helps construct inter-connected networks. This improved structure of cathode can increase the electroconductivity, confirmed by the electrochemical impedance spectroscopy (EIS), and modify the porosity, indicated through pore size distribution profiles. In this way, the polysulfides can be more efficiently trapped and utilized, realizing the promising behavior with faster charge transfer. In terms of the cycling performance at 0.2 C, the batteries with GNRs can perform 18% higher in capacity than those without GNRs, without decreasing the charge retention. According to the rate-capability tests, systems with GNRs can achieve enhanced performance compared to batteries with precursor carbon nanotubes (CNTs), especially at high C-rates. At 2 C, with 80 wt % of graphene-based materials as GNRs, batteries can achieve an increase in capacity by 78% and 41% compared with systems without GNRs and those with CNTs, respectively. Accordingly, the results testify the synergy of GNRs and rGO sheets in Li-S batteries.

25 ENERGY STORAGE↗

High Performance Flow Battery with Inexpensive Inorganic Reactants: DAYS Program (Final Technical Report)

RTRC’s DAYS projects focused on new flow battery (FB) chemistries for long duration energy storage: one that pairs aqueous polysulfide and manganese active materials in strongly alkaline electrolytes (S/Mn); another explores ligand-modified metal (LMM) chemistries in moderate pH electrolyte conditions. The S/Mn chemistry met durability targets by running for over 500 cycles and 1000 hours. Combined with this durability, power densities of up to 60 mW/cm2 at 80% round-trip efficiency, and exceptionally low-cost S and Mn active materials, the S/Mn FB offers a pathway to meeting the <5¢/kW-hr levelized cost of storage (LCOS) target first proposed by the DAYS Program and accepted by the DOE Energy Storage Grand Challenge. The LMM chemistry made impressive progress as well, including durability tests that retained performance over 600 hours of cycling. Cell optimization allowed this chemistry to operate as high as 500 mW/cm2 at 80% round-trip efficiency, nearly 10x the power density of S/Mn and comparable to the power density achieved in RTRC’s flow battery stacks using acidic vanadium battery solutions. This enabled the LMM chemistry to also offer a pathway to the <5¢/kW-hr LCOS DAYS and DOE targets. The promising results from the LMM chemistry have led to a recent DOE AMO award to advance the technology to a 5 kW, 20 kW-hr prototype.

25 ENERGY STORAGE↗

New Engineering Concepts to High Energy Density Li-S Batteries

Li-S batteries (LSBs) with energy densities > 500 Wh/kg @ C/5 and >1000 cycles, cycle life operating over wide temperatures has been identified to be critical for meeting the global energy demands. Progress is however, very much limited due to several major hurdles related to the following: (a) poor Li' reaction kinetics (conductivity/diffusivity) enabling full reversible S conversion to Li2S, (b) inferior electron (e) conductivity, specific capacity and cycle life due to electrolyte soluble species of polysulfides (PSs) formed with the reaction of Li ions with sulfur migrating to anode, (c) unstable solid electrolyte interphase (SEI) formation and finally, (d) dendrites that are formed on the Li metal anode severely limiting the cycle life due to polarization at the solid/liquid interfaces causing safety, inferior capacity, energy density, rate, and cycle life issues. Creation of a fully functional economical ≤$80/kWh, high energy density LSBs is vital for enabling its widespread commercial deployment and use in current and next generation electric vehicles.

25 ENERGY STORAGE↗

Lithium-sulfur battery with high sulfur loading

A lithium-sulfur battery cathode including conductive porous carbon particles vacuum infused with sulfur and a conductive collector substrate to which the sulfur infused porous carbon particles are deposited. The sulfur infused carbon particles are encapsulated by an encapsulation polymer, the encapsulation polymer having ionic conductivity, electronic conductivity, polysulfide affinity, or combinations thereof. A lithium-sulfur battery including the lithium-sulfur battery cathode, a lithium anode and an electrolyte disposed between the sulfur cathode and the lithium anode is also provided. Methods of producing the sulfur cathode for use in a lithium-sulfur battery by a hybrid vacuum-and-melt method are also provided.

Henslee, Brian E.↗

Rechargeable lithium sulfur and/or selenium battery

An electrochemical device includes a cathode comprising a first cathode component of lithium and Se x S y ; and a second cathode component of an alkali metal and/or alkaline earth metal sulfur and/or selenide, different from the first cathode component; an initial discharge product of a polyselenide and/or polysulfide anion charge compensated by an alkali metal and/or alkaline earth metal cation; an anode; a porous separator; and a non-aqueous electrolyte with one or more lithium salts, and one or more solvents; wherein the electrochemical device is a lithium sulfur and/or lithium selenide battery.

Li, Matthew↗