Browse
Submit Data
Databases
API
Help

Dataset Information

26 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Universal-Descriptors-Guided Design of Single Atom Catalysts toward Oxidation of Li₂ S in Lithium-Sulfur Batteries.

ABSTRACT: The sulfur redox kinetics critically matters to superior lithium-sulfur (Li-S) batteries, for which single atom catalysts (SACs) take effect on promoting Li₂ S redox process and mitigating the shuttle behavior of lithium polysulfide (LiPs). However, conventional trial-and-error strategy significantly slows down the development of SACs in Li-S batteries. Here, the Li₂ S oxidation processes over MN₄ @G catalysts are fully explored and energy barrier of Li₂ S decomposition (E_b ) is identified to correlate strongly with three parameters of energy difference between initial and final states of Li₂ S decomposition, reaction energy of Li₂ S oxidation and LiS bond strength. These three parameters can serve as efficient descriptors by which two excellent SACs of MoN₄ @G and WN₄ @G are screened which give rise to E_b values of 0.58 and 0.55 eV, respectively, outperforming other analogues in adsorbing LiPs and accelerating the redox kinetics of Li₂ S. This method can be extended to a wider range of SACs by coupling MN₄ moiety with heterostructures and heteroatoms beyond N where WN₄ @G/TiS₂ heterointerface is predicted to exhibit enhanced catalytic performance for Li₂ S decomposition with E_b of 0.40 eV. This work will help accelerate the process of designing a wider range of efficient catalysts in Li-S batteries and even beyond, e.g. alkali-ion-Chalcogen batteries.

SUBMITTER: Zeng Z

PROVIDER: S-EPMC8655168 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Interfacial "Double-Terminal Binding Sites" Catalysts Synergistically Boosting the Electrocatalytic Li2S Redox for Durable Lithium-Sulfur Batteries.

Project description:Catalytic conversion of polysulfides emerges as a promising approach to improve the kinetics and mitigate polysulfide shuttling in lithium-sulfur (Li-S) batteries, especially under conditions of high sulfur loading and lean electrolyte. Herein, we present a separator architecture that incorporates double-terminal binding (DTB) sites within a nitrogen-doped carbon framework, consisting of polar Co0.85Se and Co clusters (Co/Co0.85Se@NC), to enhance the durability of Li-S batteries. The uniformly dispersed clusters of polar Co0.85Se and Co offer abundant active sites for lithium polysulfides (LiPSs), enabling efficient LiPS conversion while also serving as anchors through a combination of chemical interactions. Density functional theory calculations, along with in situ Raman and X-ray diffraction characterizations, reveal that the DTB effect strengthens the binding energy to polysulfides and lowers the energy barriers of polysulfide redox reactions. Li-S batteries utilizing the Co/Co0.85Se@NC-modified separator demonstrate exceptional cycling stability (0.042% per cycle over 1000 cycles at 2 C) and rate capability (849 mAh g-1 at 3 C), as well as deliver an impressive areal capacity of 10.0 mAh cm-2 even in challenging conditions with a high sulfur loading (10.7 mg cm-2) and lean electrolyte environments (5.8 μL mg-1). The DTB site strategy offers valuable insights into the development of high-performance Li-S batteries.

| S-EPMC10976959 | biostudies-literature

Unifying the Clustering Kinetics of Lithium Polysulfides with the Nucleation Behavior of Li2S in Lithium-Sulfur Batteries.

Project description:Within the lithium-sulfur (Li-S) battery, a wide variety of soluble lithium polysulfide intermediates form during operation. Under lean-electrolyte or low-temperature conditions, the solution coordination of polysulfides dynamically shifts to highly clustered states, which is subsequently accompanied by inhibited electrochemical kinetics. In fact, it has been shown that the tendency for polysulfides to strongly aggregate is one of the dominant kinetically limiting obstacles towards achieving adequate utilization of active material under such conditions. While this association has been noted before, it is not explicitly understood what mechanism intrinsic to polysulfide clustering curtails the electrochemical utilization of active material, particularly during the conversion to insoluble Li2S. Here, we perform a series of investigations to unify and link the kinetic constraints that arise from polysulfide clustering to the nucleation and growth behavior of Li2S. We find that there is a drastic decrease in polysulfide diffusion coefficient arising from the advent of clustering, and that this decline functionally matches that seen for the nucleation and growth rate constants for Li2S deposition. Additionally, it is found that there is a less favorable minimization of energy during Li2S nucleation, arising from the altered solvation stability of polysulfide clusters. This knowledge expands our understanding of the Li-S materials chemistry and the primary factors dictating the electrochemical behavior.

| S-EPMC8243368 | biostudies-literature

Manipulating Li2S2/Li2S mixed discharge products of all-solid-state lithium sulfur batteries for improved cycle life.

Project description:All-solid-state lithium-sulfur batteries offer a compelling opportunity for next-generation energy storage, due to their high theoretical energy density, low cost, and improved safety. However, their widespread adoption is hindered by an inadequate understanding of their discharge products. Using X-ray absorption spectroscopy and time-of-flight secondary ion mass spectrometry, we reveal that the discharge product of all-solid-state lithium-sulfur batteries is not solely composed of Li2S, but rather consists of a mixture of Li2S and Li2S2. Employing this insight, we propose an integrated strategy that: (1) manipulates the lower cutoff potential to promote a Li2S2-dominant discharge product and (2) incorporates a trace amount of solid-state catalyst (LiI) into the S composite electrode. This approach leads to all-solid-state cells with a Li-In alloy negative electrode that deliver a reversible capacity of 979.6 mAh g-1 for 1500 cycles at 2.0 A g-1 at 25 °C. Our findings provide crucial insights into the discharge products of all-solid-state lithium-sulfur batteries and may offer a feasible approach to enhance their overall performance.

| S-EPMC10570351 | biostudies-literature

Tuning lithium-peroxide formation and decomposition routes with single-atom catalysts for lithium-oxygen batteries.

Project description:Lithium-oxygen batteries with ultrahigh energy density have received considerable attention as of the future energy storage technologies. The development of effective electrocatalysts and a corresponding working mechanism during cycling are critically important for lithium-oxygen batteries. Here, a single cobalt atom electrocatalyst is synthesized for lithium-oxygen batteries by a polymer encapsulation strategy. The isolated moieties of single atom catalysts can effectively regulate the distribution of active sites to form micrometre-sized flower-like lithium peroxide and promote the decomposition of lithium peroxide by a one-electron pathway. The battery with single cobalt atoms can operate with high round-trip efficiency (86.2%) and long-term stability (218 days), which is superior to a commercial 5?wt% platinum/carbon catalyst. We reveal that the synergy between a single atom and the support endows the catalyst with excellent stability and durability. The promising results provide insights into the design of highly efficient catalysts for lithium-oxygen batteries and greatly expand the scope of future investigation.

| S-EPMC7198606 | biostudies-literature

MnO2-graphene nanosheets wrapped mesoporous carbon/sulfur composite for lithium-sulfur batteries.

Project description:MnO2-graphene nanosheets wrapped mesoporous carbon/sulfur (MGN@MC/S) composite is successfully synthesized derived from metal-organic frameworks and investigated as cathode for lithium-ion batteries. Used as cathode, MGN@MC/S composite possesses electronic conductivity network for redox electron transfer and strong chemical bonding to lithium polysulfides, which enables low capacity loss to be achieved. MGN@MC/S cathodes exhibit high reversible capacity of 1475 mA h g-1 at 0.1 C and an ultra-low capacity fading of 0.042% per cycle at 1 C over 450 cycles.

| S-EPMC5830778 | biostudies-literature

Crumpled graphene-encapsulated sulfur for lithium-sulfur batteries.

Project description:Lithium-sulfur batteries are promising technology in electrical vehicles and large-scale energy storage systems. However, their market penetration is seriously impeded by great challenges such as the low electrical conduction of sulfur and lithium sulfides, and lithium polysulfides' shuttling effect. This work shows that such challenges can be partly resolved by encapsulating sulfur in crumpled reduced graphene oxide (S@crGO), which was synthesized by a facile and scalable one-step in situ method. The strong interaction between sulfur and the graphene host, micro- and meso-pore structures, and rich surface functional groups contribute to the high performance of the S@crGO cathode for lithium-sulfur batteries.

| S-EPMC9080550 | biostudies-literature

Battery Separators Functionalized with Edge-Rich MoS2/C Hollow Microspheres for the Uniform Deposition of Li2S in High-Performance Lithium-Sulfur Batteries.

Project description:As promising energy storage systems, lithium-sulfur (Li-S) batteries have attracted significant attention because of their ultra-high energy densities. However, Li-S battery suffers problems related to the complex phase conversion that occurs during the charge-discharge process, particularly the deposition of solid Li2S from the liquid-phase polysulfides, which greatly limits its practical application. In this paper, edge-rich MoS2/C hollow microspheres (Edg-MoS2/C HMs) were designed and used to functionalize separator for Li-S battery, resulting in the uniform deposition of Li2S. The microspheres were fabricated through the facile hydrothermal treatment of MoO3-aniline nanowires and a subsequent carbonization process. The obtained Edg-MoS2/C HMs have a strong chemical absorption capability and high density of Li2S binding sites, and exhibit excellent electrocatalytic performance and can effectively hinder the polysulfide shuttle effect and guide the uniform nucleation and growth of Li2S. Furthermore, we demonstrate that the Edg-MoS2/C HMs can effectively regulate the deposition of Li2S and significantly improve the reversibility of the phase conversion of the active sulfur species, especially at high sulfur loadings and high C-rates. As a result, a cell containing a separator functionalized with Edg-MoS2/C HMs exhibited an initial discharge capacity of 935 mAh g-1 at 1.0 C and maintained a capacity of 494 mAh g-1 after 1000 cycles with a sulfur loading of 1.7 mg cm-2. Impressively, at a high sulfur loading of 6.1 mg cm-2 and high rate of 0.5 C, the cell still delivered a high reversible discharge capacity of 478 mAh g-1 after 300 cycles. This work provides fresh insights into energy storage systems related to complex phase conversions.

| S-EPMC7770949 | biostudies-literature

Lychee-like TiO2@TiN dual-function composite material for lithium-sulfur batteries.

Project description:Lithium-sulfur (Li-S) batteries are promising candidates for next generation rechargeable batteries because of their high energy density of 2600 W h kg-1. However, the insulating nature of sulfur and Li2S, the "shuttle effect" of lithium polysulfides (LiPSs), and the volumetric change of sulfur electrodes limit the practical application of Li-S batteries. Here, lychee-like TiO2@TiN hollow spheres (LTTHS) have been developed that combine the advantages of high adsorption TiO2 and high conductivity TiN to achieve smooth adsorption/spread/conversion of LiPSs and use them as a sulfur host material in Li-S batteries for the first time. The cathode exhibits an initial specific capacity of 1254 mA h g-1 and a reversible capacity of 533 mA h g-1 after 500 cycles at 0.2C, which corresponds to an average coulombic efficiency up to 99%. The cell with the LTTHS@S cathode achieved an extended lifespan of over 1000 cycles. Such good performance can be assigned to the good adsorption and catalysis of the dual-function TiO2@TiN composite. This work proved that the TiO2@TiN composite can be an attractive matrix for sulfur cathodes.

| S-EPMC9048996 | biostudies-literature

Cofactor-Assisted Artificial Enzyme with Multiple Li-Bond Networks for Sustainable Polysulfide Conversion in Lithium-Sulfur Batteries.

Project description:Lithium-sulfur batteries possess high theoretical energy density but suffer from rapid capacity fade due to the shuttling and sluggish conversion of polysulfides. Aiming at these problems, a biomimetic design of cofactor-assisted artificial enzyme catalyst, melamine (MM) crosslinked hemin on carboxylated carbon nanotubes (CNTs) (i.e., [CNTs-MM-hemin]), is presented to efficiently convert polysulfides. The MM cofactors bind with the hemin artificial enzymes and CNT conductive substrates through FeN5 coordination and/or covalent amide bonds to provide high and durable catalytic activity for polysulfide conversions, while π-π conjugations between hemin and CNTs and multiple Li-bond networks offered by MM endow the cathode with good electronic/Li+ transmission ability. This synergistic mechanism enables rapid sulfur reaction kinetics, alleviated polysulfide shuttling, and an ultralow (<1.3%) loss of hemin active sites in electrolyte, which is ≈60 times lower than those of noncovalent crosslinked samples. As a result, the Li-S battery using [CNTs-MM-hemin] cathode retains a capacity of 571 mAh g-1 after 900 cycles at 1C with an ultralow capacity decay rate of 0.046% per cycle. Even under raising sulfur loadings up to 7.5 mg cm-2 , the cathode still can steadily run 110 cycles with a capacity retention of 83%.

| S-EPMC8787425 | biostudies-literature

Synergy between Interconnected Porous Carbon-Sulfur Cathode and Metallic MgB2 Interlayer as a Lithium Polysulfide Immobilizer for High-Performance Lithium-Sulfur Batteries.

Project description:Lithium-sulfur (Li-S) batteries are the potential candidates for developing high-energy-density electric vehicles. However, poor electrical conductivity of sulfur/discharged products, low active material utilization, shuttle mechanism, and poor cycle life remain the major challenges for the development of Li-S batteries. Herein, we report the nitrogen-doped highly porous carbon (NC) with interconnected pores as the sulfur host (NC-S), which is synthesized by a facile one-step process without using any template and activation agents. The highly interconnected porous structure of NC can accommodate a high amount of sulfur loading and provide space for sulfur volume expansion during redox reactions. Besides, to mitigate the lithium polysulfide dissolution and shuttle mechanism, metallic and polar magnesium diboride (MgB2) is used as an interlayer. Consequently, the NC-S/MgB2 cathode delivers higher specific capacity, rate capability, and excellent cyclic stability than the NC-S cathode and bulk sulfur cathode with MgB2 interlayer. The lithium polysulfide (LPS) adsorption test shows that MgB2 has strong chemisorption toward lithium polysulfides, which can inhibit the dissolution of LPS into the electrolyte and minimizes the shuttle effect. The dynamic electrochemical impedance spectroscopy analysis investigates the electrochemical reaction kinetics of the NC-S/MgB2 cathode during the charging and discharging processes. Overall, this work demonstrates that the synergy between the nitrogen-doped porous carbon-sulfur host and polar metallic MgB2 improves the performance of the Li-S battery, which is beneficial for the development of high-energy-density batteries for the future.

| S-EPMC7482300 | biostudies-literature