Origin of the High Catalytic Activity of MoS₂ in Na–S Batteries: Electrochemically Reconstructed Mo Single Atoms

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(46), P. 32124 - 32134

Published: Nov. 8, 2024

Room-temperature sodium–sulfur (RT Na–S) batteries with high energy density and low cost are considered promising next-generation electrochemical storage systems. However, their practical feasibility is seriously impeded by the shuttle effect of sodium polysulfide (NaPSs) resulting from sluggish reaction kinetics. Introducing a suitable catalyst to accelerate conversion NaPSs most used strategy inhibit effect. Traditional catalytic approaches often want avoid irreversible phase transition at deep discharge. On contrary, here, we leverage intrinsic structural tunability MoS2 in opposite direction innovatively propose voltage modulation for situ generation trace Mo single atoms (MoSAC) during first charge–discharge process, leading formation highly active phases (MoS2/MoSAC) through self-reconstruction. Theoretical calculations reveal that incorporation MoSAC modulates electronic structure d-band center, which not only effectively promotes d–p orbital hybridization but also accelerates intermediate desorption bonding transition, dynamic single-atom synergistic mechanism enhances adsorption response between metal site NaPSs, significantly improves sulfur redox (SRR), initial capacity MoS2/MoSAC/CF@S cell 0.2 A g–1 increased 46.58% compared MoS2/CF@S cell. The discovery MoS2/MoSAC/CF provides new insights into adjusting function disulfide catalysts atomic scale, offering hope development high-specific-energy RT Na–S batteries.

Language: Английский

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Balanced d-Band Model: A Framework for Balancing Redox Reactions in Lithium–Sulfur Batteries

ACS Nano, Journal Year: 2024, Volume and Issue: 18(47), P. 32732 - 32745

Published: Nov. 11, 2024

Managing the redox reactions of polysulfides is crucial for improving performance lithium-sulfur batteries (LSBs). Herein, we introduce a progressive theoretical framework: balanced d-band model, which based on classical center theory. Specifically, by optimizing position in middle between highest occupied molecular orbital (HOMO) and lowest unoccupied (LUMO) each sulfur species, fast oxidation reduction species can be achieved simultaneously. To validate this theory, synthesized catalyst featuring an situ phosphorized heterostructure (NOP) nickel oxide (NiO), effectively optimizes at HOMO LUMO species. Aided kinetics NOP-based cell high reversible capacity, superior cycling stability, prolonged cycle life. This study extends conventional theory introduces innovative model to expand our understanding internal reaction mechanisms LSBs.

Language: Английский

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MoS₂-Modified N-Doped Graphene/Organosulfide Composite Cathode Material for High-Performance Lithium–Sulfur Batteries

ACS Applied Energy Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 13, 2025

Language: Английский

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Flower-like Ti3C2T -TiO2 modified with ZnS nanoparticles as adsorption-catalytic cathodic material for lithium–sulfur batteries

Journal of Energy Storage, Journal Year: 2025, Volume and Issue: 118, P. 116241 - 116241

Published: March 17, 2025

Language: Английский

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Revisiting the Nanofluid Behavior of Polysulfides in Carbon‐Based Interlayers: Longitudinal Osmotic Diffusion and Transverse Radiation‐Distribution Induced by Mn‐Based Catalysts

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Abstract Carbon‐based interlayer as the secondary current collector is a typical approach for suppressing polysulfide shuttle effect in lithium‐sulfur batteries (LSBs). The effective operating lifespan determined by balance between local concentration and bearing capacity of interlayers. However, microscopic diffusion polysulfides within interlayers under multiple force fields remains unclear, particularly catalyst on multi‐scale behavior. Herein, first identification reported with coupling longitudinal osmotic transverse radioactive through revisiting Mn‐based catalysts (Mn‐X, X = N, O, or P). In addition to electric field forces during charging discharging, free sustain tension, leading radiation This adaptive adjustment optimizes distribution, mitigating risk deactivation caused excessive concentration. extent lateral positively correlated physicochemical adsorption interlayer. Specifically, stronger static demonstrates broader range. work re‐evaluates behavior interlayers, further guiding design high performance collector.

Language: Английский

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Axial Coordination Regulating Electronic Delocalization of p‐Block In−N₄ Sites to Accelerate Sulfur Reduction Reaction

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 21, 2025

Abstract Modulating the electron delocalization of catalysts can improve activation and conversion capabilities lithium polysulfides (LiPSs) in lithium‐sulfur batteries, while precise mechanism underlying this enhancement remains unclear. Herein, a p‐block In single‐atom (In‐N 4 ) is constructed with moderate via axial coordination engineering gallium nitride (GaN), which exhibits best adsorption electrocatalytic activity toward LiPSs. situ characterization analysis combined advanced theoretical calculations demonstrate that In‐N‐Ga induces transfer from sites N GaN unconventional sp 3 d 2 hybridization interactions sites. This further helps to optimize configuration through orbital between hybrid p S atoms LiPSs, namely − hybridization, weaken S−S covalent bonds LiPSs significantly accelerate sulfur reduction reaction. Accordingly, capacity decay battery In−SA/GaN catalyst only 0.040% per cycle over 800 cycles at 5 C. The stacked pouch cell delivers reversible 600 mAh after 100 cycles. work elaborates on origin metal provides new perspective designing for other catalytic systems.

Language: Английский

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Targeting Acceleration of the Rate-Determining Step in Sulfur Redox and Dendrite-Free Lithium: Heterointerface and Electron Structural Engineering

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: April 26, 2025

Currently, most catalysts for lithium-sulfur batteries suffer from some shortcomings, including restricted active sites and poor catalytic kinetics. Herein, we developed an advanced catalyst of V-MXene@octahedral porous carbon (MX@OPC), which features a "built-in interfacial electric field" (BIEF) "dual-functional sites" (DCASs), to target the accelerated rate-determining step in polysulfide redox kinetics dendrite-free lithium behaviors. The well-designed heterointerface forms BIEF due differences work function charge distribution, contributing enhanced electron transfer low lithium-ion diffusion barriers. DCASs with superior Li2S4 desorption efficiently catalyze conversion Li2S2 by distribution relaxation times (DRT) analysis density functional theory (DFT) calculations. V-MXene exhibits strong lithophilicity, facilitates uniform nucleation growth lithium. As result, battery MX@OPC delivers capacity fade rate per cycle as 0.017% over 1200 cycles at 2 C. Furthermore, renders Li||Li symmetric cell maintain stable overpotential 16 mV 2500 h. This provides inspiring insights into directed catalysis generation toward accelerating rate-determining-step sulfur deposition Li-S batteries.

Language: Английский

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Staged dendrite suppression for high safe and stable lithium-sulfur batteries

Journal of Energy Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 1, 2024

Language: Английский

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Phase Reconstruction‐Assisted Electron‐Li⁺ Reservoirs Enable High‐Performance Li‐S Battery Operation Across Wide Temperature Range

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 9, 2024

Abstract Lithium‐sulfur batteries (LSBs) are known as high energy density, but their performance deteriorates sharply under high/low‐temperature surroundings, due to the sluggish kinetics of sulfur redox conversion and Li + transport. Herein, a catalytic strategy phase reconstruction with abundant “electron‐Li ” reservoirs has been proposed simultaneously regulate electron exchange. As demo, 1T‐phase lithiation molybdenum disulfide grown on hollow carbon nitride (1T‐Li x MoS 2 /HC 3 N 4 ) is achieved via in situ electrochemical modulation, where 1T‐Li serves an auxiliary “Li source” for facilitating transport HC acts donor electronic supplier. From theoretical calculations, experimental post‐modern analyses, relationship between behaviors mechanism accelerating rate‐determining species deeply understood. Consequently, cells /PP functional separator demonstrate excellent long‐term stabilize areal capacity 6 mAh cm −2 5.0 mg . Even exposed robust surroundings from (60 °C) low (0 temperatures, optimized exhibit high‐capacity retention 76.2% 90.4% after 100 cycles, respectively, pointing out potential application catalysts reconstruction‐assisted LSBs.

Language: Английский

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High Spin‐State Modulation of Catalytic Centers by Weak Ligand Field for Promoting Sulfur Redox Reaction in Lithium‐Sulfur Batteries

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 8, 2024

Abstract The spin state of transition‐metal compounds in lithium‐sulfur batteries (LSBs) significantly impacts the electronic properties and kinetics sulfur redox reactions (SRR). However, accurately designing remains challenging, which is crucial for understanding structure‐performance relationship developing high‐performance electrocatalysts. Herein, CoF 2 , specifically Co 2+ with 3 d 7 electrons a high‐spin distribution (t 2g 5 e g ), were tailored predictably first time through weak coordination field effect F element. Both DFT calculations experimental results confirm that transitions from low‐ to configurations strongly interacts species Co−S Li−F bonds during SRR process. This interaction weakens S−S bond, promoting its facile cleavage both ends while also facilitating rapid uniform nucleation Li S /Li S, thus resulting LSBs capacity 447.7 mAh −1 at 10 C rates stable cycling 1000 cycles, an acceptable practical 585 high loading mass mg cm −2 . work achieves rational control active electron enriches application accelerate LSBs.

Language: Английский

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