Ordered Mesoporous Carbon Grafted MXene Catalytic Heterostructure as Li-Ion Kinetic Pump toward High-Efficient Sulfur/Sulfide Conversions for Li–S Battery

ACS Nano, Journal Year: 2023, Volume and Issue: 17(2), P. 1653 - 1662

Published: Jan. 6, 2023

Lithium–sulfur (Li–S) batteries exhibit unparalleled theoretical capacity and energy density than conventional lithium ion batteries, but they are hindered by the dissatisfactory "shuttle effect" sluggish conversion kinetics owing to low transport kinetics, resulting in rapid fading. Herein, a catalytic two-dimensional heterostructure composite is prepared evenly grafting mesoporous carbon on MXene nanosheet (denoted as OMC-g-MXene), serving interfacial kinetic accelerators Li–S batteries. In this design, grafted can not only prevent stack of nanosheets with enhanced mechanical property also offer facilitated pump for accelerating diffusion. Meanwhile, exposed defect-rich OMC-g-MXene inhibits polysulfide shuttling chemical interactions between polysulfides thus simultaneously enhances electrochemical efficiency, fully investigated situ/ex situ characterizations. Consequently, cells pumps achieve high cycling (966 mAh g–1 at 0.2 C after 200 cycles), superior rate performance (537 5 C), an ultralow decaying 0.047% per cycle 800 cycles 1 C. Even employed sulfur loading 7.08 mg cm–2 under lean electrolyte, ultrahigh areal 4.5 acquired, demonstrating future practical application.

Language: Английский

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Regulating the Spin State Configuration in Bimetallic Phosphorus Trisulfides for Promoting Sulfur Redox Kinetics

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(41), P. 22516 - 22526

Published: Oct. 3, 2023

Lithium-sulfur (Li-S) batteries suffer from sluggish kinetics due to the poor conductivity of sulfur cathodes and polysulfide shutting. Current studies on redox catalysis mainly focus adsorption catalytic conversion lithium polysulfides but ignore modulation electronic structure catalysts which involves spin-related charge transfer orbital interactions. In this work, bimetallic phosphorus trisulfides embedded in Prussian blue analogue-derived nitrogen-doped hollow carbon nanocubes (FeCoPS3/NCs) were elaborately synthesized as a host reveal relationship between activity spin state configuration for Li-S batteries. Orbital splitting FeCoPS3 drives transition low-spin high-spin states, generating more unpaired electrons 3d orbit. Specifically, nondegenerate orbitals involved result upshift energy levels, active states. Such tailored increases transfer, influences d-band center, further modifies with potential reaction pathways. Consequently, cell FeCoPS3/NC exhibits an ultralow capacity decay 0.037% per cycle over 1000 cycles. This study proposed general strategy sculpting geometric configurations enable topology regulation battery catalysts.

Language: Английский

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Cooperative Catalysis of Polysulfides in Lithium‐Sulfur Batteries through Adsorption Competition by Tuning Cationic Geometric Configuration of Dual‐active Sites in Spinel Oxides

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(8)

Published: Dec. 22, 2022

Fundamentally understanding the structure-property relationship is critical to design advanced electrocatalysts for lithium-sulfur (Li-S) batteries, which remains a formidable challenge. Herein, by manipulating regulable cations in spinel oxides, their geometrical-site-dependent catalytic activity sulfur redox investigated. Experimental and theoretical analyses validate that modulation essence of cooperative catalysis lithium polysulfides (LiPSs) dominated LiPSs adsorption competition between Co3+ tetrahedral (Td) Mn3+ octahedral (Oh) sites on Mn3+Oh -O-Co3+Td backbones. Specifically, high-spin Co3+Td with stronger Co-S covalency anchors persistently, while electron delocalized adsorptive orbital (dz2 ) functions better catalyzing specialized conversion. This work inaugurates universal strategy sculpting geometrical configuration achieve charge, spin, topological regulation Li-S batteries.

Language: Английский

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Rechargeable Metal-Sulfur Batteries: Key Materials to Mechanisms

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(8), P. 4935 - 5118

Published: April 10, 2024

Rechargeable metal-sulfur batteries are considered promising candidates for energy storage due to their high density along with natural abundance and low cost of raw materials. However, they could not yet be practically implemented several key challenges: (i) poor conductivity sulfur the discharge product metal sulfide, causing sluggish redox kinetics, (ii) polysulfide shuttling, (iii) parasitic side reactions between electrolyte anode. To overcome these obstacles, numerous strategies have been explored, including modifications cathode, anode, electrolyte, binder. In this review, fundamental principles challenges first discussed. Second, latest research on is presented discussed, covering material design, synthesis methods, electrochemical performances. Third, emerging advanced characterization techniques that reveal working mechanisms highlighted. Finally, possible future directions practical applications This comprehensive review aims provide experimental theoretical guidance designing understanding intricacies batteries; thus, it can illuminate pathways progressing high-energy-density battery systems.

Language: Английский

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Combined Defect and Heterojunction Engineering in ZnTe/CoTe₂@NC Sulfur Hosts Toward Robust Lithium–Sulfur Batteries

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(46)

Published: July 7, 2023

Abstract Lithium–sulfur batteries (LSBs) are feasible candidates for the next generation of energy storage devices, but shuttle effect lithium polysulfides (LiPSs) and poor electrical conductivity sulfur sulfides limit their application. Herein, a host based on nitrogen‐doped carbon (NC) coated with small amount transition metal telluride (TMT) catalyst is proposed to overcome these limitations. The properties redox tuned by adjusting anion vacancy concentration engineering ZnTe/CoTe 2 heterostructures. Theoretical calculations experimental data demonstrate that tellurium vacancies enhance adsorption LiPSs, while formed TMT/TMT TMT/C heterostructures as well overall architecture composite simultaneously provide high Li + diffusion fast electron transport. As result, v‐ZnTe/CoTe @NC/S cathodes show excellent initial capacities up 1608 mA h g −1 at 0.1C stable cycling an average capacity decay rate 0.022% per cycle 1C during 500 cycles. Even loading 5.4 mg cm –2 , 1273 retained, when reducing electrolyte 7.5 µL still maintains 890.8 after 100 cycles 0.1C.

Language: Английский

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A Review on Engineering Transition Metal Compound Catalysts to Accelerate the Redox Kinetics of Sulfur Cathodes for Lithium–Sulfur Batteries

Nano-Micro Letters, Journal Year: 2024, Volume and Issue: 16(1)

Published: Jan. 29, 2024

Abstract Engineering transition metal compounds (TMCs) catalysts with excellent adsorption-catalytic ability has been one of the most effective strategies to accelerate redox kinetics sulfur cathodes. Herein, this review focuses on engineering TMCs by cation doping/anion doping/dual doping, bimetallic/bi-anionic TMCs, and TMCs-based heterostructure composites. It is obvious that introducing cations/anions or constructing can boost capacity regulating electronic structure including energy band, d / p -band center, electron filling, valence state. Moreover, doped/dual-ionic are adjusted inducing ions different electronegativity, ion radius, resulting in redistribution, bonds reconstruction, induced vacancies due interaction changed crystal such as lattice spacing distortion. Different from aforementioned two strategies, heterostructures constructed types Fermi levels, which causes built-in electric field electrons transfer through interface, induces redistribution arranged local atoms regulate structure. Additionally, lacking studies three comprehensively for improving catalytic performance pointed out. believed guide design advanced boosting lithium batteries.

Language: Английский

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Development of Synergistically Efficient Ni–Co Pair Catalytic Sites for Enhanced Polysulfide Conversion in Lithium–Sulfur Batteries

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(37)

Published: March 29, 2024

Abstract The performance of Lithium–sulfur (Li–S) batteries is constrained by the migration lithium polysulfide (LiPS), slow conversion LiPS, and significant reaction barrier encountered during precipitation/dissolution Li 2 S throughout discharge/charge cycle. In this contribution, study presents Ni–Co dual‐atom catalytic sites on hollow nitrogen‐doped carbon (NiCoNC). Theoretical calculations experimental data reveal that catalysts (DACs) accelerate kinetic LiPSs facilitate formation/decomposition discharging charging, which minimizes LiPS migration. Consequently, utilization S/NiCoNC cathodes manifests a substantial initial capacity 1348.5 mAh g −1 at 0.1 C, exceptional cycling stability with an average degradation rate 0.028% per cycle over 900 cycles 0.5 noteworthy capability 626 C. Electrodes higher sulfur loading 4.5 mg cm −2 low electrolyte/sulfur ratio 8 µL exhibit specific capacities up to 1236 as well retention 494.2 after 200 0.2 This effectively showcases potential DACs for cathodes, thereby enhancing overall Li–S batteries.

Language: Английский

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Electronic Spin Alignment within Homologous NiS₂/NiSe₂ Heterostructures to Promote Sulfur Redox Kinetics in Lithium‐Sulfur Batteries

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(25)

Published: April 3, 2024

Abstract The catalytic activation of the Li‐S reaction is fundamental to maximize capacity and stability batteries (LSBs). Current research on catalysts mainly focuses optimizing energy levels promote adsorption conversion, while frequently overlooking electronic spin state influence charge transfer orbital interactions. Here, hollow NiS 2 /NiSe heterostructures encapsulated in a nitrogen‐doped carbon matrix (NiS @NC) are synthesized used as additive sulfur cathodes. heterostructure promotes splitting 3d orbital, driving Ni 3+ transformation from low high spin. This configuration raises level activates state. accelerates optimizes energy, lowering barrier polysulfides conversion. Benefiting these characteristics, LSBs based @NC/S cathodes exhibit initial (1458 mAh·g⁻ 1 at 0.1C), excellent rate capability (572 5C), stable cycling with an average decay only 0.025% per cycle 1C during 500 cycles. Even loadings (6.2 mg·cm⁻ ), capacities 1173 (7.27 mAh·cm⁻ ) measured 0.1C, 1058 retained after 300

Language: Английский

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Identifying the Role of the Cationic Geometric Configuration in Spinel Catalysts for Polysulfide Conversion in Sodium–Sulfur Batteries

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(34), P. 18992 - 19004

Published: Aug. 21, 2023

An AB2X4 spinel structure, with tetrahedral A and octahedral B sites, is a paradigmatic class of catalysts several possible geometric configurations numerous applications, including polysulfide conversion in metal–sulfur batteries. Nonetheless, the influence configuration composition on mechanisms catalysis precise manner which facilitate polysulfides remain unknown. To enable controlled exposure single active configurations, herein, Cotd2+ Cooh3+ Co3O4 for sodium are large part replaced by Fetd2+ Feoh3+, respectively, generating FeCo2O4 CoFe2O4. Through an examination electrochemical activation energies, characterization symmetric cells, theoretical calculations, we determine that serves as site breaking S–S bonds, while functions formation S–Na bonds. The current study underlines subtle relationship between activity catalysts, providing unique insights rational development improved optimizing their atomic configuration.

Language: Английский

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From Charge to Spin: An In‐Depth Exploration of Electron Transfer in Energy Electrocatalysis

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(37)

Published: March 14, 2024

Abstract Catalytic materials play crucial roles in various energy‐related processes, ranging from large‐scale chemical production to advancements renewable energy technologies. Despite a century of dedicated research, major enduring challenges associated with enhancing catalyst efficiency and durability, particularly green electrochemical reactions, remain. Focusing only on either the crystal structure or electronic is deemed insufficient break linear scaling relationship (LSR), which golden rule for design advanced catalysts. The discourse this review intricately outlines essence heterogeneous catalysis reactions by highlighting vital played electron properties. physical properties charge spin that govern efficiencies are analyzed. Emphasis placed pronounced influence external fields perturbing LSR, underscoring role plays advancing high‐performance design. culminates proffering insights into potential applications catalysis, concluding discussion extant inherent limitations.

Language: Английский

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