Electrocatalyst Modulation toward Bidirectional Sulfur Redox in Li–S Batteries: From Strategic Probing to Mechanistic Understanding

Advanced Energy Materials, Journal Year: 2022, Volume and Issue: 12(29)

Published: June 7, 2022

Abstract Electrocatalyst design has stimulated considerable attention and strenuous effort to tackle a multitude of detrimental issues in lithium–sulfur (Li–S) systems, mainly pertaining the severe polysulfide shuttle effect sluggish sulfur redox kinetics. In this context related advances expediting bidirectional reactions have lately surged. Nonetheless, structure–activity correlation electrocatalytic mechanism remain rather elusive, as result elusory active sites, complicated aprotic environments, multistep conversion pathways. This review summarizes burgeoning strategies modulation heterogeneous homogeneous electrocatalysts, wherein advanced electrokinetic measurements, operando instrumental probing, theoretical simulations are elucidated with an emphasis on deciphering electrochemistry. Notably, “3s” electrocatalysis model is proposed deepen mechanistic understanding realm. Finally, development roadmap sketched future research layouts discussed, aiming essence, realize favorable kinetics ultimately bridge gap between reality ideal systems working Li–S batteries.

Language: Английский

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Outstanding Catalytic Effects of 1T′-MoTe₂ Quantum Dots@3D Graphene in Shuttle-Free Li–S Batteries

ACS Nano, Journal Year: 2021, Volume and Issue: 15(8), P. 13279 - 13288

Published: Aug. 5, 2021

It is still challenging to develop sulfur electrodes for Li-S batteries with high electrical conductivity and fast kinetics, as well efficient suppression of the shuttling effect lithium polysulfides. To address such issues, herein, polar MoTe2 different phases (2H, 1T, 1T') were deeply investigated by density functional theory calculations, suggesting that 1T'-MoTe2 displays concentrated states (DOS) near Fermi level conductivity. By optimization synthesis, quantum dots decorated three-dimensional graphene (MTQ@3DG) was prepared overcome these it accomplished exceptional performance in batteries. Owing chemisorption catalytic dots, MTQ@3DG/S exhibits highly reversible discharge capacity 1310.1 mAh g-1 at 0.2 C 0.026% fade rate per cycle over 600 cycles. The adsorption calculation demonstrates conversion Li2S2 Li2S rate-limiting step where Gibbs free energies are 1.07 eV 0.97 1T'-MoTe2, revealing importance 1T'-MoTe2. Furthermore, situ Raman spectroscopy investigation proved shuttle LiPSs cells during cycle.

Language: Английский

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Dual‐Functional V₂C MXene Assembly in Facilitating Sulfur Evolution Kinetics and Li‐Ion Sieving toward Practical Lithium–Sulfur Batteries

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(26)

Published: March 19, 2023

Abstract Lithium–sulfur (Li–S) batteries are considered as one of the most promising candidates to achieve an energy density 500 Wh kg⁻ 1 . However, challenges shuttle effect, sluggish sulfur conversion kinetics, and lithium‐dendrite growth severely obstruct their practical implementation. Herein, multiscale V 2 C MXene (VC) with a spherical confinement structure is designed high‐efficiency bifunctional promotor for evolution lithium species in Li–S batteries. Combining synchrotron X‐ray 3D nano‐computed tomography (X‐ray nano‐CT), small‐angle neutron scattering (SANS), first‐principle calculations, it revealed that activity VC can be maximized by tuning scale, as‐attained functions conducted follows: (i) acts efficient polysulfide (LiPS) scavenger due large number active sites; (ii) exhibits significantly improved electrocatalytic function Li S nucleation decomposition reaction kinetics owing scale effect; (iii) regulate dynamic behavior Li‐ions thus stabilize plating/stripping effectively on account unique ion‐sieving effect.

Language: Английский

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Engineering Cooperative Catalysis in Li–S Batteries

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(26)

Published: June 6, 2023

Abstract Lithium–sulfur (Li–S) batteries are regarded to be one of the most promising next‐generation owing merits high theoretical capacity and low cost. However, aprotic S electrochemistry is hampered by shuttling effect sluggish conversion soluble lithium polysulfides (LiPSs). Various electrocatalysts have been designed optimize kinetics LiPSs. Heteroatom doping or polar catalyst incorporation plays an important role remedy these shortcomings. Here, cooperative catalytic effects engendered heteroatom codoping engineering, catalyst/heteroatom composite strategy, integrating polar‐metal‐based material design summarized. First, principles on conductive interface described in detail. Moreover, a systematic investigation electrocatalytic characterization techniques that establish bridge between solid–liquid macroscopic electrochemical performance highlighted, providing more scientific guidance for design. In conclusion, stemming from current achievements, future directions targeting high‐energy‐density Li–S commercialization proposed.

Language: Английский

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Sulfur–Carbon Electrode with PEO‐LiFSI‐PVDF Composite Coating for High‐Rate and Long‐Life Lithium–Sulfur Batteries

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(36)

Published: Aug. 9, 2023

Abstract To address the problem of serious capacity fading in lithium–sulfur batteries, a multi‐functional PEO(polyethylene oxide)/LiFSI (lithium bis(fluorosulfonyl)imide)/PVDF (polyvinylidene fluoride) (PLP) gel polymer electrolyte is exploited by coating PLP on carbon nanotubes (CNTs) based sulfur cathode (PLP‐S/CNTs) with controlled thermal annealing process. The process leads to conformal infusion through matrix S/CNTs retaining amorphous phase PLP, which enhance rate performance compared bare S/CNTs. drives transformation more elemental Li 2 S /Li without forming intermediary product restraining soluble‐polysulfides formation. Furthermore, successfully inhibits dissolution x ( > 4) PEO and prevents loss active material cathode, confirmed density functional theory calculations. Comprehensively, applied surface exhibit significantly suppressed shuttle effect greatly improve long‐term cycle stability battery. synthesized PLP‐coated composite demonstrates high specific 573.6 mAh g −1 at current 0.5 C after 1 000 cycles, even achieving 318.1 an extremely C‐rate (6 C). unprecedented among reported studies technology.

Language: Английский

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Air‐Stable Protective Layers for Lithium Anode Achieving Safe Lithium Metal Batteries

Small Methods, Journal Year: 2022, Volume and Issue: 7(1)

Published: Dec. 18, 2022

With markedly expansive demand in energy storage devices, rechargeable batteries will concentrate on achieving the high density and adequate security, especially under harsh operating conditions. Considering capacity (3860 mA h g-1 ) low electrochemical potential (-3.04 V vs standard hydrogen electrode), lithium metal is identified as one of most promising anode materials, which has sparked a research boom. However, intrinsically reactivity triggers repeating fracture/reconstruction process solid electrolyte interphase, side reactions with dendrites, detrimental to performance (LMBs). Even worse, when exposed air, suffer severe atmospheric corrosion, reaction moisture, leading grievous safety hazards. To settle these troubles, constructing air-stable protective layers (ASPLs) an effective solution. In this review, besides necessity ASPLs highlighted, modified design criteria, focusing enhancing chemical/mechanical stability controlling ion flux, are proposed. Correspondingly, current progress comprehensively summarized discussed. Finally, perspectives developing applicable anodes (LMAs) put forward. This review guides direction for practical use LMAs, further pushing evolution safe stable LMBs.

Language: Английский

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Interface Engineering Toward Expedited Li₂S Deposition in Lithium–Sulfur Batteries: A Critical Review

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(29)

Published: Feb. 9, 2023

Lithium-sulfur batteries (LSBs) with superior energy density are among the most promising candidates of next-generation storage techniques. As key step contributing to 75% overall capacity, Li2 S deposition remains a formidable challenge for LSBs applications because its sluggish kinetics. The severe kinetic issue originates from huge interfacial impedances, indicative interface-dominated nature deposition. Accordingly, increasing efforts have been devoted interface engineering efficient deposition, which has attained inspiring success date. However, systematic overview and in-depth understanding this critical field still absent. In review, principles interface-controlled precipitation presented, clarifying pivotal roles electrolyte-substrate electrolyte-Li2 interfaces in regulating depositing behavior. For optimization interface, on design substrates including metal compounds, functionalized carbons, organic compounds systematically summarized. Regarding regulation progress applying polysulfides catholytes, redox mediators, high-donicity/polarity electrolytes is overviewed detail. Finally, challenges possible solutions aiming at optimizing given further development practical LSBs. This review would inspire more insightful works and, importantly, may enlighten other electrochemical areas concerning heterogeneous processes.

Language: Английский

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A Li ₂ S-based all-solid-state battery with high energy and superior safety

Science Advances, Journal Year: 2022, Volume and Issue: 8(1)

Published: Jan. 5, 2022

Safe redox chemistry of Li2S and Si in solid-state polymer electrolyte enables a high-energy reliable all-solid-state battery.

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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Oxygen Defect‐Rich WO_3−x–W₃N₄ Mott–Schottky Heterojunctions Enabling Bidirectional Catalysis for Sulfur Cathode

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(42)

Published: Aug. 30, 2023

Abstract The serious shuttle effect and intrinsically sluggish oxidation–reduction reaction kinetics of polysulfides severely hinder the practical commercialization lithium–sulfur (Li–S) batteries. Herein, oxygen‐defect‐rich WO 3− x –W 3 N 4 Mott–Schottky heterojunctions are designed as efficient catalysts. Based on theoretical calculations comprehensive experimental characterization, exhibits a lower free energy change (1.03 eV) Li 2 S decomposition barrier (0.92 than W , which significantly enhances sulfur reduction (SRR) activity. Furthermore, relationship between catalytic activity gaps in d p bands centers (Δ d–p ) is also established, with low Δ heterojunction leading to antibonding state energy, promotes electron transfer interfacial redox kinetics. Oxygen vacancies can improve without affecting adsorption. Hence, Li–S battery using @CC/S exhibited outstanding rate duration performance (913.9 mAh g –1 at C, stable 400 cycles 1 C). Impressively, achieves high areal capacity 5.0 cm −2 under loading 4.98 mg .

Language: Английский

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