3d‐Orbital High‐Spin Configuration Driven From Electronic Modulation of Fe₃O₄/FeP Heterostructures Empowering Efficient Electrocatalyst for Lithium−Sulfur Batteries

Advanced Functional Materials, Год журнала: 2024, Номер 34(49)

Опубликована: Авг. 29, 2024

Abstract The intricate lithium polysulfides (LiPSs) shuttle and uncontrollable dendrite growth critically hinder the commercialization of lithium−sulfur (Li−S) batteries. rational orderly assignment multi‐electron induced flow is critical link in sulfer redox reaction. Herein, yolk‐shell Fe 3 O 4 /FeP@C heterostructure nanoreactors are fabricated to modulate electronic structure, including spin‐related charge behavior orbital orientation control, which can demonstrate interaction between catalytic activity spin‐state conformation. spin splitting induces electron transition from low‐spin high‐spin, where non‐degenerate orbitals contribute energy level up‐shift, guiding migration FeP , activating more states d orbitals. Spin polarization guides sulfur closed‐loop conversion, confirmed by DFT simulations situ Raman. Hence, electrochemical performances remarkable at ultra‐high current density loading. Even an initial specific capacity 928.5 mAh g −1 a Li−S pouch cell reveals practical prospect /FeP@C/PP separator. Li//Li symmetric cycles steadily for 4000 h, confirming interlayer simultaneously promotes evolution kinetics sieves ions. This work deciphers principles spin‐orbit coupling, achieving topological modulation “charge−spin−orbit” toward electrocatalysts.

Язык: Английский

---

Physical Field Effects to Suppress Polysulfide Shuttling in Lithium–Sulfur Battery

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Окт. 14, 2024

Lithium-sulfur batteries (LSB) with high theoretical energy density are plagued by the infamous shuttle effect of lithium polysulfide (LPS) and sluggish sulfur reduction/evolution reaction. Extensive research is conducted on how to suppress effects, including physical structure confinement engineering, chemical adsorption strategy, design redox catalysts. Recently, rational mitigate effects enhance reaction kinetics based field has been widely studied, providing a more fundamental understanding interactions species. Herein, focused their methods mechanisms interaction summarized systematically LPS. Overall, working principle LSB system, origin effect, kinetic trouble in briefly described. Then, mechanism application materials concepts external field-assisted elaborated, electrostatic force, built-in electric field, spin state regulation, strain magnetic photoassisted other strategies pivotally elaborated discussed. Finally, potential directions enhancing performance weakening high-energy anticipated.

Язык: Английский

---

Enhancing rate performance in lithium-sulfur batteries via synergistic bidirectional catalysis and improved conductivity

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 160022 - 160022

Опубликована: Янв. 1, 2025

Язык: Английский

---

Metal Doping Activation of Anion-Mediated Electron Transfer in Catalytic Reactions

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 14, 2025

Heteroatom-doping has emerged as a transformative approach to producing high-performance catalysts, yet the current trial-and-error optimize these materials remains ineffective. To enable rational design of more efficient models grounded in deeper understanding catalytic mechanisms are essential. Existing models, such d-band center theory, fall short explaining role dopants, particularly when dopants do not directly interact with reactants. In this study, we synthesize various heteroatom-doped catalysts explore correlation between electronic effects and catalyst activity. Using Co-MoS2 model Li–S redox reaction within cathode batteries test system, show interaction cobalt sites adjacent lattice sulfur atoms disrupts intrinsic structural symmetry MoS2. This disruption enhances transfer spin-polarized electrons from metal centers promotes adsorption reactant intermediates. Furthermore, by analyzing 20 different dopant elements, establish linear relationship electron density activity toward reduction species, that extends other systems, hydrogen evolution reaction.

Язык: Английский

---

Unlocking the Capacity and Stability Limitations of Perovskite Electrodes and Achieving the Design of a Flame-Retardant Supercapacitor Through the “Tree Canopy” Structure

ACS Energy Letters, Год журнала: 2025, Номер unknown, С. 1680 - 1687

Опубликована: Март 14, 2025

Язык: Английский

---

Are Sulfide‐Based Solid‐State Electrolytes the Best Pair for Si Anodes in Li‐Ion Batteries?

Advanced Energy Materials, Год журнала: 2024, Номер 14(40)

Опубликована: Авг. 19, 2024

Abstract The integration of Si‐based anodes within sulfide‐based solid electrolyte (SSE) Li‐ion batteries (LIB) has emerged as a promising avenue research and development, attracting increasing interest in recent years. This work comprehensively examines the latest directions major strides this field. It covers key advances design engineering nano‐ micro‐structured Si anode architectures, strategies surface modification. Additionally, it explores impacts external pressure, role binders conductive additives, implications varying particle size. Beyond providing detailed account evolution SSE LIBs, also identifies critical challenges that urgently need addressing. These include electrochemical‐mechanical behavior failure mechanism for structural interface modifications, methods preparing electrodes, advancements high‐performance SSEs, development scalable technologies thin films. Moreover, discusses high‐energy cathodes tailored LIBs. identified priorities are set to offer crucial guidance insights, supporting ongoing investigations innovations dynamic area research.

Язык: Английский

---

Promoting Polysulfide Redox Reactions through Electronic Spin Manipulation

ACS Nano, Год журнала: 2024, Номер 18(29), С. 19268 - 19282

Опубликована: Июль 9, 2024

Catalytic additives able to accelerate the lithium–sulfur redox reaction are a key component of sulfur cathodes in batteries (LSBs). Their design focuses on optimizing charge distribution within energy spectra, which involves refinement and occupancy electronic density states. Herein, beyond distribution, we explore role spin configuration polysulfide adsorption properties catalytic activity additive. We showcase importance this parameter by generating polarization through defect engineering approach based introduction Co vacancies surface CoSe nanosheets. show change electron state increasing number unpaired electrons with aligned spins. This local rearrangement enhances adsorption, reducing activation Li–S reactions. As result, more uniform nucleation growth Li2S an accelerated liquid–solid conversion LSB obtained. These translate into exhibiting capacities up 1089 mA h g–1 at 1 C 0.017% average capacity loss after 1500 cycles, 5.2 cm–2, 0.16% decay per cycle 200 cycles high loading cells.

Язык: Английский

---

Boosting Polysulfide Conversion on Fe‐Doped Nickel Diselenide Toward Robust Lithium–Sulfur Batteries

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 17, 2025

Abstract Sulfur offers a high‐energy‐density, low‐cost, and sustainable alternative to traditional battery cathodes, but its practical use is limited by sluggish uneven reaction polysulfide dissolution, necessitating electrocatalytic additives enhance conversion efficiency. Generating unpaired spin electrons has proven effective in enhancing performance Co‐based electrocatalysts. These increase adsorption weakening S─S bonds, facilitating their cleavage during sulfur reduction reactions. This work extends the strategy Fe–Ni‐based catalysts. The synthesis of NiSe 2 Fe‐doped particles reported investigate impact Fe doping on electronic structure, catalytic activity, introduced as coating cathode side Li–S (LSB) separator. Experimental analyses first‐principles calculations reveal that Fe‐rich cores surface density states at Fermi level introduce electrons, boosting LiPS conversion. synergistic effects significantly improve performance, cycling stability, overall LSB cells. Specifically, cells based ‐based separators achieve specific capacities 1483 mAh g⁻¹ 0.1C 1085 1C, along with remarkable retaining 84.4% capacity after 800 cycles. High sulfur‐loading tests further validate multifunctional membrane's effectiveness, showing significant retention reduced loss.

Язык: Английский

---

A Review of the Application of Metal-Based Heterostructures in Lithium–Sulfur Batteries

Catalysts, Год журнала: 2025, Номер 15(2), С. 106 - 106

Опубликована: Янв. 22, 2025

Lithium–sulfur (Li-S) batteries are recognized as a promising alternative in the energy storage domain due to their high theoretical density, environmental friendliness, and cost-effectiveness. However, challenges such polysulfide dissolution, low conductivity of sulfur, limited cycling stability hinder widespread application. To address these issues, incorporation heterostructured metallic substrates into Li-S has emerged pivotal strategy, enhancing electrochemical performance by facilitating better adsorption catalysis. This review delineates modifications made cathode separator through heterostructures. We categorize heterostructures three classifications: single metals metal compounds, MXene materials paired with formed entirely compounds. Each category is systematically examined for its contributions behavior efficiency batteries. The evaluated both contexts, revealing significant improvements lithium-ion retention. Our findings suggest that strategic design can not only mitigate inherent limitations but also pave way development high-performance systems.

Язык: Английский

---

Coupling Bifunctional Scaffolds with Slow Photon Effect for Synergistically Enhanced Photoassisted Lithium–Sulfur Battery Properties

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Янв. 25, 2025

Photoassisted lithium-sulfur (Li-S) batteries offer a promising approach to enhance the catalytic transformation kinetics of polysulfide. However, development is greatly hindered by inadequate photo absorption and severe photoexcited carriers recombination. Herein, photonic crystal sulfide heterojunction structure designed as bifunctional electrode scaffold for photoassisted Li-S batteries. Inverse opal (IO) structures utilize slow photon effect that originates from their adjustable band gaps, giving them distinctive optical response characteristics. The incorporation SnS/ZnS within these IO frameworks further broadens light spectrum enhances charge transfer process. This efficient hybrid not only adsorption conversion polysulfides at cathode but also induces uniform Li nucleation anode. These contribute full output high reversible capability 1072 mAh g-1 maintain stable cycling 50 cycles. Additionally, specific capacity 698.8 still obtained even under sulfur loading up 4 mg cm-2. present strategy on battery properties can be extended rationally construct other energy storage devices.

Язык: Английский

---