Fe3O4-doped mesoporous carbon cathode with a plumber’s nightmare structure for high-performance Li-S batteries

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 27, 2024

Shuttling of lithium polysulfides and slow redox kinetics seriously limit the rate cycling performance lithium-sulfur batteries. In this study, Fe

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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Tailoring d‐p Orbital Hybridization to Decipher the Essential Effects of Heteroatom Substitution on Redox Kinetics

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

Published: June 4, 2024

Abstract The heteroatom substitution is considered as a promising strategy for boosting the redox kinetics of transition metal compounds in hybrid supercapacitors (HSCs) although dissimilar identification and essential mechanism that dominate remain unclear. It presented d‐p orbital hybridization between electrolyte ions can be utilized descriptor understanding kinetics. Herein, series Co, Fe Cu heteroatoms are respectively introduced into Ni 3 Se 4 cathodes, among them, only moderate Co‐substituted hold optimal resulted from formed more unoccupied antibonding states π*. inevitably enhances interfacial charge transfer ensures balanced OH − adsorption‐desorption to accelerate validated by lowest reaction barrier (0.59 eV, matching well with theoretical calculations). Coupling lower diffusion energy barrier, prepared cathode delivers ultrahigh rate capability (~68.7 % capacity retention even current density increases 200 times), an assembled HSC also presents high energy/power density. This work establishes principles determining deciphers underlying effects on improving performance battery‐type electrodes novel perspective orbital‐scale manipulation.

Language: Английский

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Advances in regulating the electron spin effect toward electrocatalysis applications

eScience, Journal Year: 2024, Volume and Issue: unknown, P. 100264 - 100264

Published: March 1, 2024

Building highly reactive electrocatalysts is of great significance for addressing the energy crisis and developing green energy. Electrocatalytic reactions occur at interface catalysts, where physicochemical properties catalyst surface play a dominant role. In particular, electron spin behavior on has decisive impact catalytic reaction process. This review initially introduces definition methods manipulation. Furthermore, we summarize advanced characterization spin. Then, latest research advancements effect in oxygen reduction reaction, evolution carbon dioxide nitrogen reaction. The mechanisms manipulation these four are thoroughly discussed. Finally, propose key directions future development effects field electrocatalysis. contributes to deeper understanding micromechanisms electrocatalytic reactions.

Language: Английский

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Rare Earth Single‐Atom Catalysis for High‐Performance Li−S Full Battery with Ultrahigh Capacity

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 18, 2024

Lithium-sulfur (Li-S) batteries have many advantages but still face problems such as retarded polysulfides redox kinetics and Li dendrite growth. Most reported single atom catalysts (SACs) for Li-S are based on d-band transition metals whose d orbital constitutes active valence band, which is inclined to occur catalyst passivation. SACs 4f inner of rare earth challenging their great difficulty be activated. In this work, we design synthesize the first metal Sm has electron-rich promote catalytic conversion uniform deposition Li. enhance catalysis by activated through an f-d-p hybridization. Using Sm-N

Language: Английский

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

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

Published: Oct. 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.

Language: Английский

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

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(49)

Published: Aug. 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.

Language: Английский

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Coupling Nitrate‐to‐Ammonia Conversion and Sulfion Oxidation Reaction Over Hierarchical Porous Spinel MFe₂O₄ (M═Ni, Co, Fe, Mn) in Wastewater

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

The construction of coupled electrolysis systems utilizing renewable energy sources for electrocatalytic nitrate reduction and sulfion oxidation reactions (NO3RR SOR), is considered a promising approach environmental remediation, ammonia production, sulfur recovery. Here, simple chemical dealloying method reported to fabricate hierarchical porous multi-metallic spinel MFe2O4 (M═Ni, Co, Fe, Mn) dual-functional electrocatalysts consisting Mn-doped NiFe2O4/CoFe2O4 heterostructure networks Ni/Co/Mn co-doped Fe3O4 nanosheet networks. excellent NO3RR with high NH3 Faradaic efficiency 95.2% at -0.80 V versus reversible hydrogen electrode (vs RHE) yield rate 608.9 µmol h-1 cm-2 -1.60 vs RHE, impressive SOR performance (100 mA [email protected] achieved MFe2O4. Key intermediates such as *NO, *NH2, are identified in the process by situ Fourier transform infrared spectroscopy (in FTIR). MFe2O4-assembled two-electrode coupling system (NO3RR||SOR) shows an ultra-low cell voltage 1.14 10 cm-2, much lower than NO3RR||OER (oxygen evolution reaction, [email protected] V), simultaneously achieving two expected targets value-added generation recovery, also demonstrating durability 18 h. This work demonstrates great potential ferrite-based catalysts remediation.

Language: Английский

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Oxygen Bridges of CoTe₂/Co─O─NC Enhancing Adsorption‐Catalysis of Polysulfide for Stable Lithium–Sulfur Batteries

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

Published: Jan. 15, 2025

Abstract Lithium–sulfur batteries are regarded as candidates for next‐generation energy storage systems, but their slow reaction kinetics and shuttle effect severely hinder practical applications. One of the key solutions is to design apply efficient, highly stable, long‐life catalysts. Herein, a nanostructured CoTe 2 /Co─O─NC electrocatalytic material developed achieve effective adsorption bidirectional catalytic conversions lithium polysulfides (LiPSs). Results show that oxygen bridges (Co─O─C) formed in not only effectively shift d‐band center cobalt near its Fermi level enhance LiPSs also strengthen built‐in electric fields /Co heterojunctions reduce barrier sulfur conversion. Deposition dissociation Li S significantly enhanced during charging/discharging processes. Durability active catalyst improved, rapid cross‐interfacial charge transfer achieved. The synthesized S/CoTe cathode exhibits an initial capacity 1498 mAh g −1 at 0.1 C, decay rate over 500 cycles 0.5 C 0.046%. Li─S pouch cells using density 368 Wh kg areal 7.7 cm −2 loading 6.7 mg , with electrolyte/sulfur ratio 4 µL .

Language: Английский

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