Defect‐Rich Single Atom Catalyst Enhanced Polysulfide Conversion Kinetics to Upgrade Performance of Li–S Batteries

Jing, Weitao; Tan, Qiang; Duan, Yue; Zou, Kunyang; Dai, Xin; Song, Yuanyuan; Shi, Ming; Sun, Junjie; Chen, Yuanzhen; Liu, Yongning

doi:10.1002/smll.202204880

Cited by 31 publications

(23 citation statements)

References 65 publications

(100 reference statements)

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“…At the same time, the potential for the conversion of long-chain polysulfides to short-chain polysulfides decreases, which is more conducive to the conversion of liquid-phase long-chain polysulfides to short-chain polysulfides, proving that the 3DCS-FMO@C/PP-modified separator can perform the catalytic conversion of polysulfides. Similar cases have also been discussed in recent publications. , The 3DCS-FMO@C separator further exhibited the smallest overpotential and Q 2 /Q 1 compared with the other separators (Figure b), indicating the efficient promotion of redox reactions. , …”

Section: Results and Discussionsupporting

confidence: 88%

“…37,38 The 3DCS-FMO@C separator further exhibited the smallest overpotential and Q 2 / Q 1 compared with the other separators (Figure 5b), indicating the efficient promotion of redox reactions. 39,40 The rate performances of batteries assembled with different materials are shown in Figure 5c. The specific discharge capacities of 3DCS-FMO@C/PP material batteries at current densities of 0.1C, 0.2C, 0.5C, and 1C were 1510, 1074, 894, and 803 mAh g −1 , respectively.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Improvement of Redox Kinetics of Dendrite-Free Lithium–Sulfur Battery by Bidirectional Catalysis of Cationic Dual-Active Sites

Feng

Wang

Wen

et al. 2023

ACS Sustainable Chem. Eng.

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The practical application of lithium–sulfur batteries (LSBs) is hampered by the slow lithium polysulfide (LIPS) conversion kinetics and the uncontrollable anode-metal lithium dendrites. Herein, a three-dimensional cation dual-active-site eggshell structure compound (3DCS-FMO@C) was synthesized by soft template, ion exchange, and pyrolysis to modify the commercial separator. Experimental and theoretical analysis results showed that Mn2+ and Fe2+ sites in 3DCS-FMO@C can synergistically adsorb LIPSs, effectively regulate the bidirectional conversion dynamics of intermediate liquid-phase LIPSs and solid-phase lithium sulfide, and reduce the energy barrier of the reaction. The 3DCS-FMO@C-modified separator with high mechanical stability and no reduction in ion diffusion also had a lithiophilic central core that can homogenize the lithium-ion flow, thereby inhibiting the dendrite growth of lithium. Based on the above advantages, 3DCS-FMO@C-modified separator LSBs had better electrochemical performance, including an initial capacity of 1530 mAh g–1 at 0.1C and an ultralow decay rate of 0.029% for 1000 cycles at 0.5C. A high area capacity of 8.7 mAh cm–2 was achieved even with high sulfur loading and poor electrolyte. This work provided a basis for understanding the bidirectional catalysis for practical application in LSBs and simultaneously solved the problem of lithium dendrites.

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Section: Results and Discussionsupporting

confidence: 88%

Section: ■ Results and Discussionmentioning

confidence: 99%

Improvement of Redox Kinetics of Dendrite-Free Lithium–Sulfur Battery by Bidirectional Catalysis of Cationic Dual-Active Sites

Feng

Wang

Wen

et al. 2023

ACS Sustainable Chem. Eng.

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“…and/or nonmetal (N, S, P, etc.) heteroatom doping in carbon matrices. ,,− The generation of extrinsic defects can regulate the electronic structure, create plenty of unsaturated sites, and hence offer preferable active centers for accelerating electrochemical kinetics. For example, He et al synthesized Co/N doped carbon nanotubes (CNTs) by grinding and subsequent calcination, which showed remarkable ORR performance .…”

Section: Introductionmentioning

confidence: 99%

Intrinsic Carbon Defects in Nitrogen and Sulfur Doped Porous Carbon Nanotubes Accelerate Oxygen Reduction and Sulfur Reduction for Electrochemical Energy Conversion and Storage

Zhou

Chen

Zhang

et al. 2023

ACS Appl. Nano Mater.

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Defects and morphology engineering is a serviceable strategy to boost the electrochemical energy conversion and storage performance of carbon-based materials. In this study, nitrogen/sulfur codoped carbon nanotubes (NS-CNTs) were first obtained via the pyrolysis of presynthesized polyaniline nanotubes with micelles composed of methyl orange and ferric chloride acting as the soft template. Furthermore, intrinsic carbon defects and mesopores were introduced to obtain etched NS-CNTs (ENS-CNTs) composites by ammonia etching. The rational combination of intrinsic/extrinsic defects and porous nanotube morphology features is beneficial to the oxygen reduction reaction (ORR) and sulfur reduction reaction (SRR) performances of the ENS-CNTs electrode. The coexistence of intrinsic carbon defects and extrinsic N/S dopants can create massive catalytically active sites for electrochemical processes, while the porous one-dimensional nanotube-like carbon framework is responsible for accessibility of catalytic active sites, species hosting, electrical conductivity, mass transport, and stability. Consequently, the ENS-CNTs-30 (where 30 represents the corresponding etching time in minutes) electrode for ORR displayed a high half-wave potential of 859 mV vs RHE, a diffusion limiting current density of 6.65 mA cm–2, admirable stability, and methanol tolerance. The solid Zn–air battery (ZAB) assembled with ENS-CNTs-30 as the active material for the air cathode revealed remarkable power density (137 mW cm–2) and specific capacity (1467.4 mAh g–1 Zn). Meanwhile, the ENS-CNTs-30 electrode for SRR also demonstrated ameliorative lithium–polysulfide (LiPS) trapping capability and Li2S deposition kinetics. The lithium–sulfur battery (LSB) with ENS-CNTs-30 as sulfur host material unfolded initial capacities of 1100 and 883 mAh g–1 at 0.2 and 2 C, respectively, and a capacity retention ratio of 82.0% after 200 cycles at 0.2 C. This work provides a feasible strategy for defects and morphology engineering of multifunctional carbon-based catalysts in electrochemical energy conversion and storage fields.

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“…From the perspective of facilitating electron/ion transfer, blocking LiPS diffusion, catalyzing sulfur redox reaction, and enhancing energy density, a SAMC-modified separator could act as a multifunctional mediator for the whole sulfur transformation, which has been reported in many works. , Especially, SAMCs show an excellent catalytic role for sulfur conversion originating from the highly active valence electrons, quantum confinement of electrons in the d orbital, and quantization of the energy level. − Among them, single Fe atom catalysts are low-cost and efficient choices, which normally exist as the Fe–N 4 –C coordination type on carbon substrates. Jing et al utilized a defect-rich Fe–N 4 single-atom catalytic material (Fe–N 4 /DCS) to modify the routine PP separator, in which Fe–N 4 /DCS/PP can effectively inhibit the shuttling of polysulfides and accelerate the redox reaction . Zhang et al synthesized different single-atom metal catalysts (metal = Fe/Co/Ni) on the nitrogen-doped graphene and utilized them as separator coating layers, finally concluding that Fe SACMs may be the better option to be used in Li–S systems …”

Section: Introductionmentioning

confidence: 99%

Vanadium as Auxiliary for Fe–V Dual-Atom Electrocatalyst in Lithium–Sulfur Batteries: “3D in 2D” Morphology Inducer and Coordination Structure Regulator

Yang,

Pan,

Zhou

et al. 2023

ACS Nano

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The undesirable shuttling behavior, the sluggish redox kinetics of liquid−solid transformation, and the large energy barrier for decomposition of Li 2 S have been the recognized problems impeding the practical application of lithium−sulfur batteries. Herein, inspired by the spectacular catalytic activity of the Fe/V center in bioenzyme for nitrogen/sulfur fixation, we design an integrated electrocatalyst comprising N-bridged Fe−V dual-atom active sites (Fe/V−N 7 ) dispersed on ingenious "3D in 2D" carbon nanosheets (denoted as DAC), in which vanadium induces the laminar structure and regulates the coordination configuration of active centers simultaneously, realizing the redistribution of the 3dorbital electrons of Fe centers. The high coupling/conjunction between Fe/V 3d electrons and S 2p electrons shows strong affinity and enhanced reactivity of DAC-Li 2 S n (1 ≤ n ≤ 8) systems. Thus, DAC presents strengthened chemisorption ability toward polysulfides and significantly boosts bidirectional sulfur redox reaction kinetics, which have been evidenced theoretically and experimentally. Besides, the well-designed "3D in 2D" morphology of DAC enables uniform sulfur distribution, facilitated electron transfer, and abundant active sites exposure. Therefore, the assembled Li−S cells present outstanding cycling stability (637.3 mAh g −1 after 1000 cycles at 1 C) and high rate capability (711 mAh g −1 at 4 C) under high sulfur content (70 wt %).

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Defect‐Rich Single Atom Catalyst Enhanced Polysulfide Conversion Kinetics to Upgrade Performance of Li–S Batteries

Abstract: The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/smll.202204880.

Cited by 31 publications

References 65 publications

Improvement of Redox Kinetics of Dendrite-Free Lithium–Sulfur Battery by Bidirectional Catalysis of Cationic Dual-Active Sites

Improvement of Redox Kinetics of Dendrite-Free Lithium–Sulfur Battery by Bidirectional Catalysis of Cationic Dual-Active Sites

Intrinsic Carbon Defects in Nitrogen and Sulfur Doped Porous Carbon Nanotubes Accelerate Oxygen Reduction and Sulfur Reduction for Electrochemical Energy Conversion and Storage

Vanadium as Auxiliary for Fe–V Dual-Atom Electrocatalyst in Lithium–Sulfur Batteries: “3D in 2D” Morphology Inducer and Coordination Structure Regulator

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