Monolayer Fe<sub>3</sub>GeX<sub>2</sub> (X = S, Se, and Te) as Highly Efficient Electrocatalysts for Lithium–Sulfur Batteries

Song, Xiaohan; Qu, Yuanyuan; Zhao, Lanling; Zhao, Mingwen

doi:10.1021/acsami.0c21136

Cited by 55 publications

(73 citation statements)

References 50 publications

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“…A similar kind of improved binding energies upon the involvement of the U parameter is also observed in other works. 81 Thus, we conclude that GGA/PBE is well capable of describing the studied phenomenon.…”

Section: Resultsmentioning

confidence: 51%

Design Principles of Bifunctional Electrocatalysts for Engineered Interfaces in Na–S Batteries

Jayan

Islam

2021

ACS Catal.

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The shuttling of soluble sodium polysulfides (Na2S n ) and sluggish conversion kinetics are major roadblocks toward the practical realization of sodium–sulfur (Na–S) batteries. To undertake the challenges, we use first-principles calculations to design bifunctional electrocatalysts to achieve engineered interfaces with sulfur-based cathode materials. We illustrate the detailed behavior of Na2S n adsorption, sulfur reduction reactions (SRRs), and catalytic decomposition on transition-metal (TM)-based single-atom catalysts (SACs) embedded on MoS2 substrates (SACs@MoS2). We observe that SACs doped on sulfur substitution and molybdenum top sites result in adequate binding energies to immobilize higher-order Na2S n species. We found the d-band center as an important “descriptor” in dictating polysulfide adsorption energies and catalytic activities on SACs@MoS2. We elucidate that the larger upward shift of the d-band center toward the Fermi level and the involved higher number of vacant antibonding states are directly correlated to the adsorption strength of the Na2S n . The V and Ni SACs are found to exhibit higher and lower binding energies, respectively, consistent with the d-band theory. Furthermore, the SACs that are electron-deficient sites demonstrate bifunctional electrocatalytic activity through reduced free energy for SRR and lower the barrier for Na2S decomposition in favor of accelerated electrode kinetics during discharge and charge processes, respectively. The electronic structure calculations reveal a significantly reduced band gap of the pristine and Na2S n -adsorbed SACs@MoS2 due to mid-gap states, majorly stemming from TM-d orbitals, thus expected to improve the electronic conductivity of the substrates. The insight developed on the role of SACs in tailoring the polysulfides’ chemistry at the interfaces in relation to their d-band center is an important step toward the rational design of cathode materials for high-performance Na–S batteries.

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Section: Resultsmentioning

confidence: 51%

Design Principles of Bifunctional Electrocatalysts for Engineered Interfaces in Na–S Batteries

Jayan

Islam

2021

ACS Catal.

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“…This indicates D-UiO-66-NH 2 can weaken the Li−S bond and thus reduce the decomposition barriers of Li 2 S due to the largest amount of charge transfer among them. 49 In this regard, the defects engineering strategy will further allow the D-UiO-66-NH 2 to be a bidirection The further interaction between D-UiO-66-NH 2 -4 and LiPSs was profoundly validated by its UV−vis spectrum and XPS analysis prior to and after the adsorption. The UV−vis results indicate an efficient confinement of D-UiO-66-NH 2 -4 toward polysulfides migration (Figure S14A).…”

Section: Resultsmentioning

confidence: 99%

“…As shown in Figure D – F, our calculations show the amount of charge transfer from Li 2 S to the UiO is 0.40 e (UiO-66), 0.43 e (UiO-66-NH 2 ), and 0.48 e (D-UiO-66-NH 2 ), respectively. This indicates D-UiO-66-NH 2 can weaken the Li–S bond and thus reduce the decomposition barriers of Li 2 S due to the largest amount of charge transfer among them . In this regard, the defects engineering strategy will further allow the D-UiO-66-NH 2 to be a bidirection electrocatalyst for the conversion reaction between the intermediates of LiPSs and the final product of Li 2 S.…”

Section: Resultsmentioning

confidence: 99%

Defects Engineering of Lightweight Metal–Organic Frameworks-Based Electrocatalytic Membrane for High-Loading Lithium–Sulfur Batteries

Lin

Ding

et al. 2021

ACS Nano

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The sluggish kinetics and shuttle effect of lithium polysulfide intermediates are the major issues that retard the practical applications of lithium–sulfur (Li–S) batteries. Herein, we introduce a defect engineering strategy to construct a defected-UiO-66-NH2-4/graphene electrocatalytic membrane (D-UiO-66-NH2-4/G EM) which could accelerate the conversion of lithium polysulfides in high sulfur loadings and low electrolyte/sulfur (E/S) ratio Li–S batteries. Metal–organic frameworks (UiO-66-NH2) can be directionally chemical engraved to form concave octahedra with abundant defects. According to electrocatalytic kinetics and DFT calculations studies, the D-UiO-66-NH2-4 architecture effectively provides ample sites to capture polysulfides via strong chemical affinity and effectively delivers electrocatalytic activity of polysulfide conversion. As a result, a Li–S battery with such an electrocatalytic membrane delivers a high capacity of 12.3 mAh cm–2 (1013 mAh g–1) at a sulfur loading up to 12.2 mg·S cm–2 under a lean electrolyte condition (E/S = 5 μL mg–1-sulfur) at 2.1 mA cm–2 (0.1 C). Moreover, a prototype soft package battery also exhibits excellent cycling stability with a maintained capacity of 996 mAh g–1 upon 100 cycles.

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“…Based on these models, Zhao and coauthors predicted that two-dimensional magnetic Fe 3 GeX 2 (X = S, Se, and Te) monolayers could be potential candidates which possess bifunctional electrocatalytic activity to the SRR and the Li 2 S decomposition reaction. 103 Zhang and coauthors explored the possibility of α-tellurene as the host material in Li-S batteries. 104 Xiong's group proposed a novel kind of tungsten (W) single atomic catalyst with high LiPSs adsorption ability and catalytic activity (Figure 6).…”

Section: Lithium-ion Diffusion and LI 2 S Decomposition Modelsmentioning

confidence: 99%

Section: Theoretical Models For Sulfur Cathode Conversionsmentioning

confidence: 99%

A review on theoretical models for lithium–sulfur battery cathodes

Feng

Chen

et al. 2022

InfoMat

191

119

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Lithium-sulfur (Li-S) batteries have been considered as promising battery systems due to their huge advantages on theoretical energy density and rich resources. However, the shuttle effect and sluggish transformation of soluble lithium polysulfides (LiPSs) hinder the practical application of Li-S batteries.Tremendous sulfur host materials with unique catalytic activity have been exploited to inhibit the shuttle effect and accelerate LiPSs redox reactions, in which theoretical simulations have been widely adopted. This review aims to summarize the fundamentals and applications of theoretical models in sulfur cathodes. Concretely, the integration of theoretical models provides insights into the adsorption and conversion mechanisms of LiPSs and is further utilized in the smart design of catalysts for the exploitation of practical Li-S batteries. Finally, a perspective on the future combination of calculation technology and theoretical models is provided.

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Monolayer Fe₃GeX₂ (X = S, Se, and Te) as Highly Efficient Electrocatalysts for Lithium–Sulfur Batteries

Cited by 55 publications

References 50 publications

Design Principles of Bifunctional Electrocatalysts for Engineered Interfaces in Na–S Batteries

Design Principles of Bifunctional Electrocatalysts for Engineered Interfaces in Na–S Batteries

Defects Engineering of Lightweight Metal–Organic Frameworks-Based Electrocatalytic Membrane for High-Loading Lithium–Sulfur Batteries

A review on theoretical models for lithium–sulfur battery cathodes

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Monolayer Fe3GeX2 (X = S, Se, and Te) as Highly Efficient Electrocatalysts for Lithium–Sulfur Batteries

Cited by 55 publications

References 50 publications

Design Principles of Bifunctional Electrocatalysts for Engineered Interfaces in Na–S Batteries

Design Principles of Bifunctional Electrocatalysts for Engineered Interfaces in Na–S Batteries

Defects Engineering of Lightweight Metal–Organic Frameworks-Based Electrocatalytic Membrane for High-Loading Lithium–Sulfur Batteries

A review on theoretical models for lithium–sulfur battery cathodes

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Monolayer Fe₃GeX₂ (X = S, Se, and Te) as Highly Efficient Electrocatalysts for Lithium–Sulfur Batteries