Elaboration of Aggregated Polysulfide Phases: From Molecules to Large Clusters and Solid Phases

Xiao, Jiewen; Zhou, Guangmin; Chen, Hetian; Feng, Xiang; Legut, Dominik; Fan, Yanchen; Wang, Tianshuai; Cui, Yi; Zhang, Qianfan

doi:10.1021/acs.nanolett.9b03297

Cited by 16 publications

(12 citation statements)

References 26 publications

(41 reference statements)

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“…We consider a (Li 2 S) 8 cluster adsorbed on the SAC to calculate this barrier quantitatively (Table S2, Supporting Information). The (Li 2 S) 8 cluster adopted here has the lowest energy configuration, as verified in our previous work, [ 32 ] and is a more realistic model compared to the single‐molecule Li 2 S adsorption with high energy dangling bonds. As shown in Figure 1d, SAC binds with sulfur in the (Li 2 S) 8 cluster.…”

Section: Resultsmentioning

confidence: 59%

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Engineering d‐p Orbital Hybridization in Single‐Atom Metal‐Embedded Three‐Dimensional Electrodes for Li–S Batteries

et al. 2021

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Li-S) batteries is seriously restricted by their low sulfur loading and utilization, sluggish reaction kinetics, and poor cycling stability. [4,5] So far, appropriate active adsorption [6,7] and catalytic centers, such as metal sulfides, [8][9][10] oxides, [11][12][13] nitrides, [14] and vanadium compounds, [15] have been introduced to enhance the sulfur utilization and accelerate the reversible conversion between lithium polysulfides (LiPSs) and Li 2 S. [16,17] However, high weight percentages of these additives sacrifice the overall energy density of Li-S batteries. Single-atom metal catalysts (SACs) comprising monodispersed metal atoms on appropriate substrates have a theoretical 100% atom utilization efficiency, and therefore have a much higher activity than conventional bulk metal and nanoparticle catalysts. [18,19] Various SACs have been introduced into Li-S batteries to improve their electrochemical performance. [20][21][22] Generally, the effects of SACs have been attributed to their good adsorption ability to LiPSs and their high catalytic activity. However, the lack of a fundamental understanding of the catalysis mechanism and the material properties that govern catalytic activity have hindered the selection and rational design of SACs for Li-S batteries. In previous studies, the SACs were usually Single-atom metal catalysts (SACs) are used as sulfur cathode additives to promote battery performance, although the material selection and mechanism that govern the catalytic activity remain unclear. It is shown that d-p orbital hybridization between the single-atom metal and the sulfur species can be used as a descriptor for understanding the catalytic activity of SACs in Li-S batteries. Transition metals with a lower atomic number are found, like Ti, to have fewer filled anti-bonding states, which effectively bind lithium polysulfides (LiPSs) and catalyze their electrochemical reaction. A series of single-atom metal catalysts (Me = Mn, Cu, Cr, Ti) embedded in threedimensional (3D) electrodes are prepared by a controllable nitrogen coordination approach. Among them, the single-atom Ti-embedded electrode has the lowest electrochemical barrier to LiPSs reduction/Li 2 S oxidation and the highest catalytic activity, matching well with the theoretical calculations. By virtue of the highly active catalytic center of single-atom Ti on the conductive transport network, high sulfur utilization is achieved with a low catalyst loading (1 wt.%) and a high area-sulfur loading (8 mg cm −2 ). With good mechanical stability for bending, these 3D electrodes are suitable for fabricating bendable/foldable Li-S batteries for wearable electronics.

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Section: Resultsmentioning

confidence: 59%

“…[49][50][51][52] To simulate the energy barrier to delithiation, we used the (Li 2 S) 8 cluster adsorption model, where the cluster structure has been evaluated in our previous work. [32]…”

Section: Supporting Informationmentioning

confidence: 99%

Engineering d‐p Orbital Hybridization in Single‐Atom Metal‐Embedded Three‐Dimensional Electrodes for Li–S Batteries

et al. 2021

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“…Obviously, Li 2 S has the lowest reaction energy in these polysulfide products, and other researches also prove that Li 2 S has the lowest formation energy. [ 30 ] It indicates that Li 2 S is the main ingredient in the in situ formed SEI layer on the surface of metallic Li.…”

Section: Resultsmentioning

confidence: 99%

“…Lithium sulfide (Li 2 S) has an outstanding chemical stability against Li and the lowest formation energy among lithium polysulfides. [30][31][32] Moreover, Li 2 S has a superior ionic conductivity of ≈10 −5 S cm −1 , [33,34] as compared with lithium carbonate (≈10 −8 S cm −1 ) [35] and LiF (≈10 −9 S cm −1 ). [36] Besides, inorganic SEI usually protects the metallic Li anode better than organic components which are generated by the reactions between Li and carbonate electrolyte.…”

Section: Introductionmentioning

confidence: 99%

A Facile Way to Construct Stable and Ionic Conductive Lithium Sulfide Nanoparticles Composed Solid Electrolyte Interphase on Li Metal Anode

Cui

Liu

Wang

et al. 2020

Adv Funct Materials

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Due to the high theoretical capacity and low reduction potential, metallic lithium is a promising anode material for the next generation of high-energydensity batteries. However, the dynamic Li plating/stripping process can easily destroy the unstable solid electrolyte interphase (SEI) and cause dendrite growth. Here, an artificial lithium sulfide nanoparticle composed SEI layer with superior stability and high ionic conductivity is designed by a spray quenching method. The artificial SEI layer on Li surface can effectively minimize the side reactions and suppress Li dendrite growth, and the metal electrode delivers stable cycling for 500 cycles in the symmetrical cell with carbonate electrolyte. Moreover, when this SEI-modified Li anode is coupled with a LiFePO 4 cathode, the full cell shows promoted cycling stability and rate capability. This work provides a broadly applicable and facile strategy to address the intrinsic issues of lithium metal anodes.

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“…We revealed a more realistic LiPSs conversion process through ab-initio simulations. [13] People conventionally regard LiPSs as molecules. However, in well encapsulated cathodes, LiPSs may tend to exist as aggregated phases.…”

Section: The Electrolytesmentioning

confidence: 99%

Ab-Initio Simulations Accelerate the Development of High-Performance Lithium-Sulfur Batteries

Zhang¹

2022

MatLab

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Lithium-sulfur batteries (LSBs) are promising candidates for next-generation cost-effective and high-energy-density rechargeable batteries. However, cathodes, anodes, and electrolytes of LSBs all face multiple technological challenges. Nowadays, theoretical models play an increasingly important role in LSBs in probing highly catalytic cathodes, dendrite-free anodes, and stable electrolytes. In this perspective, first, the LSBs theoretical research projects our group participated in are reviewed, focusing on highlighting the interpretation and guidance of ab-initio simulations on experiments. Next, the prospect of combining automated workflow managers, machine learning techniques with ab-initio simulations is presented, hoping to introduce a new paradigm for LSBs research and development.

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Elaboration of Aggregated Polysulfide Phases: From Molecules to Large Clusters and Solid Phases

Cited by 16 publications

References 26 publications

Engineering d‐p Orbital Hybridization in Single‐Atom Metal‐Embedded Three‐Dimensional Electrodes for Li–S Batteries

Engineering d‐p Orbital Hybridization in Single‐Atom Metal‐Embedded Three‐Dimensional Electrodes for Li–S Batteries

A Facile Way to Construct Stable and Ionic Conductive Lithium Sulfide Nanoparticles Composed Solid Electrolyte Interphase on Li Metal Anode

Ab-Initio Simulations Accelerate the Development of High-Performance Lithium-Sulfur Batteries

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