Dual redox mediators accelerate the electrochemical kinetics of lithium-sulfur batteries

Liu, Fang; Sun, Geng; Wu, Hao; Chen, Gen; Xu, Duo; Mo, Runwei; Shen, Li; Li, Xianyang; Ma, Shengxiang; Tao, Ran; Tan, Xin; Xu, Bin; Wang, Ge; Dunn, Bruce; Sautet, Philippe; Lu, Yunfeng

doi:10.1038/s41467-020-19070-8

Cited by 131 publications

(93 citation statements)

References 63 publications

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“…First, the confinement effect brought by Nb 2 O 5 layers, including physical-and chemical-confinement, could retain the sulfur species in the electrode, which prohibits the sulfur losing of the active material. Second, Nb 2 O 5 layers could work as the electron-ion source, as verified by peer work, [13] to accelerate the redox processes of the sulfur species, which may also facilitate the reformation of Sb 2 S 3 . Moreover, Nb 2 O 5 and Sb 2 S 3 are well dispersed on the shell and core layers of the carbon nanofibers, and further crosslink into the network structure, which provides a highway for electrons transfer.…”

Section: Resultsmentioning

confidence: 97%

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Stimulating the Reversibility of Sb₂S₃ Anode for High‐Performance Potassium‐Ion Batteries

Liu

Cao

et al. 2021

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working mechanism of LIBs, K ions in the potassium-ion batteries (KIBs) also shuttle between the cathode and anode through the separator. Luckily, the potassium resources are much sufficient in the crust (2.09 wt%), [1] which may endow the KIBs low cost. Moreover, merits such as low standard reduction potential of K + (−2.93 V vs SHE), fast K ions transport kinetics in electrolyte, and "internal fuse" effect brought by the low melting point of K metal (63.4 °C), [2] make KIBs potential alternatives to LIBs in some scenarios. Therefore, it is meaningful and urgent to develop KIBs electrode materials with excellent K ions storage properties. Among the candidates for KIBs anode, conversion-alloy reaction materials have attracted considerable attention recently. [3-7] These materials are always have high theoretical specific capacity and suitable working potentials. For example, antimony tri-sulfide (Sb 2 S 3) proceeds a conversion reaction for the formation of Sb and subsequent alloy reaction for the formation of K 3 Sb, delivering a theoretical capacity of 974 mAh g −1. [6] However, an inevitable volume expansion is companied and that destroy the microstructure of the active materials, leading the capacity degradation. What is worse, sulfur species in the intermediate products are ambiguous and readily dissolved in the electrolyte, resulting in the loss of sulfur in the sulfides. Liu et al. reported the by-product sulfur and poly-sulfides in the intermediates of Sb 2 S 3 anode, and the irreversible conversion of Sb 2 S 3 could be the main reason for the failure of Sb 2 S 3 anode in KIBs. [8] Wang et al. observed the formation of poly-sulfides (K 2 S 4) when adopting Bi 1.11 Sb 0.89 S 3 nanotube as KIBs anode. [7] Recently, Zhang and coauthors found that the potassiated products (K 3 Sb and K 2 S) can transform into the original Sb 2 S 3 when they evaluated Sb 2 S 3 @C nanowire for KIBs anode using in situ transmission electron microscopy (TEM), though the electrode also suffered a capacity degeneration. [3] These works suggest that the total electrochemical reaction reversibility of Sb 2 S 3 anode for KIBs is viable in thermodynamics, while the reaction route and the intermediate products may be mainly controlled by the kinetics. However, few works on Sb 2 S 3 anode achieved the full reversibility and long cycling stability up to now. Therefore, it is meaningful to stimulate reversibility of Sb 2 S 3 anode via constructing neat Conversion-alloy sulfide materials for potassium-ion batteries (KIBs) have attracted considerable attention because of their high capacities and suitable working potentials. However, the sluggish kinetics and sulfur loss result in their rapid capacity degeneration as well as inferior rate capability. Herein, a strategy that uses the confinement and catalyzed effect of Nb 2 O 5 layers to restrict the sulfur species and facilitate them to form sulfides reversibly is proposed. Taking Sb 2 S 3 anode as an example, Sb 2 S 3 and Nb 2 O 5 are dispersed in the core and shell layers of carbon nanofib...

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Section: Resultsmentioning

confidence: 97%

“…[12] Liu et al found that Nb 2 O 5 along with its lithiation products could work as electron-ion reservoirs to accelerate the electrochemical kinetics of sulfur intermediates. [13] Thus, it is fascinating to stimulate the reversibility of Sb 2 S 3 anode by cooperating with Nb 2 O 5 .…”

Section: Introductionmentioning

confidence: 99%

Stimulating the Reversibility of Sb₂S₃ Anode for High‐Performance Potassium‐Ion Batteries

Liu

Cao

et al. 2021

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“…Local electrical and electrochemical measurements and imaging at the nanoscale are crucial for the future development of molecular sensors, [ 1 ] materials engineering, [ 2 ] electro‐physiology, [ 3,4 ] and various energy applications from artificial photosynthesis [ 5 ] to batteries. [ 6 ] Additionally, it allows us to increase our understanding of molecular interactions in liquid, which is currently based on theoretical models of ensemble measurements. Towards these goals, scanning electrochemical microscopy (SECM), including the use of nanopipettes, [ 7–9 ] has been developed to sense electrochemical reactions locally, providing spatial resolution of typically μm to the sub‐μm range, [ 10–12 ] but also fast reactions on nanometric particles could be resolved when well isolated.…”

Section: Introductionmentioning

confidence: 99%

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Attoampere Nanoelectrochemistry

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Pavoni

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to batteries. [6] Additionally, it allows us to increase our understanding of molecular interactions in liquid, which is currently based on theoretical models of ensemble measurements. Towards these goals, scanning electrochemical microscopy (SECM), including the use of nanopipettes, [7][8][9] has been developed to sense electrochemical reactions locally, providing spatial resolution of typically μm to the sub-μm range, [10][11][12] but also fast reactions on nanometric particles could be resolved when well isolated. [13,14] SECM techniques are now well-established for probing electrochemical systems at the micro-and nanoscale levels. [15,16] Scanning probes have exploited redox-cycling amplification to reduce the electrode dimensions while keeping a reasonable signal level. [11,17,18] Electrochemical scanning tunneling microscopy (EC-STM) has been used to study electrochemistry indirectly from a molecular electronics perspective. [19,20] To date, these techniques have enabled measurements down to the fA (10 −15 Ampere) range, [11,[21][22][23][24][25] which is still not sensitive enough to obtain electrochemical signals at the nanoscale, except in the specific case of redox cycling amplification when ferrocene (Fc) is confined between 2 neighboring electrodes at the nanoscale. [23,25] For the versatile measurement of electrochemical currents at the nanoscale aA (10 −18 Ampere) sensitivity is crucial.Electrochemical microscopy techniques have extended the understanding of surface chemistry to the micrometer and even sub-micrometer level. However, fundamental questions related to charge transport at the solidelectrolyte interface, such as catalytic reactions or operation of individual ion channels, require improved spatial resolutions down to the nanoscale. A prerequisite for single-molecule electrochemical sensitivity is the reliable detection of a few electrons per second, that is, currents in the atto-Ampere (10 −18 A) range, 1000 times below today's electrochemical microscopes. This work reports local cyclic voltammetry (CV) measurements at the solid-liquid interface on ferrocene self-assembled monolayer (SAM) with sub-atto-Ampere sensitivity and simultaneous spatial resolution < 80 nm. Such sensitivity is obtained through measurements of the charging of the local faradaic interface capacitance at GHz frequencies. Nanometer-scale details of different molecular organizations with a 19% packing density difference are resolved, with an extremely small dispersion of the molecular electrical properties. This is predicted previously based on weak electrostatic interactions between neighboring redox molecules in a SAM configuration. These results open new perspectives for nano-electrochemistry like the study of quantum mechanical resonance in complex molecules and a wide range of applications from electrochemical catalysis to biophysics.

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“…The escalating demand for high energy density rechargeable batteries has not only driven the research on the improvement of traditional lithium ion batteries, but also spurred the development of next generation ultra-high energy density battery technologies such as lithium-oxygen and lithium-sulfur batteries (LSBs) 1,2 . In particular, LSBs possessing a high theoretical speci c energy of 2600 Wh kg -1 together with the very low cost of sulfur have attracted extensive attention for energy storage applications in recent years 1,[3][4][5][6] . However, there are still numerous issues that impede commercializing LSBs.…”

Section: Introductionmentioning

confidence: 99%

Zinc Complex-Based Multifunctional Reactive Lithium Polysulfide Trapper Approaching Its Theoretical Efficiency

Zuo

2021

ACS Appl. Mater. Interfaces

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The "shuttle effect" of soluble lithium polysul des (LPS), which causes rapid capacity fading, remains a lingering issue for lithium-sulfur batteries (LSBs). Herein, we report a new type of reactive molecule-based (or molecular) LPS trapper, zinc acetate-diethanolamine (Zn(OAc) 2 •DEA), which demonstrated a molecular e ciency of 1.8 for LPS trapping, approaching its theoretical limit of 2. This is the highest trapping capability among all reported LPS trappers. During discharge the trapped polysul des are much more thermodynamically favored for reduction compared to the non-trapped ones, while during charge the complex Zn(SLi) 2 •DEA formed in the previous discharging process can be more easily oxidized due to its lower energy barrier in comparison to Li 2 S, indicating the catalytic effects of Zn 2+ •DEA on the redox of sulfur species. Zn(OAc) 2 •DEA is also an excellent binder owing to its multiple intermolecular hydrogen bonds. LSBs using Zn(OAc) 2 •DEA as a LPS trapper, a binder, and a redox catalyst exhibited excellent longterm cycling stability (with a capacity retention of 85% after 1000 cycles at a rate of 0.5 C) and enhanced rate performance. The work demonstrated the potential of this novel type of multifunctional metal complex-based reactive molecular LPS trappers for high capacity and stable LSBs.

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Dual redox mediators accelerate the electrochemical kinetics of lithium-sulfur batteries

Cited by 131 publications

References 63 publications

Stimulating the Reversibility of Sb₂S₃ Anode for High‐Performance Potassium‐Ion Batteries

Stimulating the Reversibility of Sb₂S₃ Anode for High‐Performance Potassium‐Ion Batteries

Attoampere Nanoelectrochemistry

Zinc Complex-Based Multifunctional Reactive Lithium Polysulfide Trapper Approaching Its Theoretical Efficiency

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Dual redox mediators accelerate the electrochemical kinetics of lithium-sulfur batteries

Cited by 131 publications

References 63 publications

Stimulating the Reversibility of Sb2S3 Anode for High‐Performance Potassium‐Ion Batteries

Stimulating the Reversibility of Sb2S3 Anode for High‐Performance Potassium‐Ion Batteries

Attoampere Nanoelectrochemistry

Zinc Complex-Based Multifunctional Reactive Lithium Polysulfide Trapper Approaching Its Theoretical Efficiency

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Stimulating the Reversibility of Sb₂S₃ Anode for High‐Performance Potassium‐Ion Batteries

Stimulating the Reversibility of Sb₂S₃ Anode for High‐Performance Potassium‐Ion Batteries