Asymmetric allyl-activation of organosulfides for high-energy reversible redox flow batteries

Weng, Guoming; Yang, Boguang; Liu, Chi You; Du, Guan Ying; Li, Elise Y.; Lu, Yi‐Chun

doi:10.1039/c9ee00336c

Cited by 48 publications

(35 citation statements)

References 56 publications

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“…While the main emphasis in the development of RFBs has been on experimental efforts to improve their performance, a number of recent attempts have been made to rationally design the structural, electronic, and other properties of RFBs from a theoretical point of view. [81][82][83][84][85] In these and other studies, [86][87][88][89][90][91] where experiment is complemented with computational modeling, density functional theory (DFT) calculations are usually employed to model the redox properties of the charge carriers with the aim of increasing cell voltage and solubility of active species, enhancing stability and reversibility of redox species, and shedding light into reaction kinetics. Since the energy density of an RFB is a function of cell potential and solubility, improving these two parameters represents a major challenge for researchers working in this field.…”

Section: Recent Advancesmentioning

confidence: 99%

A Comparative Review of Metal‐Based Charge Carriers in Nonaqueous Flow Batteries

et al. 2020

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Energy storage is becoming the chief barrier to the utilization of more renewable energy sources on the grid. With independent service operators aiming to acquire gigawatts in the next 10–20 years, there is a large need to develop a suite of new storage technologies. Redox flow batteries (RFB) may be part of the solution if certain key barriers are overcome. This Review focuses on a particular kind of RFB based on nonaqueous media that promises to meet the challenge through higher voltages than the organic and aqueous variants. This class of RFB is divided into three groups: molecular, macromolecular, and redox‐targeted systems. The growing field of theoretical modeling is also reviewed and discussed.

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Section: Recent Advancesmentioning

confidence: 99%

A Comparative Review of Metal‐Based Charge Carriers in Nonaqueous Flow Batteries

et al. 2020

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“…In this study, we take advantage of organodisulfides to design stable and highly concentrated electrolytes. Though organodisulfides (two‐electron transfer reaction) show a lower capacity in comparison with trisulfide compounds (four‐electron), it is able to circumvent the possible formation of Li 2 S (solid phase) to ensure the high reversibility and high utilization of active materials [16c] . Herein, tetramethylthiuram disulfide (TMTD) and tetraethylthiuram disulfide (TETD) are adopted as new‐type redox‐active molecules for nonaqueous RFB design given their ultralow material cost and stable resonance structures, which can provide good electrochemical stability in different organic electrolytes.…”

Section: Introductionmentioning

confidence: 99%

Insights into the Redox Chemistry of Organosulfides Towards Stable Molecule Design in Nonaqueous Energy Storage Systems

Zhao

Zhang

2020

Angew Chem Int Ed

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Nonaqueous redox flow batteries (RFBs) have great potential to achieve high‐energy storage systems. However, they have been limited by low solubility and poor stability of active materials. Here we demonstrate organosulfides as a new‐type model material system to explore the rational design of redox‐active molecules in nonaqueous systems. The tetraethylthiuram disulfide (TETD) molecule shows high solubility in various common organic solvents and achieves a high reversible capacity of ca. 50 Ah L−1 at a high concentration of 1 M. The resonance structures in the reduced product endow the molecule with high electrochemical stability in different organic electrolytes. The underlying mechanism in redox chemistry of organodisulfides involving the cleavage and reformation of disulfide bonds is revealed by material/structural characterizations. This study provides a new perspective of molecule designs for the development of redox‐active materials for high‐performance nonaqueous RFBs.

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“…Different from N‐MC, the discharge profiles of N 0.8 S 0.2 ‐MC and N 0.5 S 0.5 ‐MC consist of two distinct sloped‐regions with the ranges of 0.01–0.8 and 0.8–2.4 V, respectively . The former one refers to the absorption and intercalation of sodium ion within carbon layers and pores, while the latter is directly ascribed to faraday reactions between sodium ions and organosulfides, thus giving a higher capacity of 348 and 425 mAh g −1 . As the sulfur content further increased in N 0.2 S 0.8 ‐MC and S‐MC, two obvious plateaus appear in voltage profiles, in good accordance with CVs.…”

Section: Resultsmentioning

confidence: 99%

Accurate Control Multiple Active Sites of Carbonaceous Anode for High Performance Sodium Storage: Insights into Capacitive Contribution Mechanism

Liang

et al. 2020

Advanced Energy Materials

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Heteroatom doping is widely recognized as an appealing strategy to break the capacitance limitation of carbonaceous materials toward sodium storage. However, the concrete effects, especially for heteroatomic phase transformation, during the sodium storage reaction remain a confusing topic. Here, a novel hypercrosslinked polymerization approach is demonstrated to fabricate pyrrole/thiophene hypercrosslinked microporous copolymer and further give porous carbonaceous materials with accurately regulated N/S dual doping corresponding to starting feeding ratios. Significantly, the N doping contributes to the conductivity and surface wettability, while the S doping is bridged to build stable active sites, which can be electrochemically converted into mercaptan anions via faraday reaction and further enhancing reversible capacities. Meanwhile, the abundant S doping can also conduce to the expanded interlayer spacing to shorten the ions diffusion distance, thus optimizing the reaction kinetic. As a result, the N0.2S0.8‐micro‐dominant porous carbon delivers the highest reversible capacity of 521 mAh g−1 at 100 mA g−1 and excellent cyclic stability over 2000 cycles at 2000 mA g−1 with a capacity decay of 0.0145 mAh g−1 per cycle. This work is anticipated to provide an in‐depth understanding of capacitance contribution and illuminate the heteroatomic phase transformation during sodium storage reactions for doping carbonaceous anodes.

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Asymmetric allyl-activation of organosulfides for high-energy reversible redox flow batteries

Abstract: This work demonstrates an effective and universal strategy to improve the sluggish organosulfides (R–Sn–R) for redox flow batteries by asymmetric allylsubstituted organosulfides (R–Sn–A).

Cited by 48 publications

References 56 publications

A Comparative Review of Metal‐Based Charge Carriers in Nonaqueous Flow Batteries

A Comparative Review of Metal‐Based Charge Carriers in Nonaqueous Flow Batteries

Insights into the Redox Chemistry of Organosulfides Towards Stable Molecule Design in Nonaqueous Energy Storage Systems

Accurate Control Multiple Active Sites of Carbonaceous Anode for High Performance Sodium Storage: Insights into Capacitive Contribution Mechanism

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