An Organic–Inorganic Hybrid Cathode Based on S–Se Dynamic Covalent Bonds

Zhao, Jiawei; Si, Yubing; Han, Zixiao; Li, Junjie; Guo, Wei; Fu, Yongzhu

doi:10.1002/anie.201913243

Cited by 38 publications

(44 citation statements)

References 32 publications

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“…The proposed reaction process is shown in Figure 10 b. The Se-doping in SPAN can significantly enhance the redox conversion of polysulfides andr eaction kinetics, thus [35] and [36].Copyright2 020, Wiley-VCH, Weinheim, and copyright2 019,Nature Publishing Group, respectively. leadingt ot he compatibility with ether electrolyte and suppression of dissolution of polysulfides.…”

Section: Se-doping In Sulfur Compositesmentioning

confidence: 99%

“…Recently, our group reported a diphenyl trisulfide (Ph‐S 3 ‐Ph)‐Se nanowire (DPTS‐Se) hybrid cathode based on S−Se dynamic covalent bonds for Li batteries . This is the first time an organic polysulfide was combined with an inorganic Se electrode.…”

Section: Hybrid Materials Containing S−se Bondsmentioning

confidence: 99%

Section: Hybrid Materials Containing S−se Bondsmentioning

confidence: 99%

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Electrochemistry of Electrode Materials Containing S−Se Bonds for Rechargeable Batteries

Guo

2020

Chemistry A European J

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Sulfur (S) and selenium (Se) have been considered as promising high capacity cathode materials for rechargeable batteries. They have differencesintheir physical properties (e.g.,e lectronic conductivity) but the same number of electrons in their outermost shells,w hichl eads to similarity in their electrochemical behavior in batteries. In recent years, some efforts have been taken to combine them in electrodes in the hope of improved battery performance. The SÀSe bonds of these electrode materials lead to unusual properties and intriguing electrochemical behavior,w hich have attracted increasing interest. In thisM inireview,e lectrode materials containing SÀSe bonds are summarized, including inorganic S x Se y solid solutions, organic compounds, and organic-inorganic hybrid materials. Our understanding in these materials is still premature, but they have shown unique properties to be electrode materials. We hope this Minireview could provideanew insight into the design,s ynthesis, and understanding of thesem aterials, which could enable high energy density rechargeable batteries.

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Section: Se-doping In Sulfur Compositesmentioning

confidence: 99%

Section: Hybrid Materials Containing S−se Bondsmentioning

confidence: 99%

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Electrochemistry of Electrode Materials Containing S−Se Bonds for Rechargeable Batteries

Guo

2020

Chemistry A European J

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“…Recently, Li and Lu [26] designed a charge-reinforced ion-selective (CRIS) membrane to retain polysulfide/polyiodide, achieving a superior stable cycling of 17.9 Ah L -1 negolyte+posolyte over 500 cycles. Organosulfides [19,20,[27][28][29][30][31] are attractive materials in energy storage owing to their high theoretical capacity, high structure diversity, and environmental friendliness. The S-S bond is reversibly broken and reformed upon cycling, involving two-electron transfer [32,33].…”

Section: Introductionmentioning

confidence: 99%

A Low-Crossover and Fast-Kinetics Thiolate Negolyte for Aqueous Redox Flow Batteries

Yang

Wang

et al. 2022

Energy Mater Adv

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Aqueous redox flow batteries (ARFBs) are a promising technology for large-scale energy storage. Developing high-capacity and long-cycle negolyte materials is one of major challenges for practical ARFBs. Inorganic polysulfide is promising for ARFBs owing to its low cost and high solubility. However, it suffers from severe crossover resulting in low coulombic efficiency and limited lifespan. Organosulfides are more resistant to crossover than polysulfides owing to their bulky structures, but they suffer from slow reaction kinetics. Herein, we report a thiolate negolyte prepared by an exchange reaction between a polysulfide and an organosulfide, preserving low crossover rate of the organosulfide and high reaction kinetics of the polysulfide. The thiolate denoted as 2-hydroxyethyl disulfide+potassium polysulfide (HEDS+K2S2) shows reduced crossover rate than K2S2, faster reaction kinetics than HEDS, and longer lifespan than both HEDS and K2S2. The 1.5 M HEDS+1.5 M K2S2 static cell demonstrated 96 Ah L-1negolyte over 100 and 200 cycles with a high coulombic efficiency of 99.2% and 99.6% at 15 and 25 mA cm-2, respectively. The 0.5 M HEDS+0.5 M K2S2 flow cell delivered a stable and high capacity of 30.7 Ah L-1negolyte over 400 cycles (691 h) at 20 mA cm-2. This study presents an effective strategy to enable low-crossover and fast-kinetics sulfur-based negolytes for advanced ARFBs.

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“…[ 19,20 ] More recently, polymers containing multiple SS bonds that have been synthesized through inverse vulcanization, [ 21,22 ] incorporation of covalent frameworks, [ 22–25 ] and condensation reactions have been reported. [ 26–29 ] In addition to polymers, linear compounds, [ 15,30,31 ] cyclics, [ 32 ] hybrids, [ 33,34 ] and compounds with unique functional groups have also been reported. [ 35–37 ]…”

Section: Introductionmentioning

confidence: 99%

Xanthogen Polysulfides as a New Class of Electrode Material for Rechargeable Batteries

Bhargav

Manthiram

2020

Advanced Energy Materials

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electrochemical reversibility. In addition to their favorable redox behavior, these compounds are also naturally abundant, environmentally friendly, inexpensive, and easy to process into battery electrodes. [12] While sulfur offers a high energy density exceeding 2500 W h kg −1 , it is beleaguered by three major issues. First, the electrical conductivity of sulfur is extremely low, necessitating the addition of a large amount of conductive hosts (e.g., carbon) in the battery electrode. Second, the difference in density between sulfur and its discharge product, Li 2 S, is quite large. This results in a volume change of nearly 80% during cycling, thus requiring a cathode structure to accommodate the large volume fluctuation and the resulting stresses generated. Third, the lithium polysulfides formed during cycling are electrolyte-soluble and thus shuttle between the electrodes. This "shuttle effect" results in a loss of active material, poor Coulombic efficiency, and short cycle life. [8] On the other hand, organic compounds (e.g., carbonyls, organosulfides, imines, and nitriles) present three distinct advantages. First, the functional groups in the organic moieties can alter the physical properties of these materials including their electrical conductivity. [9] Second, the difference in density between the delithiated and the lithiated forms of these compounds is low, resulting in a smaller volume change and stress in the cathode. [13] Finally, the bulkiness and polarity of the organic functional groups can be used to alter their solubility in the electrolyte, thus minimizing parasitic shuttle effects. [12,14] Organosulfur compounds combine the multi-electron, highenergy-density characteristics of sulfur with the distinct advantages of organic compounds. Specifically, the ability to tune the physical and chemical properties of organosulfur materials with various functional groups allows for optimization of their conductivity, solubility, and density. [9,15-17] Recognizing these advantages, various organosulfur compounds have been reported since the late 1980s. [18,19] Early reports of such materials focused on polymers that functioned according to the disulfide-thiolate redox behavior. [19,20] More recently, polymers containing multiple SS bonds that have been synthesized through inverse vulcanization, [21,22] incorporation of covalent frameworks, [22-25] and condensation reactions have been reported. [26-29] In addition to polymers, linear compounds, [15,30,31] cyclics, [32] hybrids, [33,34] and compounds with unique functional groups have also been reported. [35-37] Organosulfides are an emerging class of alternative sulfur-based cathode materials. This work explores a new member in this family of active materials, viz., xanthogen polysulfides. Diisopropyl xanthogen polysulfide (DIXPS) is used as a model compound in a lithium battery to understand the chemical changes and the unique electrochemical behavior of this class of materials by employing various materials characterization methodologies. As a cathode ma...

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An Organic–Inorganic Hybrid Cathode Based on S–Se Dynamic Covalent Bonds

Cited by 38 publications

References 32 publications

Electrochemistry of Electrode Materials Containing S−Se Bonds for Rechargeable Batteries

Electrochemistry of Electrode Materials Containing S−Se Bonds for Rechargeable Batteries

A Low-Crossover and Fast-Kinetics Thiolate Negolyte for Aqueous Redox Flow Batteries

Xanthogen Polysulfides as a New Class of Electrode Material for Rechargeable Batteries

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