Differences in Electrochemistry between Fibrous SPAN and Fibrous S/C Cathodes Relevant to Cycle Stability and Capacity

Warneke, Sven; Eusterholz, Michael K.; Zenn, Roland K.; Hintennach, Andreas; Dinnebiér, Robert E.; Buchmeiser, Michael R.

doi:10.1149/2.0061801jes

Cited by 33 publications

(41 citation statements)

References 42 publications

(68 reference statements)

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“…The good processability of PAN means that SPAN cathode materials with expected structures can be obtained via vulcanization of PAN samples with specific morphologies. For example, porous, fibrous, and porous fibrous SPAN cathode materials, all of which help to further enhance Li–S battery performance, have been developed. Recently, Frey et al reported a facile, low‐cost, and scalable synthesis of fibrous SPAN with cylindrical macropores, as shown in the SEM image in Figure a, through the thermal conversion of commercially available polymethyl methacrylate (PMMA)/PAN‐based nonwovens.…”

Section: Vulcanization/inverse Vulcanization Polysulfide Polymer Basementioning

confidence: 99%

Recent Advances in Applying Vulcanization/Inverse Vulcanization Methods to Achieve High‐Performance Sulfur‐Containing Polymer Cathode Materials for Li–S Batteries

2018

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Lithium–sulfur (Li–S) batteries have great prospects as next‐generation energy storage devices because of their high energy density, inexpensive raw materials, and low pollution. However, the development of Li–S batteries is currently restricted by the shuttle effect that occurs during the charge–discharge process. Sulfur‐containing polymers are attractive for use as Li–S battery cathode materials to alleviate the shuttle effect through chemical bonds as well as physical confinement. Moreover, polymers have numerous different molecular structures and definable functional groups. A suitable monomer design can result in a final sulfur‐containing polymer possessing favorable properties such as ion and electron conductivity, high sulfur content, appropriate viscosity, processability, and controllable morphology. These characteristics are of great benefit for use in Li–S battery cathodes to achieve high capacity and stable discharge at high rates. This review summarizes recent developments in sulfur‐containing polymer cathode materials. Focusing on polymers prepared by the facile and low‐cost vulcanization/inverse vulcanization methods and the polymer‐based composites, the chemical structures and electrochemical mechanisms are clarified, and the relationship between their structures and performances is discussed comprehensively. It is expected that more polymer electrode materials with high performance will emerge in the coming years.

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Section: Vulcanization/inverse Vulcanization Polysulfide Polymer Basementioning

confidence: 99%

Recent Advances in Applying Vulcanization/Inverse Vulcanization Methods to Achieve High‐Performance Sulfur‐Containing Polymer Cathode Materials for Li–S Batteries

2018

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“…A linear correlation between the viscosity of the electrolyte and the structure of the ionic dendrimers is shown in Figure S3, Supporting Information. The fact that viscosity can influence electrochemistry was already shown for carbonate‐based electrolytes containing LiTFSI as conducting salt and has now been found true for ionic dendrimer‐based electrolytes, too. Discharge capacities of the cells decreased with increasing chain length of the rest R .…”

Section: Resultsmentioning

confidence: 80%

“…Since SPAN‐based cathodes are compatible with carbonate‐based electrolytes, a mixture of ethylene carbonate and dimethyl carbonate (1:1, v/v) was used as solvent. The ionic dendrimers were dissolved in the solvent mixture to achieve a [TFSI − ] concentration of 1 mol L −1 .…”

Section: Resultsmentioning

confidence: 99%

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Synthesis of Ionic Dendrimers and Their Potential Use as Electrolytes for Lithium–Sulfur Batteries

Lebherz

Weldin

Hintennach

et al. 2019

Macro Chemistry & Physics

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A series of ionic dendrimers is synthesized and used as conducting salt in carbonate‐based electrolytes for Li/S‐cells. The resulting electrolytes display increasing viscosity with increasing chain length of the side chains, both in the first‐ and second‐generation dendrimers. Higher conductivity is observed for the first‐generation dendrimers as compared to the second‐generation ones. While all cells show high cycle stability, the differences in dendrimer structure also influence the electrochemical behavior of the Li–S cells. Thus, discharge capacities of the corresponding Li–S cells correlate both with the viscosity and the conductivity of the electrolytes. The best electrolyte system is obtained with a first‐generation dendrimer having a short side chain, D1‐1, having the lowest viscosity and the highest conductivity, which delivers discharge capacities of 1150 mAh gsulfur−1 @ 0.5 C and 780 mAh gsulfur−1 @ 1 C.

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“…One of the most promising materials is sulfurized polyacrylonitrile (PAN‐S) . Owing to the good processability of PAN, porous, fibrous, and porous fibrous PAN‐S cathode materials were investigated to further enhance the performance of Li–S batteries. In addition, Pyun and co‐workers reported an inverse vulcanized polymer using 1,3‐diisopropenylbenzene (DIB) as linker monomers .…”

Section: Introductionmentioning

confidence: 99%

Trapping of Polysulfides with Sulfur‐Rich Poly Ionic Liquid Cathode Materials for Ultralong‐Life Lithium–Sulfur Batteries

Liu

Zeng

et al. 2020

ChemSusChem

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Sulfur‐rich polymers synthesized by inverse vulcanization are promising cathodes for Li–S batteries and can suppress the shuttle effect to improve the cycling properties of Li–S batteries. However, developing a sulfur‐rich copolymer with new chemical functionality to enhance performance of Li–S batteries remains a huge challenge. In this report, a sulfur‐rich polymer cathode containing ionic liquid segments named poly(sulfur‐co‐1‐vinyl‐3‐allylimidazolium bromide) [poly(S‐co‐DVIMBr)] was obtained by the inverse vulcanization of S8 with DVIMBr and used as cathode for the first time. This sulfur‐rich poly ionic liquid cathode showed effective suppression of the shuttle effect through joint effects of the stable chemical bonding of C−S and strong cation absorption for lithium polysulfides, which was confirmed by DFT calculations. In particular, the Li–S cell with poly(S‐co‐DVIMBr) cathode delivered high capacity retention of 90.22 % even over 900 cycles. Developing sulfur‐rich poly ionic liquids may provide a new strategy of introducing the functional groups with cations into the cathode materials for suppressing the shuttle effect and improving the performance of Li–S batteries.

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Differences in Electrochemistry between Fibrous SPAN and Fibrous S/C Cathodes Relevant to Cycle Stability and Capacity

Cited by 33 publications

References 42 publications

Recent Advances in Applying Vulcanization/Inverse Vulcanization Methods to Achieve High‐Performance Sulfur‐Containing Polymer Cathode Materials for Li–S Batteries

Recent Advances in Applying Vulcanization/Inverse Vulcanization Methods to Achieve High‐Performance Sulfur‐Containing Polymer Cathode Materials for Li–S Batteries

Synthesis of Ionic Dendrimers and Their Potential Use as Electrolytes for Lithium–Sulfur Batteries

Trapping of Polysulfides with Sulfur‐Rich Poly Ionic Liquid Cathode Materials for Ultralong‐Life Lithium–Sulfur Batteries

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