Improving the Charge Conductance of Elemental Sulfur via Tandem Inverse Vulcanization and Electropolymerization

Dirlam, Philip T.; Simmonds, Adam G.; Shallcross, R. Clayton; Arrington, Kyle J.; Chung, Woo Jin; Griebel, Jared J.; Hill, Lawrence J.; Glass, Richard S.; Char, Kookheon; Pyun, Jeffrey

doi:10.1021/mz500730s

Cited by 63 publications

(43 citation statements)

References 30 publications

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“…Dirlam et al first enhanced the conductivity of sulfur polymers by incorporating polythiophene moieties into sulfur‐based copolymers with a very high sulfur content ( Figure a) via the tandem inverse vulcanization and electropolymerization of S 8 and styrene‐functionalized 3,4‐propylenedioxythiophene (ProDOT‐Sty). Zentel and co‐workers.…”

Section: Vulcanization/inverse Vulcanization Polysulfide Polymer Basementioning

confidence: 99%

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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%

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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“…84 These organosulfur species act as plasticizers and co-deposit onto the cathode framework along with other low-order LiPSs during discharge. A few other comonomers, such as diethynylbenzene (DEB), 85 oleyamine, 86 styrenic propylenedioxythiophene 87 and 1,4-diphenylbutadiyne (DiPhDY) 88 have also been attempted for inverse-vulcanization. In particular, S-r-DiPhDY has shown good performance with an initial capacity of 1500 mA·h·g −1 and a decay rate of 0.085% per cycle over 800 cycles.…”

Section: Chemical Bonding Within Polymer Chainsmentioning

confidence: 99%

Review—The Importance of Chemical Interactions between Sulfur Host Materials and Lithium Polysulfides for Advanced Lithium-Sulfur Batteries

Pang

Liang

Kwok

et al. 2015

J. Electrochem. Soc.

293

199

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This overview details the recently recognized importance of strong chemical interactions between sulfur host materials and lithium polysulfides/sulfide to improve the performance of Li-S batteries, especially with respect to cycle life. Sulfur hosts consisting of: functionally modified surfaces, metal oxides and carbides that rely on either polar interactions or the thiosulfate mechanism for sulfide binding, metal-organic frameworks that exhibit Lewis-acid behavior, and functional polymers are reviewed. We summarize a variety of studies that explore the nature and strength of the interaction of these materials with polysulfides and its effect on cycle life, showing that capacity fading is reduced to as low as 0.03% per cycle with effective functional cathode host surfaces. The ever-growing demand and consumption of energy as well as the depletion of fossil fuels and its associated environmental pollution have driven scientists to pursue renewable energy alternatives. Photovoltaic panels and wind farms are being installed worldwide. However, to fully utilize the electricity generated by these inherently intermittent sources, rechargeable battery systems are a vital part of the system, enabling grid-scale electric storage and benefitting electric and hybrid-electric vehicular transport. 1Amongst all the rechargeable battery systems that have serviced mankind for decades, lithium-ion batteries (LIBs) have dominated the commercial battery market, owing to their high cell voltage, low self-discharge rate, and stable cycling performance.2-4 However, the applications of these batteries have been somewhat limited due to their low energy density (100-220 W·h·kg −1 ) and high cost. 5,6 These battery systems -which consist of a graphite anode and a lithium metal oxide cathode and rely on a Li-ion intercalation mechanismare very attractive for the electric vehicle market. Nonetheless, they do not enable a long driving range unless very large battery packs are utilized, which comes at very high cost and weight. Thus the goal of traveling 500 km per charge is still unattainable. Electrochemical systems that offer a higher capacity and energy density as well as a longer life-time at a lower cost are becoming promising options, but are definitely challenging to bring into practice.Lithium-sulfur (Li-S) batteries are considered as one of the most promising candidates for the next-generation energy storage systems, because of their high theoretical energy density and the natural abundance of sulfur.7-10 A conventional Li-S cell consists of a lithium metal anode and an elemental sulfur cathode in an ether-based electrolyte. The coupling of the high-capacity electrodes of lithium (3840 mA·h·g −1 ) and sulfur (1675 mA·h·g −1 ) affords an average cell voltage of 2.2 V and a theoretical energy density of 2570 W·h·kg −1 . The reversible conversion reaction between sulfur and lithium sulfide (Li 2 S) is accompanied by a series of intermediate lithium polysulfides (LiPSs, Li 2 S n , 2 ≤ n ≤ 8). The electrochemical reactions of Li-S batte...

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“…[12][13][14][15][16] The analogous electrochemical reactivity of the high S-S bond content of these copolymers compared with elemental sulfur (S 8 ) enables their use as the active material in lithium-sulfur (Li-S) batteries. 23 In an effort to further expand the scope of inverse vulcanization and produce a copolymer with additional functionality capable of enhancing performance as the active cathode material for Li-S batteries we have investigated 1,4diphenylbutadiyne (DiPhDY) as a new comonomer. Furthermore, sulfur is an economical, earth abundant material making its direct use with inverse vulcanization attractive for development of sustainable next generation electrochemical storage technology.…”

mentioning

confidence: 99%

Inverse vulcanization of elemental sulfur with 1,4-diphenylbutadiyne for cathode materials in Li–S batteries

et al. 2015

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High sulfur content copolymers were prepared via inverse vulcanization of sulfur with 1,4-diphenylbutadiyne (DiPhDY) for use as the active cathode material in lithium-sulfur batteries. These sulfur-rich polymers exhibited excellent capacity retention (800 mA h g À1 at 300 cycles) and extended battery lifetimes of over 850 cycles at C/5 rate. Fig. 3 (a) Cycling performance at C/5 of Li-S battery fabricated with poly(S-co-DiPhDY) prepared with a 10 wt% DiPhDY, 90 wt% sulfur feed ratio. (b) Plot of potential versus charge/discharge capacity for the Li-S cell shown in (a) at 100 cycle intervals. (c) Charge/discharge rate performance of Li-S battery with poly(S-co-DiPhDY) (10 wt% DiPhDY) at various current densities (1 C ¼ 1672 mA h). All capacities are specific capacity based on sulfur loading.This journal is

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Improving the Charge Conductance of Elemental Sulfur via Tandem Inverse Vulcanization and Electropolymerization

Cited by 63 publications

References 30 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

Review—The Importance of Chemical Interactions between Sulfur Host Materials and Lithium Polysulfides for Advanced Lithium-Sulfur Batteries

Inverse vulcanization of elemental sulfur with 1,4-diphenylbutadiyne for cathode materials in Li–S batteries

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