Solution processible hyperbranched inverse-vulcanized polymers as new cathode materials in Li–S batteries

Wei, Yangyang; Li, Xiang; Xu, Zhen; Sun, Haiyan; Zheng, Yaochen; Peng, Li; Liu, Zheng; Gao, Chao; Gao, Mingxia

doi:10.1039/c4py01055h

Cited by 58 publications

(50 citation statements)

References 82 publications

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“…24 The front edge of this very recent research line includes also the introduction of new functionalities in the S polymer networks, such as polythiophene segments considering electropolymerization 31 and the direct polymerization of S with poly(3-hexylthiophene-2,5-diyl), 32 the changing of the functionalities of the cross-linker (e.g., using 1,4-diphenylbutadiyene) 33 or the improvement of the processability of the materials through the synthesis of S hyperbranched networks. 34 These researches aimed at the improvement of the performance of cathodes based on S-rich polymer networks, namely by increasing their conductivity and minimizing the PS shuttle effect. The production of sulfur/thiirane copolymers considering reversible addition-fragmentation chain transfer (RAFT) polymerization [35][36][37] in mild reaction conditions (e.g., temperature range 20-90 8C and in a presence of a solvent), leading to high S content (up to 80%) soluble polymeric materials [e.g., in toluene and tetrahydrofuran (THF)] was also recently reported in literature.…”

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Electrochemical activity of sulfur networks synthesized through RAFT polymerization

Almeida

Costa

Kadhirvel

et al. 2016

J of Applied Polymer Sci

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Novel results concerning the inverse vulcanization of sulfur using reversible addition-fragmentation chain transfer (RAFT) polymerization are here reported. It is shown that RAFT polymerization can be used to carry out this cross-linking process, with the additional possibility to extend the reaction time from a few minutes as with classical free radical polymerization (FRP) to several hours. Higher control on viscosity and processability of the synthesized networks, as well as, the implementation of semibatch feed policies during cross-linking are important advantages of the RAFT process here explored comparatively to the FRP inverse vulcanization. Using cyclic voltammetry, it was assessed the electrochemical activity of the synthesized sulfur-rich polymer networks. It is shown that the fundamental electrochemical activity of the elemental sulfur was preserved in the produced materials. Testing of electrochemical cells assembled with lithium in the anode and different sulfur based materials in the cathode, including the synthesized RAFT networks, is also shown. The results here presented highlight the new opportunities introduced by reversible-deactivation radical polymerization mechanisms on the control of the synthesis process and in the design of such advanced materials and show also that many potential derivatizing possibilities can be achieved.

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confidence: 99%

Electrochemical activity of sulfur networks synthesized through RAFT polymerization

Almeida

Costa

Kadhirvel

et al. 2016

J of Applied Polymer Sci

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“…2 Thus, the challenge remains to develop electroactive components for battery electrodes which utilize sustainable, earth abundant materials that also possess improved electrochemical properties. [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. [3][4][5][6][7][8][9][10][11] High sulfur content copolymers have recently been of particular interest as a class electroactive polymeric cathode materials for secondary lithium batteries due to their high specic capacity and exceptional cycle life.…”

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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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“…Wei et al recently utilized a modified inverse vulcanization methodology to generate a soluble inverse vulcanized hyperbranched polymer (SIVHP) (Fig. 26) [290]. Postfunctionalization of the poly(S-r-DIB) copolymer by a thiol-ene reaction, followed by a Menschutkin click reaction afforded a water-soluble copolymer.…”

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confidence: 99%

Polymerizations with elemental sulfur: A novel route to high sulfur content polymers for sustainability, energy and defense

Griebel

Glass

Char

et al. 2016

Progress in Polymer Science

375

254

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Recent developments in the polymerizations of elemental sulfur (S 8 ) to prepare high sulfur content polymers are reviewed. While the homopolymerization of S 8 via ring-opening processes to prepare high molar mass polymeric sulfur has long been known, this form of polymeric sulfur is chemically unstable and depolymerizes back to S 8 . In the current report, we discuss the background into the production of sulfur via petroleum refining and the challenges associated with utilizing S 8 as a chemical reagent for materials synthesis. To circumvent these long standing challenges in working with sulfur, the use of S 8 as a reaction medium and comonomer in a process termed, inverse vulcanization, was developed to prepare chemically stable and processable sulfur copolymers. Furthermore, access to polymeric materials with a very high content of sulfur-sulfur (S-S) bonds enabled for the first time the creation of materials with useful (electro)chemical and optical properties which are reviewed for use in Li-S batteries, IR imaging technology and self-healing materials.

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Solution processible hyperbranched inverse-vulcanized polymers as new cathode materials in Li–S batteries

Abstract: Highly soluble inverse-vulcanized hyperbranched polymers were synthesized as cathode-active materials in Li–S batteries.

Cited by 58 publications

References 82 publications

Electrochemical activity of sulfur networks synthesized through RAFT polymerization

Electrochemical activity of sulfur networks synthesized through RAFT polymerization

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

Polymerizations with elemental sulfur: A novel route to high sulfur content polymers for sustainability, energy and defense

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