Understanding of Sulfurized Polyacrylonitrile for  Superior Performance Lithium/Sulfur Battery

Zhang, Sheng S.

doi:10.3390/en7074588

Cited by 210 publications

(226 citation statements)

References 33 publications

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“…75,76 Specifically, the sulfur molecule reacts with PAN to form a heterocyclic polymeric matrix by attaching to the acryl-backbone (Figure 12a), while the sp 3 -hybridzed carbon becomes sp 2 -conjugated with the cyclized nitrile group. 77 The formation of S-S, C-S and C=C bonds is evidenced by FTIR spectroscopy (Figure 12c). 78,79 This structure bypasses the polysulfide shuttle by avoiding the formation of the soluble LiPSs (Li 2 S x , 4 ≤ x ≤ 8).…”

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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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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“…35 However, the Li 2 S cathode is equally challenging because of its insulating nature and generation of soluble polysulfides upon oxidation, similar to issues with a normal sulfur cathode. [36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53] These issues can be overcome by encapsulating Li 2 S cathodes within electronically conductive carbon-based materials such as graphene and porous carbon. Nevertheless, the use of Li 2 S may not be as appealing for high-energy Li-S cells, (even with Si anodes), because of the loss of active Li toward passivation and also the reduced voltage (∼0.5 V) inherent to the Si anode vs. Li metal.…”

mentioning

confidence: 99%

Metal Sulfide-Blended Sulfur Cathodes in High Energy Lithium-Sulfur Cells

Bugga

Jones

Pasalic

et al. 2016

J. Electrochem. Soc.

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Lithium-sulfur cells exhibit poor cycle life, due to the well-known 'polysulfide shuttle' enabled by the dissolution of the sulfur reduction products in organic electrolyte. Different strategies have been implemented to reduce the shuttle effects, with limited success, especially through use of low sulfur loadings (1-2 mg/cm 2 ). Dense electrodes with high sulfur loadings are essential for high energy cells, however, such electrodes experience more serious polysulfide effects. In this paper, we describe the benefits of blending sulfur with a transition metal sulfide (here, TiS 2 and MoS 2 ) to form dense composite cathodes with enhanced conductivity. There is an improvement in both the initial capacity from sulfur utilization (∼800 mAh/g based on sulfur content), the coulombic efficiency (>96%) and also in cycle life upon blending with the metal sulfide. High sulfur loadings (>12 mg/cm 2 or ∼6 mAh/cm 2 per side) were demonstrated to display high sulfur utilization in Li-S cells containing the metal sulfide blends either with or without coatings over the sulfur cathode. XRD studies were carried out to understand the redox behavior of the metal sulfide additive during charge/discharge cycling of the sulfur cathodes. DC polarization and Potentiometric Intermittent Titration Technique (PITT) measurements were made on sulfur cathodes with and without metal sulfide blends to determine the charge transfer and diffusional kinetics. Since their inception in 1991, Li-ion batteries 1 have progressed at a rapid pace, with a three-fold enhancement in their performance achieved through many advances in both electrode materials and electrolytes.2-9 Current Li-ion cells from commercial vendors (e.g., Panasonic, LG and Samsung) provide an impressive specific energy of >250 Wh/kg and energy density of >600 Wh/l which are benefiting a wide range of applications including portable electronic devices, electric vehicles and aerospace needs. Yet, many of the emerging markets such as electric vehicles and renewable energy technologies place even higher demands on the battery technologies, both in terms of performance and cost. It is believed that the performance of lithium-ion technologies has reached a plateau, and any future improvements will only be marginal. Replacement of graphite anodes with Si, and conventional 4 V cathodes with the high voltage Li-rich layered-layered composite cathodes, 10,11 has not yet successfully been applied to commercial batteries. Accordingly, any gains in specific energy and energy density have been modest so far after a decade of development. 12,13 There is, thus, a pursuit for more energetic battery technologies beyond Li-ion batteries. This has led to a renewed interest in the lithiumsulfur system, which has the highest theoretical specific energy of all the known rechargeable systems (due to the high capacity of sulfur, 1672 mAh/g, ∼ 6-10x of Li-ion cathodes), with the notable exception of Li-O 2 which itself has several serious fundamental hurdles that are not close to being overcome.14-16 The spe...

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“…As shown in Figure 1, the double-plateau profiles disappeared after the first lithiation: this is due to the nanoscopic redistribution of sulfur/polysulfides that is a well-known phenomenon among S/PANbased composites (Wang et al, 2002;Yu et al, 2004;Fanous et al, 2011;Doan et al, 2013;Zhang, 2014).…”

Section: Figurementioning

confidence: 96%

“…So far, S/PAN composites show relatively stable cycle life performance even in LiPF 6 /carbonate-based electrolyte solutions (note that any other composites cannot be used in LiPF 6 /carbonate-based electrolyte solutions because of irreversible polysulfides-carbonate reactions) (Wang et al, 2002(Wang et al, , 2003Yu et al, 2004;Fanous et al, 2011;Doan et al, 2013Doan et al, , 2014Zhang et al, 2013d,e;Konarov et al, 2014;Li et al, 2014;Zhang, 2014): it has been explained that the nanoscopic (or sub-nanoscopic) distribution of sulfur/polysulfides in cyclized PAN contributes to the polysulfide stabilization (Wang et al, 2002(Wang et al, , 2003Yu et al, 2004;Fanous et al, 2011;Doan et al, 2013;Zhang, 2014). S/PAN binary composites (Wang et al, 2002) or S/PAN/conducting carbon ternary composites (Wang et al, 2003) were first suggested by Wang et al Recently, S/PAN composites with nanosized additives, such as S/PAN/nanosized Mg 0.6 Ni 0.4 O (MNO) (Zhang et al, 2013d), S/PAN/graphene (Zhang et al, 2013e), and S/PAN/reduced graphene oxide (RGO) , were intensively investigated by the research groups of University of Waterloo (Canada) and Nazarbayev University (Kazakhstan), and it is likely that the use of nanosized filler (either conducting or non-conducting; conducting ones tend to show better rate performance, of course) can contribute to a better cycle life performance than the composites without nanosized fillers probably owing to the more homogeneous sulfur distribution.…”

Section: Introductionmentioning

confidence: 99%

High Mass-Loading of Sulfur-Based Cathode Composites and Polysulfides Stabilization for Rechargeable Lithium/Sulfur Batteries

Hara

Konarov²,

Mentbayeva

et al. 2015

Front. Energy Res.

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Citation:Hara T, Konarov A, Mentbayeva A, Kurmanbayeva I and Bakenov Z (2015) Although sulfur has a high theoretical gravimetric capacity, 1672 mAh/g, its insulating nature requires a large amount of conducting additives: this tends to result in a low massloading of active material (sulfur), and thereby, a lower capacity than expected. Therefore, an optimal choice of conducting agents and of the method for sulfur/conductingagent integration is critically important. In this paper, we report that the areal capacity of 4.9 mAh/cm 2 was achieved at sulfur mass loading of 4.1 mg/cm 2 by casting sulfur/polyacrylonitrile/ketjenblack (S/PAN/KB) cathode composite into carbon fiber paper. This is the highest value among published/reported ones even though it does not contain expensive nanosized carbon materials such as carbon nanotubes, graphene, or graphene derivatives, and competitive enough with the conventional LiCoO 2 -based cathodes (e.g., LiCoO 2 , <20 mg/cm 2 corresponding to <2.8 mAh/cm 2 ). Furthermore, the combination of sulfur/PAN-based composite and PAN-based carbon fiber paper enabled the sulfurbased composite to be used even in carbonate-based electrolyte solution that many lithium/sulfur battery researchers avoid the use of it because of severer irreversible active material loss than in electrolyte solutions without carbonate-based solutions, and even at the highest mass-loading ever reported (the more sulfur is loaded, the more decomposed sulfides deposit at an anode surface).

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Understanding of Sulfurized Polyacrylonitrile for Superior Performance Lithium/Sulfur Battery

Cited by 210 publications

References 33 publications

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

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

Metal Sulfide-Blended Sulfur Cathodes in High Energy Lithium-Sulfur Cells

High Mass-Loading of Sulfur-Based Cathode Composites and Polysulfides Stabilization for Rechargeable Lithium/Sulfur Batteries

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