Preparation and electrochemical properties of sulfur–acetylene black composites as cathode materials

Zhang, B.; Lai, Chao; Zhou, Zhen; Gao, Xueping

doi:10.1016/j.electacta.2009.01.056

Cited by 193 publications

(101 citation statements)

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“…A much higher Q low /Q up ratio of 2.10 can be observed in the cell after 50 cycles compared with that after the first cycle (Q low /Q up ¼ 1.06). As the representative microporous carbonsulphur composite cathodes exhibit only the lower discharge plateau during cycling 16,18 , the stretching Q low corresponds to the capacity contribution from the micropore-trapped active material. In addition, it appears that the active material needs to take a few cycles to reach a steady state in the cathode region to offer stable electrochemical performance because of the solubility of the intermediate lithium polysulphides in the electrolyte 14 .…”

Section: Resultsmentioning

confidence: 99%

“…Employing sulphur-carbon composites and applying conductive polymer surface modification are the main approaches in laboratories around the world to realize high capacity and improved cycle life [2][3][4][5][13][14][15][16][17][18][19][20] . Both approaches enhance the electrical conductivity of the cathode and suppress the loss of soluble polysulphide intermediates during cycling and thereby improve the active material utilization and cyclability.…”

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Lithium–sulphur batteries with a microporous carbon paper as a bifunctional interlayer

2012

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The limitations in the cathode capacity compared with that of the anode have been an impediment to advance the lithium-ion battery technology. The lithium-sulphur system is appealing in this regard, as sulphur exhibits an order of magnitude higher capacity than the currently used cathodes. However, low active material utilization and poor cycle life hinder the practicality of lithium-sulphur batteries. Here we report a simple adjustment to the traditional lithium-sulphur battery configuration to achieve high capacity with a long cycle life and rapid charge rate. With a bifunctional microporous carbon paper between the cathode and separator, we observe a significant improvement not only in the active material utilization but also in capacity retention, without involving complex synthesis or surface modification. The insertion of a microporous carbon interlayer decreases the internal charge transfer resistance and localizes the soluble polysulphide species, facilitating a commercially feasible means of fabricating the lithium-sulphur batteries.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

Lithium–sulphur batteries with a microporous carbon paper as a bifunctional interlayer

2012

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“…This type of behavior schematically presented in Fig. 1b is generally observed for organic carbonatebased electrolyte solutions, [13][14][15][16][17][18][19][20][21][22]24,25,27,31,33,35,36,39,40 as well as for bis(fluorosulfonyl)imide (FSI) anion-based ionic liquid electrolyte solutions. 28,37,38 For this type of the operation of Li-S cells voltage profiles differ from those commonly measured for conventioanal Li-S composite electrodes and are characterized by a single galvanostatic charge/discharge voltage plateau observed around 2.0 V vs. Li/Li + .…”

Section: -10mentioning

confidence: 99%

“…15,45 In most cases this mechanism is observed for composite S/C electrodes with very narrow micropores which width is lower than 1 nm, [14][15][16]19,20,22,23,28,40 but in some cases this type of operation was described also for larger pore size. 13,29,[37][38][39] Several explanations for this single-plateau behavior can be found in the literature.1. The formation of special complexes of the sulfur embedded in the fine pores with carbon or surface-bound oxygen.…”

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confidence: 99%

Review—On the Mechanism of Quasi-Solid-State Lithiation of Sulfur Encapsulated in Microporous Carbons: Is the Existence of Small Sulfur Molecules Necessary?

Markevich

Salitra

Talyosef

et al. 2016

J. Electrochem. Soc.

102

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In this work we analyzed the phenomenon of quasi solid state (QSS) lithiation of sulfur-carbon (S/C) composite electrodes with sulfur confined in the micropores of carbon matrices based on our recent studies and data published in literature. We demonstrated that the existence of sulfur in the form of small molecules is not a necessary condition for the realization of QSS mechanism. QSS operation behavior was demonstrated both for carbons with small up to 1nm micropores and for carbons with larger pore size up to 2-3 nm. A key role in the operation of S/C electrodes via a QSS mechanism plays surface electrolyte interphase (SEI) which is formed on the surface of S/C composite during the initial discharge. The formation of SEI was supported by X-ray photoelectron spectroscopy and by scanning electron microscopy. Small pore size (up to 1 nm) of the carbon matrices has a positive effect on the cycling of S/C electrodes. A superior cycling performance for more than 3500 charge-discharge cycles was demonstrated for S/C composite electrodes based on carbons synthesized by carbonization of polyvinylidene dichloride (PVDC) resin. In recent years lithium-sulfur batteries have been the subject of very intensive research due to the high theoretical specific capacity of sulfur cathodes (1672 mA h g −1 ) which is an order of magnitude higher than that of lithiated transition-metal oxides and phosphates cathode materials used in commercial Li-ion batteries (140-200 mA h g −1 ). [1][2][3][4][5][6] This high capacity relates to the ability of sulfur atoms to accept two electrons resulting in the conversion of elemental sulfur to lithium sulfide (Li 2 S). Furthermore, sulfur is naturally abundant, environmentally friendly and relatively cheap.Due to the low electrical conductivity of elementary sulfur the addition of conductive additives or the use of conductive host materials it is necessary to ensure good performance of sulfur electrodes. Besides, during the discharge process elemental sulfur S 8 accepts electrons to give a chain of electroactive Li-polysulfides (Fig. 1a). The long-chain polysulfides Li 2 S n (4 ≤ n ≤ 8) are soluble in commonly used ethereal solvents and diffuse freely throughout the cell to the anode side where they are chemically reduced. This phenomenon known as the shuttle effect presents one of the main problems of Li-S cells. 7 The shuttle reactions prevent the possibility of extracting the full capacity of sulfur cathodes and lead to low Coulombic efficiency. Encapsulation of sulfur within activated carbons with high pores volume is one of the most effective approaches to mitigate the detrimental shuttle mechanism and stabilize composite sulfur cathodes during prolong cycling. 8-10The typical cyclic voltammetry and galvanostatic charge-discharge curves of the Li-S cell with C/S encapsulated cathode are shown in Fig. 1a. Two peaks observed in the cathodic voltammetric response of sulfur electrodes correspond to two plateaus observed in the voltage profiles of the discharge processes of these cathodes upon ...

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“…[5][6][7] However, lithium-sulfur batteries have critical drawbacks in the aspect of cycle life, rate capability, and sulfur utilization. 8,9 There were many attempts to overcome these problems, [10][11][12][13][14][15][16] such as optimization of the organic electrolyte and room-temperature ionic liquid, sulfurhigh porous carbon composite, and sulfur-coated multiwalled carbon nanotube composite. Some interesting cathode developments involving sulfides have been reported recently: highly ordered interwoven C-S composites were created and its polymer modification reached reversible capacities up to 1320 mAh g −1 .…”

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confidence: 99%

Influence of pH of Gelatin Solution on Cycle Performance of the Sulfur Cathode

Zhang

Huang

Wang

et al. 2010

J. Electrochem. Soc.

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The influence of pH of the gelatin solution on the cycle performance of the sulfur cathode for lithium-sulfur batteries was studied. Scanning electron microscopy measurements revealed that the cathode prepared with pH 10.0 gelatin solution as a binder showed a uniform distribution. The charge/discharge experiments of the lithium-sulfur batteries showed that an initial capacity of 1137 mAh g −1 and a reversible capacity of 642 mAh g −1 after 30 cycles were achieved, which were higher than those of the cathodes prepared at pH 5.0 and 8.0. To understand the effect of the pH value of the gelatin solution on the cycle performance of sulfur cathodes, electrochemical impedance spectroscopy and X-ray diffractometry were carried out. © 2010 The Electrochemical Society. ͓DOI: 10.1149/1.3299323͔ All rights reserved. There is an ever increasing demand for the development of rechargeable lithium batteries with high energy density and long cycle life suitable for a variety of applications ranging from microbatteries of miniature electronic devices to large power sources of electric vehicles. [1][2][3][4] Elemental sulfur is an active mass which has a high theoretical specific capacity of 1672 mAh g −1 , assuming the complete reaction of lithium with sulfur to Li 2 S. Moreover, many advantages such as low cost, abundance in nature, and environment friendliness make the lithium-sulfur battery a great potential for future use, thereby attracting considerable interests. 5-7 However, lithium-sulfur batteries have critical drawbacks in the aspect of cycle life, rate capability, and sulfur utilization. 8,9 There were many attempts to overcome these problems, 10-16 such as optimization of the organic electrolyte and room-temperature ionic liquid, sulfurhigh porous carbon composite, and sulfur-coated multiwalled carbon nanotube composite. Some interesting cathode developments involving sulfides have been reported recently: highly ordered interwoven C-S composites were created and its polymer modification reached reversible capacities up to 1320 mAh g −1 . 17 Besides, the investigation on the cathode binders of lithium-sulfur batteries also showed improvement. 18 Jung and Kim improved the cycle performance of lithium-sulfur batteries by using a mixed binder system of poly͑4-vinyl͒pyridine and poly͑ethyleneimine͒, which can maintain the morphology of the cathode during charge-discharge cycles. 19 In our previous work, we found that the gelatin had multifunctional effects on the sulfur cathode in the lithium-sulfur battery: It was not only a high adhesion agent and a strong dispersion agent for the cathode materials but also an electrochemically stable binder. Our research showed that it is more suitable for use in lithiumsulfur batteries than some conventional binders, such as poly͑vi-nylidene fluoride͒ and poly͑ethylene oxide͒. [20][21][22][23] Gelatin contains both acidic carboxyl and basic amino groups, which can transform into the corresponding negatively and positively charged groups in solution. [24][25][26] When the pH value of t...

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Preparation and electrochemical properties of sulfur–acetylene black composites as cathode materials

Cited by 193 publications

References 29 publications

Lithium–sulphur batteries with a microporous carbon paper as a bifunctional interlayer

Lithium–sulphur batteries with a microporous carbon paper as a bifunctional interlayer

Review—On the Mechanism of Quasi-Solid-State Lithiation of Sulfur Encapsulated in Microporous Carbons: Is the Existence of Small Sulfur Molecules Necessary?

Influence of pH of Gelatin Solution on Cycle Performance of the Sulfur Cathode

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